TW202239866A - resin composition - Google Patents

Abstract

The present invention addresses the problem of providing: a resin composition with which it is possible to obtain a cured product having excellent copper plating peel strength and stain removability, while suppressing the arithmetic average roughness (Ra) of the surface of an insulating layer after roughening treatment to a low level; and a resin composition from which a cured product having a low dielectric loss tangent (Df) and excellent base copper adhesion strength (copper foil peel strength) after an accelerated environment test (HAST) and elongation at break can be obtained. The solution of the present invention is: a resin composition containing (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound; and a resin composition containing (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, the content of the component (C) being 10% by mass or more when the non-volatile components in the resin composition are 100% by mass, and the content of the component (C) being 10% by mass or more when the non-volatile components in the resin composition are 100% by mass, and the content of the component (C) being 10% by mass or more when the non-volatile components in the resin composition are 100% by mass. The content of the component (D) is 60 mass% or more.

Description

resin composition

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

As a manufacturing technique of a printed wiring board, the manufacturing method by the stacking system which alternately stacks an insulating layer and a conductor layer is known. In the manufacturing method by the deposition method, generally, the insulating layer is formed by hardening the resin composition. In recent years, the pursuit of lowering the dielectric loss tangent of the insulating layer has been pursued.

Hitherto, it is known that the dielectric loss tangent of the insulating layer can be further reduced by using an epoxy resin composition blended with an active ester compound as a resin composition for forming an insulating layer (Patent Document 1). In addition, it is known that the dielectric loss tangent of the insulating layer can be further reduced by using an epoxy resin composition in which a large amount of inorganic filler is mixed in addition to the active ester compound as the resin composition for forming the insulating layer (patent Literature 1).

However, when an epoxy resin composition blended with an active ester compound is used, there are problems such as a reduction in smear removability. Also, although the smear removability can be improved if a low molecular weight (meth)acrylate compound is used (Patent Document 2), the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment or the peeling of the copper plating Intensity is problematic.

Also, when using an epoxy resin composition blended with a large amount of active ester compound and inorganic filler, the elongation at breaking point decreases, and the substrate copper adhesion strength (copper foil peel strength) decreases after accelerated environmental testing (HAST). Waiting to become a topic.

In addition, allyl compounds having an alicyclic structure have been known so far (Patent Documents 3 and 4). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-23714 [Patent Document 2] Japanese Patent Laid-Open No. 2019-183071 [Patent Document 3] Japanese Patent Laid-Open No. 2019-89967 [Patent Document 4] Japanese Patent Laid-Open No. 2020-136311

[Problem to be Solved by the Invention]

The first object of the present invention is to provide a resin composition capable of reducing the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment, and having a hardened product having excellent copper plating peel strength and smear removability.

The second subject of the present invention is to provide a resin composition that can obtain a low dielectric loss tangent (Df), elongation at break and substrate copper adhesion strength (copper foil peel strength) after accelerated environmental testing (HAST). ) Excellent hardened product. [Means to solve the problem]

In order to achieve the first subject of the present invention, as a result of in-depth research, the present inventors found that by further using (A) an alicyclic structure compound in the epoxy resin composition blended with (C) active ester compound Unexpectedly, the allyl compound can reduce the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment, and can obtain a cured product that is excellent in copper plating peel strength and smear removability, and finally completed the first implementation The invention of form.

In order to achieve the second subject of the present invention, as a result of intensive research, the present inventors found that by blending a large amount of 10% by mass or more and 60% by mass or more of ring In the epoxy resin composition, further use (A) of an allyl compound having an alicyclic structure, surprisingly, can obtain a low dielectric loss tangent (Df), elongation at breaking point and accelerated environmental test (HAST) The hardened product with excellent base copper adhesion strength (copper foil peel strength) finally completed the invention of the second embodiment.

That is, the present invention includes the following matters. [1] A resin composition comprising (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound. [2] The resin composition according to the above [1], further comprising (D) a (meth)acrylate compound having a molecular weight of less than 1,000. [3] The resin composition as described in [2] above, wherein the mass ratio of (D) component to (A) component ((D) component/(A) component) is 0.1-10. [4] The resin composition as described in [1] above, wherein the content of the component (C) is 10% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. [5] The resin composition as described in [1] above, further comprising (E) an inorganic filler. [6] The resin composition described in [5] above, wherein the content of the component (E) is 60% by mass or more when the non-volatile components in the resin composition are 100% by mass. [7] A resin composition comprising (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound, and (E) an inorganic filler, When the non-volatile components in the resin composition are defined as 100% by mass, the content of component (C) is 10% by mass or more, The content of (E) component is 60 mass % or more when the non-volatile matter in a resin composition is made into 100 mass %. [8] The resin composition as described in [1] or [7] above, wherein the component (A) has a group represented by the formula (a-1):

[wherein, * represents a bonding site]. [9] The resin composition as described in [1] or [7] above, wherein the component (A) has a group represented by the formula (A3):

[In the formula, X represents a single bond, -C(R ⁵ ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -, R ² and R ⁵ are each independently representing a hydrogen atom Or hydrocarbon group, R ³ and R ⁴ are independent, representing a hydrocarbon group, at least one of R ² and b R ³ is an allyl group, b and c are independently representing an integer of 0 to 3, * represents a bond part]. [10] The resin composition as described in [1] or [7] above, wherein the weight average molecular weight of the component (A) is 1,000 to 20,000. [11] The resin composition as described in [1] or [7] above, wherein the allyl equivalent of component (A) is 200 g/eq. to 2000 g/eq. [12] The resin composition described in [1] or [7] above, wherein the content of component (A) is 0.01% by mass or more when the non-volatile components in the resin composition are 100% by mass. [13] The resin composition as described in [1] or [7] above, wherein the content of the component (A) is 5% by mass or less when the non-volatile components in the resin composition are 100% by mass. [14] The resin composition described in [1] or [7] above, wherein the content of the component (B) is 1% by mass to 20% by mass when the non-volatile components in the resin composition are defined as 100% by mass . [15] The resin composition described in [1] or [7] above, wherein the mass ratio of component (B) to component (A) (component (B)/component (A)) is 1.5 to 100. [16] The resin composition according to the above [5] or [7], wherein the component (E) is silica. [17] The resin composition described in [5] or [7] above, wherein the content of the component (E) is 70% by mass or more when the non-volatile components in the resin composition are 100% by mass. [18] The resin composition according to the above [1] or [7], further comprising an imidazole-based hardening accelerator. [19] The resin composition according to the above [1] or [7], further comprising a curing agent selected from the group consisting of a phenol-based curing agent and a carbodiimide-based curing agent. [20] The resin composition described in [1] or [7] above, wherein the elongation at breaking point of the cured product of the resin composition is 1.0% or more when measured at 23°C. [21] The resin composition described in [1] or [7] above, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23°C. [22] A cured product of the resin composition described in the above [1] or [7]. [23] A sheet-like laminate comprising the resin composition described in [1] or [7] above. [24] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer being formed of the resin composition described in [1] or [7] above. [25] A printed wiring board comprising an insulating layer made of a cured resin composition as described in [1] or [7] above. [26] A semiconductor device comprising the printed wiring board as described in [25] above. [Invention effect]

According to the resin composition in the first embodiment of the present invention, it is possible to obtain a cured product capable of reducing the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment, and having excellent copper plating peel strength and smear removability.

According to the resin composition in the second embodiment of the present invention, the dielectric loss tangent (Df) is low, the elongation at breaking point and the base copper adhesion strength (copper foil peel strength) after the accelerated environmental test (HAST) can be obtained. ) Excellent hardened product.

Hereinafter, the present invention will be described in detail according to preferred embodiments of the present invention. However, the present invention is not limited to the following embodiments and illustrations, and can be implemented with arbitrary changes within the range not departing from the scope of claims and equivalents of the present invention.

＜Resin composition＞ The resin composition in the first embodiment of the present invention includes (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 roughened surface of the insulating layer can be reduced, and a hardened product having excellent copper plating peel strength and smear removability can be obtained.

The resin composition in the first embodiment of the present invention may further contain any Element. Examples of optional components include (C') other hardeners, (D) (meth)acrylate compounds with a molecular weight of less than 1,000, (E) inorganic fillers, and (F) radical polymerizable compounds with a molecular weight of 1,000 or more. Compound, (G) hardening accelerator, (H) thermoplastic resin, (I) other additives, and (J) organic solvent.

The resin composition in the second embodiment of the present invention includes (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound, and (E) an inorganic filler, ( C) The content of the active ester compound is 10% by mass or more, and (E) The content of the inorganic filler is 60% by mass or more. By using such a resin composition, it is possible to obtain a cured product with a low dielectric loss tangent (Df) and excellent elongation at break and base copper adhesion strength (copper foil peel strength) after the accelerated environmental test (HAST). things.

The resin composition in the second embodiment of the present invention is composed of (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound, and (E) an inorganic filler. In addition, arbitrary components may be contained further. Examples of optional components include (C') other hardeners, (F') radically polymerizable compounds, (G) hardening accelerators, (H) thermoplastic resins, (I) other additives, and (I) organic solvent.

Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) Allyl compound having an alicyclic structure> The resin composition of the present invention contains (A) an allyl compound having an alicyclic structure. (A) The allyl compound which has an alicyclic structure may be used individually by 1 type, and may be used combining 2 or more types in arbitrary ratios.

(A) The allyl compound having an alicyclic structure preferably has two or more allyl groups in one molecule. Also, (A) an allyl compound having an alicyclic structure preferably has an aromatic ring, an allyl group, through a direct bond to the aromatic ring, or a heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom (Preferably an oxygen atom) Bonding is preferred.

The so-called aromatic ring means a ring according to Huckel's rule that the number of electrons contained in the π-electron system on the cycle 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, or a sulfur atom as a ring constituting atom in addition to a carbon atom, but in one In the embodiment, an aromatic carbocyclic ring is preferred. As for the aromatic ring, in one embodiment, an aromatic ring with 5 to 14 members is preferable, and an aromatic ring with 5 to 10 members is more preferable. Suitable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

(A) an allyl compound having an alicyclic structure, in one embodiment, preferably having a group represented by formula (A1):

[In the formula, R ¹ are each independently representing a substituent, at least one of a R ¹ is allyl or allyloxy, a represents an integer of 1 to 4, and * represents a bonding site], having the formula The basis shown in (A2) is better:

[In the ^formula , R2 represents a hydrogen atom or a hydrocarbon group, each ^R3 independently represents a hydrocarbon group, at least one of one R2 and b ^R3s is an allyl group, b represents an integer from 0 to ³ , and * represents a bond Knot site], it is better to have the group shown in formula (A3):

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

R ¹ are each independently represented a substituent. Each R is independently, preferably allyl, allyloxy, hydroxyl, alkyl, aryl, alkyl ^- oxyl or aryl-oxyl, more preferably allyl, allyloxy or hydroxyl.

In this specification, the "substituent" is not particularly limited, but examples include allyl, allyloxy, amino, hydroxyl, alkyl, aryl, alkyl-aryl (substituted by alkyl aryl), aryl-alkyl (aryl substituted alkyl), alkyl-oxy, aryl-oxy, alkyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, aryl Monovalent substituents such as radical-oxy-carbonyl, alkyl-carbonyl-oxy, aryl-carbonyl-oxy, mono- or di(alkyl)amine, mono- or di(aryl)amine, and the like.

The term "alkyl" means a linear and/or branched monovalent aliphatic saturated hydrocarbon group. Alkyl (alkyl) Unless otherwise specified, an alkyl (alkyl) with 1 to 6 carbon atoms is preferred. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, hexyl, cyclopentyl, cyclopentyl, Hexyl etc. The term "aryl" means a monovalent aromatic hydrocarbon group. Aryl (aryl) Unless otherwise specified, an aryl (aryl) having 6 to 14 carbon atoms is preferred. As aryl (aryl), phenyl, 1-naphthyl, 2-naphthyl etc. are mentioned, for example. The halogen atom is a fluorine atom, chlorine atom, bromine atom or iodine atom.

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

R ² 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. R ³ are each independently representing a hydrocarbon group. R ³ is preferably allyl or alkyl, more preferably allyl.

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

b represents an integer from 0 to 3. b is preferably 0, 1 or 2, more preferably 0 or 1.

In the first embodiment, it is preferred that R ² is an allyl group, R ³ are each independently a hydrocarbon group, and b is 0, 1 or 2; more preferably R ² is an allyl group, and each R ³ is independently an alkane base, and b is 0 or ¹ ; particularly preferably R is allyl, and b is 0.

In the second embodiment, it is preferred that R ² is a hydrogen atom, R ³ is independently a hydrocarbon group, b is 1 or 2, and at least one of the b R ³ is an allyl group; more preferably R ² is Hydrogen atom, R ³ are independently allyl or alkyl, b is 1 or 2, and at least 1 of b R ³ is allyl; particularly preferably R ² is hydrogen atom, R ³ is alkenyl Propyl, 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 -.

R ⁵ are each independently representing a hydrogen atom or a hydrocarbon group. R ⁵ are each 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.

R ⁴ are each independently, and represent a hydrocarbon group. R ⁴ is preferably allyl or alkyl, more preferably allyl.

c represents an integer from 0 to 3. c is preferably 0, 1 or 2, more preferably 0 or 1. In the first embodiment, c is particularly preferably 0. In the 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 double or triple bonds, but a saturated ring consisting only of single bonds is preferred . The saturated ring may be a saturated carbocyclic ring having a carbon atom as a ring constituting atom, or a saturated heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring constituting atom in addition to a carbon atom.

環、四氫哌喃環、1,3-二

烷環、1,4-二

烷環、四氫噻喃(thiane)環、1,3-二噻烷環、1,4-二噻烷環、嗎啉環、硫代嗎啉環、

唑啶環等之單環系之飽和雜環、7-氧雜二環[4.1.0]庚烷環(1,2-環氧環己烷環)、1-氮雜雙環[2.2.2]辛烷(奎寧環)、十氫喹啉環、十氫異喹啉環等之二環系之飽和雜環、1-氮雜三環[3.3.1.1 ^3,7]癸烷(1-氮雜金剛烷環)、2-氮雜三環[3.3.1.1 ^3,7]癸烷(2-氮雜金剛烷環)等之三環系之飽和雜環等之飽和雜環。 The saturated ring is preferably a saturated ring with 3 to 18 carbon atoms, more preferably a saturated ring with 5 to 16 carbon atoms. Examples of the saturated ring include cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclodecane ring, and cyclodecane ring. Saturated carbocyclic rings such as monocycloalkane rings such as dioxane rings, bicyclo[2.2.1]heptane rings (norbornane rings), bicyclo[4.4.0]decane rings (decalin rings) , bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (octahydroindene ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[ 3.3.0] octane ring, bicyclo [3.3.1] nonane ring and other saturated carbocycles of bicyclic rings, tricyclo [5.2.1.0 ^2,6 ] decane ring (tetrahydrodicyclopentadiene ring) , tricyclic [3.3.1.1 ^3,7 ] decane ring (adamantane ring), tricyclic [6.2.1.0 ^2,7 ] undecane ring and other saturated carbocyclic rings of the tricyclic system, tetracyclic [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane ring and other tetracyclic saturated carbocyclic rings, pentacyclic rings [9.2.1.1 ^4,7 .0 ^2,1 0.0 ^3,8 ] pentadecane rings, pentacyclic rings [ 6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadecane ring (tetrahydrotricyclopentadiene ring) ring and other saturated carbocyclic rings of the five-ring system; pyrrolidine ring , pyrazolidine ring, imidazolidine ring, tetrahydrofuran ring, 1,3-dioxolane ring, piperidine ring, piperidine

ring, tetrahydropyran ring, 1,3-di

Alkane ring, 1,4-bis

Alkane ring, thiane ring, 1,3-dithiane ring, 1,4-dithiane ring, morpholine ring, thiomorpholine ring,

Monocyclic saturated heterocyclic rings such as oxazidine ring, 7-oxabicyclo[4.1.0]heptane ring (1,2-epoxycyclohexane ring), 1-azabicyclo[2.2.2] Octane (quinuclidine), decahydroquinoline ring, decahydroisoquinoline ring and other bicyclic saturated heterocycles, 1-azatricyclo[3.3.1.1 ^3,7 ]decane (1-aza Heteroadamantane ring), 2-azatricyclo[3.3.1.1 ^3,7 ]decane (2-azaadamantane ring) and other saturated heterocycles of the tricyclic system.

(A) Among allyl compounds having an alicyclic structure, the non-aromatic ring is preferably a saturated carbocyclic ring, and a saturated carbocyclic ring of a bicyclic or higher type is more preferred. A saturated carbocycle, a tetracyclic saturated carbocycle, or a pentacyclic saturated carbocycle is more preferred.

(A) An allyl compound having an alicyclic structure. In one embodiment, it is preferred to have a group represented by formulas (a-1) to (a-8) containing a saturated carbocycle of more than two ring systems:

[wherein, * represents a bonding site]. Among them, it is preferable to have a group represented by formula (a-1).

(A) An allyl compound having an alicyclic structure. In one embodiment, it is preferable to include a carbonate resin having an alicyclic structure and an allyl group. Although it is not particularly limited, it includes the compound represented by formula (A). The carbonate resin is especially good:

[In the formula, A ¹ is independently represented as the base shown in the formula (A3) described above; A ² is independently represented as the base shown in the formula (Aa) or the base shown in the formula (Ab):

(In the formula, Y each independently represents a single bond or an alkylene group, each ring Cy independently represents a non-aromatic ring which may have a substituent, and * represents a bonding site).

(In the formula, Z represents a single bond, -C(R ⁸ ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -, R ⁶ and R ⁷ are each independently representing a hydrocarbon group , R ⁸ are each independently representing a hydrogen atom or a hydrocarbon group, e and d are independently representing an integer of 0 to 3, and * represents a bonding site). At least one of the n pieces of A ² is a group represented by the formula (Aa); n represents an integer of 0 or more].

Y each 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.

The term "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 the alkylene group include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, Straight-chain alkylene such as decamethylene; branched-chain alkylene such as ethylene, propylene, isopropylene, ethylmethylmethylene, diethylmethylene, etc.

Each ring Cy independently represents a non-aromatic ring which may have a substituent. The ring Cy is independently a bicyclic or higher saturated carbocycle which may have a substituent, particularly preferably a tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydrodicyclopentadiene ring).

R ⁶ and R ⁷ are each independent and represent a hydrocarbon group. R ⁶ and R ⁷ are each independently, preferably allyl or alkyl, more preferably allyl.

e and d are independent of each other and 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 -.

R ⁸ are each independently representing a hydrogen atom or a hydrocarbon group. R ⁸ are each 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 to 200, more preferably an integer of 0 to 100. At least one of the n pieces of A ² is a group represented by formula (Aa). The proportion of the group represented by the ^formula (Aa) in n A2 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, particularly preferably 2,000 or more. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

(A) The allyl equivalent of the allyl compound having an alicyclic structure is preferably 150g/eq.~5000g/eq., more preferably 200g/eq.~2000g/eq., and more preferably 250g/eq. eq.~1500g/eq., and more preferably 300g/eq.~1200g/eq. Allyl equivalent is the mass of allyl compound per 1 equivalent of allyl.

(A) Commercially available allyl compounds having an alicyclic structure include, for example, "FTC809AE" and "FATC809" manufactured by Qunyei 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 of the first embodiment is not particularly limited, but from the viewpoint of lowering the dielectric loss tangent of the cured product further, the When the non-volatile content in the resin composition is 100% by mass, it is preferably at most 10% by mass, more preferably at most 7% by mass, still more preferably at most 5% by mass, even more preferably at most 4% by mass, 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 in the first embodiment is not particularly limited, but the arithmetic mean roughness of the surface of the insulating layer after the roughening treatment is lowered. From the viewpoint of increasing the peel strength (Ra), when the non-volatile content in the resin composition is 100% by mass, it is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and even more preferably at least 0.1% by mass. % by mass or more, more preferably at least 0.5% by mass, particularly preferably at least 1% by mass.

The content of (A) the allyl compound having an alicyclic structure in the resin composition of the second embodiment is not particularly limited, but from the viewpoint of further reducing the dielectric loss tangent of the cured product, the When the non-volatile content in the resin composition is 100% by mass, it is preferably at most 10% by mass, more preferably at most 7% by mass, still more preferably at most 5% by mass, even more preferably at most 4% by mass, particularly preferably 3% by mass or less. The lower limit of the content of the (A) allyl compound having an alicyclic structure in the resin composition of the second embodiment is not particularly limited, but it can be further enhanced by elongation at breaking point and accelerated environmental test (HAST) From the viewpoint of the substrate copper adhesion strength (copper foil peel strength), when the non-volatile content in the resin composition is 100 mass%, it is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, More preferably, it is at least 0.1% by mass, still more preferably at least 0.2% by mass, and most preferably at least 0.3% by mass.

＜(B) Epoxy resin＞ The resin composition of this invention contains (B) epoxy resin. The so-called (B) epoxy resin is a curable resin having an epoxy group.

As (B) epoxy resin, for example, bisphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin , dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tertiary 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 Oxygen resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, ring Hexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthyl ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanuric acid Ester type epoxy resin, phenolbenzyl lactam type epoxy resin, phenolphthalein type epoxy resin, etc. (B) Epoxy resins may be used alone 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 the (B) epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably at least 50% by mass, more preferably 60% by mass, relative to 100% by mass of the non-volatile components of the epoxy resin (B) Above, especially preferably 70% by mass or more.

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

As a liquid epoxy resin, what has 2 or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, epoxy Propylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin with butadiene structure Epoxy resins are preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL" and "jER828EL" manufactured by Mitsubishi Chemical Corporation ", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation (phenol novolak type epoxy resin); Mitsubishi Chemical Corporation's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA Corporation's "ED-523T" (licorice epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Materials Chemical Co., Ltd.; "EX-721" (glycidyl ester type) manufactured by Nagase ChemteX Co., Ltd. epoxy resin); "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL; "PB-3600" manufactured by DAICEL; "JP-100" manufactured by Nippon Soda Corporation; "JP- 200" (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. These may be used individually by 1 type, and may use it in combination of 2 or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in 1 molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule is more preferable. good.

As the solid epoxy resin, double stubble phenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4 functional epoxy resin, naphthol novolak type epoxy resin, cresol novolac type epoxy resin, bicyclo Pentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin Resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol benzyl lactam type epoxy resin, phenolphthalein type epoxy resin are preferable.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; ); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200" manufactured by DIC Corporation ", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene-type epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Japan "NC7000L" (naphthol novolak type epoxy resin) manufactured by Kayaku Corporation; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy Resin); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Nippon Steel Chemical & Materials Co., Ltd. "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Materials Corporation; "YX4000H", "YX4000", "YX4000HK", "YL7890" (double stubble phenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka "PG-100" and "CG-500" manufactured by Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ; "jER1010" (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol A) manufactured by Nippon Kayaku Corporation benzyl lactamide type epoxy resin), etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

In the first embodiment, when (B) epoxy resin is used in combination of liquid epoxy resin and solid epoxy resin, the mass ratio of these (liquid epoxy resin:solid epoxy resin) is preferably 10:1~1:50, more preferably 2:1~1:20, especially preferably 1:1~1:10. In the second embodiment, when (B) epoxy resin is used in combination of liquid epoxy resin and solid epoxy resin, the mass ratio of these (liquid epoxy resin:solid epoxy resin) is preferably 20:1~1:20, more preferably 10:1~1:10, especially 7:1~1:7.

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

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

The content of (B) epoxy resin in the resin composition in the first embodiment is not particularly limited, but when the non-volatile components in the resin composition are defined as 100% by mass, it is preferably 30% by mass or less. More preferably, it is 25 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less, Most preferably, it is 10 mass % or less. The content of (B) epoxy resin in the resin composition in the second embodiment is not particularly limited, but when the non-volatile components in the resin composition are defined as 100% by mass, it is preferably less than 30% by mass , more preferably at most 25% by mass, more preferably at most 20% by mass, even more preferably at most 15% by mass, and most preferably at most 10% by mass. The lower limit of the content of (B) epoxy resin in the resin composition in the first embodiment and the second embodiment is not particularly limited, but when the non-volatile component in the resin composition is defined as 100% by mass, it is relatively It is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, still more preferably at least 1% by mass, still more preferably at least 3% by mass, and most preferably at least 5% by mass.

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 More than 1.5, especially better than 2. The upper limit of the mass ratio ((B) component/(A) component) of (B) epoxy resin to (A) allyl compound having an alicyclic structure in the resin composition is preferably 1000 or less, more preferably The best is below 100, and the most preferable is below 50.

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

As the (C) active ester compound, it is generally preferable to use one having two or more highly reactive compounds in one molecule of phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. Ester-based compounds. The active ester compound is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, 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, phloroglycerol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol Phenolic varnish, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Specifically, as the (C) active ester compound, dicyclopentadiene type active ester compound, naphthalene type active ester compound containing naphthalene structure, active ester compound containing acetylated phenol novolac, phenol novolac The active ester compound of the benzoyl compound of the varnish is preferably at least one selected from the dicyclopentadiene-type active ester compound and the naphthalene-type active ester compound, and the dicyclopentadiene-type active ester compound is And then better. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

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

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

The content of the (C) active ester compound in the resin composition in the first embodiment is preferably 0.1 mass % or more, more preferably 1 mass % when the non-volatile content in the resin composition is 100 mass % or more, more preferably at least 5% by mass, still more preferably at least 10% by mass, particularly preferably at least 13% by mass. The content of the (C) active ester compound in the resin composition in the second embodiment is 10% by mass or more, preferably 11% by mass or more when the non-volatile content in the resin composition is 100% by mass. More preferably, it is 12 mass % or more, More preferably, it is 13 mass % or more, Most preferably, it is 14 mass % or more. The upper limit of the content of the (C) active ester compound in the resin composition in the first embodiment and the second embodiment is not particularly limited, but when the non-volatile components in the resin composition are defined as 100% by mass, it is relatively It is preferably at most 50 mass %, more preferably at most 40 mass %, further preferably at most 30 mass %, still more preferably at most 25 mass %, and most preferably at most 20 mass %.

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

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

系硬化劑、氰酸酯系硬化劑及硫醇系硬化劑。本發明之樹脂組成物，包含選自由苯酚系硬化劑及碳二亞胺系硬化劑所成群組中之硬化劑特佳。(C') Other curing agents are not particularly limited, but examples include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzo

Hardeners, cyanate-based hardeners, and mercaptan-based hardeners. The resin composition of the present invention preferably contains a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.

骨架之苯酚系硬化劑更佳。其中，由高度滿足耐熱性、耐水性及密著性之觀點來看，以含有三

骨架之苯酚酚醛清漆樹脂較佳。作為苯酚系硬化劑之具體例，可舉例例如明和化成公司製之「MEH-7700」、「MEH-7810」、「MEH-7851」，日本化藥公司製之「NHN」、「CBN」、「GPH」，日鐵化學＆材料公司製之「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製之「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」、「TD-2090-60M」等。As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. Also, from the point of view of the adhesion of the substrate, nitrogen-containing phenol-based hardeners are preferred, containing three

The phenolic hardener of the skeleton is better. Among them, from the standpoint of highly satisfying heat resistance, water resistance and adhesion, the three

Skeleton phenol novolac resin is preferred. Specific examples of phenolic hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH","SN-170","SN-180","SN-190","SN-475","SN-485","SN-495","SN-375","SN-395","LA-7052","LA-7054","LA-3018","LA-3018-50P","LA-1356","TD2090","TD-2090-60M", etc.

Examples of carbodiimide-based hardeners include those having one or more, preferably two or more, carbodiimide structures in one molecule, such as tetramethylene-bis(t-butyl Carbodiimide), cyclohexanebis(methylene-t-butylcarbodiimide) and other aliphatic biscarbodiimides; phenylene-bis(xylylcarbodiimide) and other Biscarbodiimide such as aromatic biscarbodiimide; polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly(ethylene Aliphatic polycarbodiimides such as methylbiscyclohexylcarbodiimide), poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly(naphthylcarbodiimide) imine), poly(benzylidenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylenecarbodiimide) Phenylcarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(scylenecarbodiimide), poly(tetrafluoroethylene Aromatic polycarbonate such as methyl stubble carbodiimide), poly(methylene diphenylene carbodiimide), poly[methylene bis(methyl phenylene carbodiimide], etc. Polycarbodiimide such as diimide.

Examples of commercially available carbodiimide curing agents include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and " CARBODILITE V-09"; "Stabaxol P", "Stabaxol P400", "Hikazil 510" manufactured by RHEIN CHEMIE, etc.

Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule, and those having two or more acid anhydride groups in one molecule are preferred. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated formaldehyde. Genadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dipentoxytetrahydro-3-furyl)-3-methyl-3-cyclohexene -1,2-Dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic acid Dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-two Copolymerized with oxy-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), styrene and maleic acid Polymeric anhydrides of styrene/maleic acid resins, etc. Examples of commercially available acid anhydride hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Nippon Chemical Corporation, and "HNA-100" manufactured by Mitsubishi Chemical Corporation. YH-306", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., "EF-30", "EF-40", "EF-60", "EF-60" manufactured by Cray Valley Corporation EF-80" and so on.

Examples of amine-based hardeners include those having one or more, preferably two or more, amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic Amines etc. Among them, aromatic amines are preferable from the viewpoint of exerting the desired effect of the present invention. For amine hardeners, the primary amine or secondary amine is preferred, and the primary amine is more preferred. Specific examples of amine-based hardeners include 4,4'-methylene bis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-bis Amino diphenyl diamine, 3,3'-diamino diphenyl diamine, m-phenylene diamine, m-stem diamine, diethyltoluenediamine, 4,4'-diamino diamine Phenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Hydroxybenzidine, 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)pyridine, bis(4-(3-aminophenoxy)phenyl)pyridine, etc. Commercially available amine hardeners can also be used, for example, "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc.

系硬化劑之具體例，可舉例JFE化學公司製之「JBZ-OP100D」、「ODA-BOZ」；昭和高分子公司製之「HFB2006M」；四國化成工業公司製之「P-d」、「F-a」等。as benzo

Specific examples of hardening agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd. Wait.

化而成之預聚物等。作為氰酸酯系硬化劑之具體例，可舉例Lonza Japan公司製之「PT30」及「PT60」(皆為苯酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸鹽之一部分或全部經三

化成為三量體之預聚物)等。Examples of cyanate-based hardeners include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4' -Methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide and bis(4-cyanate phenyl)ether 2 functional cyanate resins, multifunctional cyanate resins derived from phenol novolaks and cresol novolacs, etc., some of these cyanate resins are three

Formed prepolymers, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resins), "BA230" and "BA230S75" (bisphenol A part or all of one of the dicyanates

into a prepolymer of three volume bodies), etc.

Examples of thiol-based hardeners include trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol tetramethylene (3-mercaptobutyrate), ginseng (3-mercaptopropyl) isocyanurate Wait.

(C') The reactive group equivalent weight of other curing agents is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., and even more preferably 100g/eq.~500g/eq. , especially 100g/eq.~300g/eq. Reactive group equivalent is the mass of hardener per 1 equivalent of reactive group.

The content of (C') other hardeners in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass % or less, more preferably 7 mass % or less, particularly preferably 5 mass % or less. The lower limit of the content of (C') other hardeners in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it can be, for example, 0% by mass or more, 0.01% by mass More than, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

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

<(D) (Meth)acrylate compounds with a molecular weight of less than 1,000> The resin composition of the present invention in the first embodiment may further contain (D) a (meth)acrylate compound having a molecular weight of less than 1,000 as an optional component. (D) The (meth)acrylate compound whose molecular weight is less than 1000 may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

(D) A (meth)acrylate compound having a molecular weight of less than 1000 is a radically polymerizable compound having one or more acryl and/or methacryl groups in one molecule. (D) The (meth)acrylate compound having a molecular weight of less than 1000 preferably has two or more acryl groups and/or methacryl groups in one molecule.

烷二醇二(甲基)丙烯酸酯等之分子量未達1000之含脂環式結構的分子量未達1000之(甲基)丙烯酸酯化合物；新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,8-辛二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、3,6-二氧雜-1,8-辛二醇二(甲基)丙烯酸酯、3,6,9-三氧十一烷-1,11-二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀、乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯等之不含脂環式結構的分子量未達1000之(甲基)丙烯酸酯化合物，但其中，以含脂環式結構的分子量未達1000之(甲基)丙烯酸酯化合物較佳。As (D) (meth)acrylate compounds with a molecular weight of less than 1000, for example, cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di

(Meth)acrylic ester compounds with a molecular weight of less than 1000, such as alkanediol di(meth)acrylate, containing an alicyclic structure; 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, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, Glycerin tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxodeca Mono-alkane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2- Acryloxyethoxy) phenyl] fen, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc. do not contain alicyclic structure (meth)acrylate compounds with a molecular weight of less than 1,000, but among them, (meth)acrylate compounds with a molecular weight of less than 1,000 containing an alicyclic structure are preferred.

(D) The alicyclic structure in the (meth)acrylate compound with 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 with a molecular weight of less than 1000 may have a substituent at a substitutable position. A non-aromatic ring may be a saturated ring consisting only of single bonds, or a non-aromatic unsaturated ring having at least any one of a double bond and a triple bond, but a saturated ring consisting only of single bonds is more good. The saturated ring may be a saturated carbocyclic ring having a carbon atom as a ring constituting atom, or a saturated heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring constituting atom in addition to a carbon atom. As a saturated ring, the thing similar to what was illustrated above can be mentioned.

烷環，或三環[5.2.1.0 ^2,6]癸烷環(四氫二環戊二烯環)進而佳。 (D) Among (meth)acrylate compounds with a molecular weight of less than 1000, the non-aromatic ring is preferably a saturated carbocyclic ring with 3 to 18 carbon atoms, or a saturated heterocyclic ring with 3 to 18 carbon atoms. A saturated carbocyclic ring with a number of 5 to 16, or a saturated heterocyclic ring with a carbon number of 5 to 16 is more preferable, and 1,3-di

An alkane ring, or a tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydrodicyclopentadiene ring) is more preferred.

(D) The acryl group and/or methacryl group in the (meth)acrylate compound with a molecular weight of less than 1000, in one embodiment, passes through a heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom ( preferably an oxygen atom) or a combination of a heteroatom (preferably an oxygen atom) and an alkylene group (more preferably an acryl or methacryl side is a heteroatom and a non-aromatic ring side is an alkylene group) Bonding to a non-aromatic ring is preferred.

烷二醇二丙烯酸酯)，共榮社化學公司製之「DCP-A」(三環癸烷二甲醇二丙烯酸酯)、「DCP」(三環癸烷二甲醇二甲基丙烯酸酯)，日本化藥股份有限公司之「KAYARAD　R-684」(三環癸烷二甲醇二丙烯酸酯)、「KAYARAD　R-604」(二

烷二醇二丙烯酸酯)等。As a commercial product of (D) (meth)acrylate compound whose molecular weight is less than 1000, for example, "A-DOG" (two

Alkanediol diacrylate), "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., Japan "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (two

alkanediol diacrylate), etc.

(D) The (meth)acrylic group equivalent weight of the (meth)acrylate compound whose molecular weight is less than 1000 is preferably 30g/eq.~500g/eq., more preferably 40g/eq.~400g/eq., More preferably, it is 50g/eq.~300g/eq., especially preferably, it is 75g/eq.~200g/eq. The (meth)acrylic group equivalent is the mass of acryl and methacryl compounds per 1 equivalent.

(D) The molecular weight of the (meth)acrylate compound whose molecular weight is less than 1000 is preferably 800 or less, more preferably 600 or less. The lower limit is not particularly limited, but may be, for example, 100 or more.

The content of the (meth)acrylate compound in the resin composition of the first embodiment (D) with a molecular weight of less than 1000 is not particularly limited, but when the non-volatile components in the resin composition are defined as 100% by mass , preferably 25% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 7% by mass or less, particularly preferably 5% by mass or less. The lower limit of the content of the (meth)acrylate compound in the resin composition in the first embodiment (D) whose molecular weight is less than 1000 is not particularly limited, but the non-volatile component in the resin composition is defined as 100 mass %, for example, 0 mass % or more, 0.01 mass % or more, preferably 0.1 mass % or more, more preferably 0.5 mass % or more, further preferably 1 mass % or more, particularly preferably 1.5 mass % or more.

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

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

As a material of (E) inorganic filler, an inorganic compound is used. Examples of materials for (E) inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, aluminum hydrochloride Stone, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth oxide, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among them, silicon dioxide is particularly suitable. Silica may, for example, be amorphous silica, fused silica, crystalline silica, synthetic silica, or hollow silica. Also, spherical silica is preferable as silica. (E) Inorganic fillers may be used alone or in combination of two or more in arbitrary ratios.

Examples of commercially available (E) inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs; "DAW-03" and "FB-105FD" manufactured by Denka Corporation.

(E) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.7 μm or less. (E) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, still more preferably at least 0.1 μm, particularly preferably at least 0.2 μm. (E) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis with a laser diffraction scattering type particle size distribution measuring device, and can be measured by setting the median diameter as the average particle diameter. As a measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample is used to measure the particle size distribution of the laser diffraction type, and the wavelength of the light source is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured in a flow cell. The obtained particle size distribution is used as The average particle diameter was calculated from the median diameter. As a laser diffraction type particle size distribution measuring device, "LA-960" by Horiba Manufacturing Co., Ltd. etc. are mentioned, for example.

(E) Although the specific surface area of the inorganic filler is not particularly limited, it is preferably at least 0.1m ² /g, more preferably at least 0.5m ² /g, still more preferably at least 1m ² /g, and most preferably at least 3m ² /g. more than g. (E) Although the upper limit of the specific surface area of the inorganic filler is not particularly limited, it is preferably at most 100 m ² /g, more preferably at most 70 m ² /g, still more preferably at most 50 m ² /g, most preferably at most 40 m ² /g below g. The specific surface area of the inorganic filler was calculated by BET multi-point method by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.).

(E) Inorganic fillers are preferably treated with surface treatment agents from the viewpoint of improving 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, and organosilazane compounds , Titanate coupling agent, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

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

The degree of surface treatment by the surface treatment agent is preferably limited to a specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is 100% by mass, and the surface treatment agent is preferably 0.2% to 5% by mass, more preferably 0.2% to 3% by mass, and 0.3% to 2% by mass. It is better to carry out 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 0.2 mg/m ² or more from the viewpoint of improving the dispersibility of the inorganic filler. good. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition or the melt viscosity in the sheet form from increasing, 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 And then better.

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

The content of the (E) inorganic filler in the resin composition in the first embodiment is not particularly limited when the non-volatile content in the resin composition is 100% by mass, but it is preferably 10% by mass or more, More than 20% by mass, more preferably more than 30% by mass, more than 40% by mass, more preferably more than 50% by mass, more than 55% by mass, more preferably more than 60% by mass, more than 63% by mass, especially preferably more than 65% by mass % or more, 67 mass % or more. The content of (E) inorganic filler in the resin composition in the second embodiment is 60% by mass or more, preferably 63% by mass or more when the non-volatile content in the resin composition is 100% by mass. More preferably, it is 66 mass % or more, More preferably, it is 68 mass % or more, Most preferably, it is 70 mass % or more. The upper limit of the (E) inorganic filler content in the resin composition in the first embodiment and the second embodiment is not particularly limited, but when the non-volatile content in the resin composition is set as 100% by mass, it is relatively The best is at most 90% by mass, more preferably at most 85% by mass, still more preferably at most 80% by mass, and most preferably at most 75% by mass.

The mass ratio of (E) the inorganic filler in the resin composition to (A) the allyl compound having an alicyclic structure ((E) component/(A) component) is preferably 10 or more, more preferably More than 15, especially better than 20. The upper limit of the mass ratio ((E) component/(A) component) of the (E) inorganic filler in the resin composition to (A) the allyl compound having an alicyclic structure is preferably 10000 or less, more preferably The best is below 1000, and the best is below 400.

<(F) Radical polymerizable compound with a molecular weight of 1000 or more> The resin composition in the first embodiment of the present invention may contain (F) a radically polymerizable compound having a molecular weight of 1000 or more as an optional component. (F) The radically polymerizable compound having a molecular weight of 1000 or more may be used alone or in any combination of two or more.

(F) A 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) A radically polymerizable compound having a molecular weight of 1000 or more is not particularly limited, but may have, for example, allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-ethylene Unsaturated hydrocarbon groups such as phenyl, o-vinylphenyl, etc.; acryl, methacryl, maleimide (2,5-dihydro-2,5-diendoxy-1H Radical polymerizable groups such as α,β-unsaturated carbonyl groups such as -pyrrol-1-yl). (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) Radical polymerizable compounds having a molecular weight of 1000 or more include, for example, (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, maleimide radical polymerizable compounds, etc. .

The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more acryl groups and/or methacryl groups. Examples thereof include (meth)acryl-based modified polyphenylene ether resins and the like. As a commercial item of a (meth)acrylic-type radically polymerizable compound, "SA9000" and "SA9000-111" (methacryl-modified polyphenylene ether resin) etc. by SABIC INNOVATIVE PLASTICS CO., LTD. are mentioned, for example.

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 the styrene-based radically polymerizable compound include vinylbenzyl-modified polyphenylene ether resin, styrene-divinylbenzene copolymer, and the like. Examples of commercially available styrene-based radically polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)" and "ODV-XET (X05)" manufactured by Nippon Steel Chemical & Materials Co., Ltd. " (styrene-divinylbenzene copolymer), "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. Maleimide-based free radical polymerizable compounds can be aliphatic maleimide compounds containing an aliphatic amine skeleton, or aromatic maleimide compounds containing an aromatic amine skeleton, commercially available as As a product, for example, "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd. may be mentioned.

(F) The ethylenic unsaturated bond equivalent weight of the radically polymerizable compound with a molecular weight of 1000 or more is preferably 20g/eq.~3000g/eq., more preferably 50g/eq.~2500g/eq., still more preferably 70g /eq.~2000g/eq., especially 90g/eq.~1500g/eq. The ethylenically unsaturated bond equivalent is the mass of a radically polymerizable compound per 1 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, further preferably 6,000 or less, most preferably 4,000 or less. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

The content of (F) the radically polymerizable compound having a molecular weight of 1000 or more in the resin composition in the first embodiment is not particularly limited, but it is preferable when the non-volatile components in the resin composition are 100% by mass. It is 25 mass % or less, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less, Most preferably, it is 3 mass % or less. The lower limit of the content of the (F) radically polymerizable compound having a molecular weight of 1000 or more in the resin composition of the first embodiment is not particularly limited, but when the non-volatile components in the resin composition are defined as 100% by mass, For example, it is at least 0% by mass, at least 0.001% by mass, preferably at least 0.01% by mass, more preferably at least 0.05% by mass, still more preferably at least 0.1% by mass, and most preferably at least 0.5% by mass.

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

(F') The radically polymerizable compound is, in one embodiment, a radically polymerizable compound having an ethylenically unsaturated bond. (F') Radical polymerizable compounds, although not particularly limited, include, for example, allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-vinylphenyl , o-vinylphenyl and other unsaturated hydrocarbon groups; 1-radical) and other radical polymerizable groups such as α,β-unsaturated carbonyl groups. (F') The radical polymerizable compound preferably has two or more radical polymerizable groups in one molecule.

(F') Radical polymerizable compounds include, for example, (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide Department of free radical polymerizable compounds.

烷二醇二(甲基)丙烯酸酯、3,6-二氧雜-1,8-辛二醇二(甲基)丙烯酸酯、3,6,9-三氧十一烷-1,11-二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀、乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯等之低分子量(分子量未達1000)之含醚之(甲基)丙烯酸酯化合物；參(3-羥基丙基)異三聚氰酸酯三(甲基)丙烯酸酯、參(2-羥基乙基)異三聚氰酸酯三(甲基)丙烯酸酯、乙氧基化異三聚氰酸三(甲基)丙烯酸酯等之低分子量(分子量未達1000)之含異三聚氰酸酯之(甲基)丙烯酸酯化合物；(甲基)丙烯酸基改質聚苯醚樹脂等之高分子量(分子量1000以上)之丙烯酸酯化合物等。作為(甲基)丙烯酸系自由基聚合性化合物之市售品，可舉例例如新中村化學工業公司製之「A-DOG」(二

烷二醇二丙烯酸酯)、共榮社化學公司製之「DCP-A」(三環癸烷二甲醇二丙烯酸酯)、「DCP」(三環癸烷二甲醇二甲基丙烯酸酯)、日本化藥股份有限公司之「KAYARAD R-684」(三環癸烷二甲醇二丙烯酸酯)、「KAYARAD R-604」(二

烷二醇二丙烯酸酯)、SABIC INNOVATIVE PLASTICS公司製之「SA9000」、「SA9000-111」(甲基丙烯酸基改質聚苯醚)等。The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more acryl groups and/or methacryl groups. Examples of (meth)acrylic radical polymerizable compounds include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylic acid ester, tricyclodecane dimethanol 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 Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. Aliphatic (meth)acrylate compounds of molecular weight (molecular weight less than 1000);

Alkanediol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxyundecane-1,11- Diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloxyethoxy ) phenyl] fennel, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc. Meth)acrylate compounds; ginseng(3-hydroxypropyl)isocyanurate tri(meth)acrylate, ginseng(2-hydroxyethyl)isocyanurate tri(meth)acrylate Low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as ethoxylated isocyanuric acid tri(meth)acrylate; (meth)acrylic acid group High molecular weight (more than 1000 molecular weight) acrylate compounds such as modified polyphenylene ether resins, etc. As a commercial product of (meth)acrylic radical polymerizable compound, for example, "A-DOG" (2

alkanediol diacrylate), "DCP-A" (tricyclodecane dimethanol diacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "DCP" (tricyclodecane dimethanol dimethacrylate), Japan "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (two

alkanediol diacrylate), "SA9000" and "SA9000-111" (methacryl-modified polyphenylene ether) manufactured by SABIC INNOVATIVE PLASTICS, etc.

The styrene-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based radically polymerizable compounds include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'- Divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, etc. Styrenic compounds with molecular weight (molecular weight less than 1000); high molecular weight (molecular weight above 1000) styrenic compounds such as vinylbenzyl modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Examples of commercially available styrene-based radically polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)" and "ODV-XET (X05)" manufactured by Nippon Steel Chemical & Materials Co., Ltd. " (styrene-divinylbenzene copolymer), "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

-3-基)苯基]甲烷等之含苯并

之芳香族烯丙基化合物；1,3,5-三烯丙基醚苯等之含醚之芳香族烯丙基化合物；二烯丙基二苯基矽烷等之烯丙基矽烷化合物等。作為烯丙基系自由基聚合性化合物之市售品，可舉例日本化成公司製之「TAIC」(1,3,5-三烯丙基異三聚氰酸酯)、Nisshoku Techno Fine Chemical公司製之「DAD」(聯苯二甲酸二烯丙酯)、和光純藥工業公司製之「TRIAM-705」(偏苯三甲酸三烯丙酯)、日本蒸餾工業公司製之商品名「DAND」(2,3-萘羧酸二烯丙酯)、四國化成工業公司製「ALP-d」(雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯并

-3-基)苯基]甲烷)、日本化藥公司製之「RE-810NM」(2,2-雙[3-烯丙基-4-(環氧丙氧基)苯基]丙烷)、四國化成公司製之「DA-MGIC」(1,3-二烯丙基-5-環氧丙基異三聚氰酸酯)等。The allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of allyl-based radically polymerizable compounds include diallyl biphthalate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, terephthalic acid Diallyl ester, diallyl 2,6-naphthalene dicarboxylate, diallyl 2,3-naphthalene carboxylate and other aromatic carboxylic acid allyl compounds; 1,3,5-triallyl Allyl isocyanurate compounds such as isocyanurate and 1,3-diallyl-5-epoxypropyl isocyanurate; 2,2-bis[3-ene Epoxy-containing aromatic allyl compounds such as propyl-4-(glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro-2H-1 ,3-Benzo

-3-yl)phenyl]methane containing benzo

Aromatic allyl compounds such as 1,3,5-triallyl ether benzene and other ether-containing aromatic allyl compounds; allyl silane compounds such as diallyldiphenylsilane, etc. Commercially available allyl-based radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemicals Co., Ltd., and Nisshoku Techno Fine Chemical Co., Ltd. "DAD" (diallyl diphenylcarboxylate), "TRIAM-705" (triallyl trimellitic acid) manufactured by Wako Pure Chemical Industries, Ltd., "DAND" ( Diallyl 2,3-naphthalenecarboxylate), "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzene and

-3-yl)phenyl]methane), Nippon Kayaku "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), "DA-MGIC" (1,3-diallyl-5-epoxypropyl isocyanurate) manufactured by Shikoku Chemicals Co., Ltd., etc.

The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. Maleimide-based radical polymerizable compounds can be aliphatic maleimide compounds containing an aliphatic amine skeleton, or aromatic maleimide compounds containing an aromatic amine skeleton. Commercially available Products, such as "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500" manufactured by Designer Molecules, "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500 "(dimer diamine structure containing maleimide compound), "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd. ", "MIR-3000-70MT" (biphenylaralkyl-type maleimide compound), "BMI-70" manufactured by K･I Chemicals Corporation, "BMI-80" manufactured by Daiwa Chemical Industry Co., Ltd. "BMI -2300", "BMI-TMH", etc. Also, as (maleimide-based free radical polymerizable compound, the maleimide resin (maleimide resin containing dihydroindane ring skeleton) disclosed in the Technical Publication No. 2020-500211 of the Invention Association can be used. amine compounds).

(F') The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20g/eq.~3000g/eq., more preferably 50g/eq.~2500g/eq., still more preferably 70g/eq. ~2000g/eq., especially 90g/eq.~1500g/eq. The ethylenically unsaturated bond equivalent is the mass of a radically polymerizable compound per 1 equivalent of ethylenically unsaturated bond.

(F') The weight average molecular weight (Mw) of the radically polymerizable compound is preferably at most 40,000, more preferably at most 10,000, still more preferably at most 5,000, particularly preferably at most 3,000. Although the lower limit is not particularly limited, for example, it can be set to 150 or more.

The content of the (F') radical polymerizable compound in the resin composition in the second embodiment is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 25% by mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, further preferably 5 mass % or less, particularly preferably 3 mass % or less. The lower limit of the content of the (F') radically polymerizable compound in the resin composition in the second embodiment is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, for example, 0 mass % or more, 0.001 mass % or more, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, still more preferably 0.1 mass % or more, most preferably 0.5 mass % or more.

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

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

As the phosphorus-based hardening accelerator, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium Butylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methyl Aliphatic phosphonium salts such as phenoxide, di-tertiary butyldimethylphosphonium tetraphenylborate, etc.; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylbromide Phosphonium chloride, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylphosphonium borate, tetraphenylphosphonium tetra Phenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenyl borate, ginseng (3-methylphenyl) ethylphosphonium tetraphenyl borate, ginseng (2 -Methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate Aromatic phosphonium salts such as acid salts; Aromatic phosphine and borane complexes such as triphenylphosphine and triphenylborane; Aromatic phosphine and quinone such as triphenylphosphine and p-benzoquinone addition reactants Addition reactants; tributylphosphine, tri-tertiary butylphosphine, trioctylphosphine, di-tertiary butyl (2-butenyl) phosphine, di-tertiary butyl (3-methyl- Aliphatic phosphines such as 2-butenyl)phosphine and tricyclohexylphosphine; dibutylphenylphosphine, di-tertiary butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyl Diphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, reference (4-ethylphenyl ) phosphine, ginseng (4-propylphenyl) phosphine, ginseng (4-isopropylphenyl) phosphine, ginseng (4-butylphenyl) phosphine, ginseng (4-tertiary butylphenyl) phosphine, ginseng (2,4-Dimethylphenyl) phosphine, ginseng (2,5-dimethylphenyl) phosphine, ginseng (2,6-dimethylphenyl) phosphine, ginseng (3,5-dimethyl Phenyl) phosphine, ginseng (2,4,6-trimethylphenyl) phosphine, ginseng (2,6-dimethyl-4-ethoxyphenyl) phosphine, ginseng (2-methoxyphenyl) ) phosphine, ginseng (4-methoxyphenyl) phosphine, ginseng (4-ethoxyphenyl) phosphine, ginseng (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridyl phosphine , 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis Aromatic phosphines such as (diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, etc.

Examples of urea-based hardening accelerators include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1 , 1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea and other aliphatic 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-methoxy phenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)benzene base]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)benzene base]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1 , 3-phenylene) bis (N', N'-dimethylurea) [toluene bisdimethylurea] and other aromatic dimethylureas.

As the guanidine hardening accelerator, for example, dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dicyandiamide, Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl- 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide , 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三

、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三

、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三

異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂的加成物。Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 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-tri

, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-tri

, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri

, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri

Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2- Imidazole compounds such as methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

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

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

As the amine-based hardening accelerator, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-paraffin (dimethylaminopyridine) Methyl)phenol, 1,8-diacribicyclo(5,4,0)-undecene, etc.

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

The content of the (G) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass At most, more preferably at most 5% by mass, particularly preferably at most 1% by mass. The lower limit of the content of the (G) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 0.001% by mass More than, 0.01% by mass or more, 0.05% by mass or more, etc.

＜(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) an allyl compound having an alicyclic structure, (F) a radically polymerizable compound with a molecular weight of 1000 or more, and (F') a radical Components other than polymeric compounds.

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

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

As the phenoxy resin, for example, one having a structure selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fennel skeleton, dicyclopentadiene A phenoxy resin having one or more skeletons in the group consisting of a norcamphene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be a functional group of any one of phenolic hydroxyl group and epoxy group.

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

The polyvinyl acetal resin may, for example, be polyvinyl formal resin or polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include "DENKABUTYRAL 4000-2", "DENKABUTYRAL 5000-A", "DENKABUTYRAL 6000-C", and "DENKABUTYRAL 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd.; S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series; etc.

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

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, polybutadiene resins containing Anhydride-based polybutadiene resin, epoxy-containing polybutadiene resin, isocyanate-containing polybutadiene resin, urethane-containing polybutadiene resin, polyphenylene ether-polybutadiene diene resin etc.

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

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

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

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

As polycarbonate resins, hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, acid anhydride-containing carbonate resins, isocyanate-containing carbonate resins, carbamic acid-containing Ester-based carbonate resin, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-1090" manufactured by Kuraray Co., Ltd. , "C-2090", "C-3090" (polycarbonate diol), etc. Specific examples of the polyetheretherketone resin include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene Terephthalate resin, polytrimethylene naphthalene dicarboxylic acid resin, polycyclohexane dimethyl terephthalate resin, etc.

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

The content of the (H) thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are defined as 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is relatively low. Preferably, it is 20 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 3 mass % or less, Most preferably, it is 1 mass % or less. The lower limit of the (H) thermoplastic resin content in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 0.01% by mass More than, 0.1% by mass or more, 0.3% by mass or more, etc.

樹脂、不飽和聚酯樹脂、酚樹脂、三聚氰胺樹脂、聚矽氧樹脂等之環氧樹脂以外之熱硬化性樹脂；橡膠粒子等之有機填充材；有機銅化合物、有機鋅化合物、有機鈷化合物等之有機金屬化合物；酞青素藍、酞青素綠、碘綠、重氮黃、結晶紫、氧化鈦、碳黑等之著色劑；氫醌、兒茶酚、五倍子酚、啡噻

等之聚合抑制劑；聚矽氧系流平劑、丙烯酸基聚合物系流平劑等之流平劑；本頓、蒙脫石等之增黏劑；聚矽氧系消泡劑、丙烯酸系消泡劑、氟系消泡劑、乙烯基樹脂系消泡劑等之消泡劑；苯并三唑系紫外線吸收劑等之紫外線吸收劑；尿素矽烷等之接著性提升劑；三唑系密著性賦予劑、四唑系密著性賦予劑、三

系密著性賦予劑等之密著性賦予劑；受阻酚系抗氧化劑等之抗氧化劑；茋衍生物等之螢光增白劑；氟系界面活性劑、聚矽氧系界面活性劑等之界面活性劑；磷系阻燃劑(例如磷酸酯化合物、膦氮烯化合物、次膦酸化合物、紅磷)、氮系阻燃劑(例如硫酸三聚氰胺)、鹵素系阻燃劑、無機系阻燃劑(例如三氧化銻)等之阻燃劑；磷酸酯系分散劑、聚氧化烯系分散劑、乙炔系分散劑、聚矽氧系分散劑、陰離子性分散劑、陽離子性分散劑等之分散劑；硼酸鹽系安定劑、鈦酸酯系安定劑、鋁酸鹽系安定劑、鋯酸鹽系安定劑、異氰酸酯系安定劑、羧酸系安定劑、羧酸酐系安定劑等之安定劑等。(I)其他添加劑，可單獨使用1種，亦可以任意之比率組合2種以上使用。(I)其他添加劑之含量，該業者可適當地設定。 <(I) Other additives> The resin composition of the present invention may further contain arbitrary additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, etc. resin, urethane resin, cyanate resin, benzo

Thermosetting resins other than epoxy resins such as resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organic copper compounds, organic zinc compounds, organic cobalt compounds, etc. organometallic compounds; coloring agents of phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.;

Polymerization inhibitors such as polysiloxane-based leveling agents, acrylic-based polymer-based leveling agents, etc.; tackifiers such as Benton, montmorillonite, etc.; Defoamers, fluorine-based defoamers, vinyl resin-based defoamers, etc.; benzotriazole-based UV absorbers, etc.; UV absorbers, such as urea silane; Adhesive imparting agent, tetrazole-based adhesive imparting agent, three

Adhesive imparting agents such as adhesive imparting agents; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; fluorine-based surfactants, polysiloxane-based surfactants, etc. Surfactants; phosphorus flame retardants (such as phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (such as melamine sulfate), halogen flame retardants, inorganic flame retardants Flame retardants such as antimony trioxide; phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, polysiloxane dispersants, anionic dispersants, cationic dispersants, etc. stabilizers; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylic anhydride-based stabilizers, etc. . (I) Other additives may be used alone or in combination of two or more at any ratio. (I) The content of other additives can be set appropriately by the industry.

烷、二乙醚、二異丙基醚、二丁基醚、二苯基醚、苯甲醚等之醚系溶劑；甲醇、乙醇、丙醇、丁醇、乙二醇等之醇系溶劑；乙酸2-乙氧基乙酯、丙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇乙酸酯、γ-丁內酯、甲氧基丙酸甲酯等之醚酯系溶劑；乳酸甲酯、乳酸乙酯、2-羥基異丁酸甲酯等之酯醇系溶劑；2-甲氧基丙醇、2-甲氧基乙醇、2-乙氧基乙醇、丙二醇單甲基醚、二乙二醇單丁基醚(丁基卡必醇)等之醚醇系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等之醯胺系溶劑；二甲基亞碸等之亞碸系溶劑；乙腈、丙腈等之腈系溶劑；己烷、環戊烷、環己烷、甲基環己烷等之脂肪族烴系溶劑；苯、甲苯、二甲苯、乙苯、三甲基苯等之芳香族烴系溶劑等。(J)有機溶劑，可單獨使用1種，亦可以任意之比率組合2種以上使用。 <(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 above-mentioned non-volatile components. As (J) organic solvent, a well-known thing can be used suitably, and the kind is not specifically limited. Examples of (J) organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. , isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-di

Ether-based solvents such as alkanes, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; acetic acid 2-Ethoxyethyl Ester, Propylene Glycol Monomethyl Ether Acetate, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Acetate, Gamma-Butyrolactone, Methyl Methoxypropionate Ether ester solvents; methyl lactate, ethyl lactate, 2-hydroxyisobutyrate methyl ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxy Ether alcohol solvents such as ethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, N,N-dimethylacetamide Amide-based solvents such as amines and N-methyl-2-pyrrolidone; Arthrine-based solvents such as dimethylsulfide; Nitrile-based solvents such as acetonitrile and propionitrile; Hexane, cyclopentane, cyclohexane Aliphatic hydrocarbon solvents such as alkane and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (J) Organic solvents may be used alone or in combination of two or more at any ratio.

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

＜Manufacturing method of resin composition＞ The resin composition of the present invention, for example, can be added (A) allyl compound having an alicyclic structure, (B) epoxy resin, (C) Active ester compound, if necessary (C') other hardener, if necessary (D) (meth)acrylate compound with molecular weight less than 1000, if necessary (E) inorganic filler, if necessary (F) molecular weight More than 1000 free radical polymerizable compounds, optional (F') free radical polymerizable compounds, optional (G) hardening accelerators, optional (H) thermoplastic resins, optional (I) other additives and optional ( J) Organic solvents and mixing to manufacture. In addition, in the process of adding and mixing each component, the temperature may be set appropriately, and heating and/or cooling may be performed temporarily or all the time. In addition, during or after addition and mixing, the resin composition may be uniformly dispersed by stirring or shaking using a stirring device such as a mixer or an oscillating device, for example. Moreover, you may perform defoaming under low pressure conditions, such as a vacuum, simultaneously with stirring or shaking.

＜Characteristics of resin composition＞ The resin composition in the first embodiment of the present invention includes (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 roughened surface of the insulating layer can be reduced, and a hardened product having excellent copper plating peel strength and smear removability can be obtained.

The cured product of the resin composition in the first embodiment of the present invention can be characterized in that the arithmetic mean roughness (Ra) of the roughened surface is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the cured product after the roughening treatment as measured in Test Example 2 below is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 200 nm or less. 170nm or less, more preferably 150nm or less, and most preferably 130nm or less. There is no particular limitation on the lower limit, and for example, it can be set to 1 nm or more, 2 nm or more, and the like.

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

The cured product of the resin composition in the first embodiment of the present invention can be characterized by excellent smear removability. Therefore, in one embodiment, as in the following test example 1, a through hole with a top diameter of 50 μm on the surface of the hardened product and a diameter of 40 μm on the bottom surface of the through hole is formed. Over time, the maximum size of smear can become less than 5 μm.

In one embodiment, the cured product of the resin composition in the first embodiment of the present invention may have 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. in Test Example 4 below is preferably 0.0200 or less, 0.0100 or less, more preferably 0.0100 or less. It is 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, 0.0026 or less.

The resin composition in the second embodiment of the present invention includes (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound, and (E) an inorganic filler, ( C) The content of the active ester compound is 10% by mass or more, and (E) The content of the inorganic filler is 60% by mass or more. By using such a resin composition, it is possible to obtain a cured product with a low dielectric loss tangent (Df), excellent elongation at breaking point and excellent substrate copper adhesion strength (copper foil peel strength) after the accelerated environmental test (HAST) .

The cured product of the resin composition in the second embodiment of the present invention can have 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. in the following test example 2' is preferably 0.0200 or less, more preferably 0.0100 or less. It can be 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, and particularly preferably 0.0028 or less, 0.0027 or less.

The cured product of the resin composition in the second embodiment of the present invention can be characterized in that it has a high base copper adhesion strength (copper foil peel strength) after an accelerated environmental test (HAST). Therefore, in one embodiment, the substrate copper adhesion strength (copper foil peeling strength) after the accelerated environmental test (HAST) measured according to JIS C6481 as in the following test example 1' is preferably 0.1kgf/cm or more, more preferably It can be 0.13kgf/cm or more, 0.15kgf/cm or more, more preferably 0.16kgf/cm or more, 0.17kgf/cm or more, still more preferably 0.18kgf/cm or more, 0.19kgf/cm or more, especially preferably 0.16kgf/cm or more. 0.20kgf/cm or more. Also, the base copper adhesion strength (copper foil peel strength) before the accelerated environmental test (HAST) measured in the same way is preferably 0.2kgf/cm or more, more preferably 0.3kgf/cm or more, and even more preferably 0.4kgf/cm kgf/cm or more, more preferably 0.5 kgf/cm or more, particularly preferably 0.6 kgf/cm or more.

The cured product of the resin composition in the second embodiment of the present invention can be characterized by excellent elongation at breaking point. Therefore, in one embodiment, the elongation at breaking point as measured in the following test example 3' is preferably 0.5% or more, more preferably 0.8% or more, and even more preferably 1.0% when measured at 23°C. More than 1.2% is especially good. The upper limit of elongation at breaking point can usually be set as below 10%, below 5%, etc.

＜Applications of resin composition＞ The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, and is particularly suitably used as a resin composition for forming an insulating layer. Specifically, as a resin composition for forming a conductive layer (including a rewiring layer) formed on an insulating layer (resin composition for forming an insulating layer for forming a conductive layer) for forming the insulating layer is suitably used . Moreover, in the printed wiring board mentioned later, the resin composition (resin composition for insulating layer formation of a printed wiring board) as a resin composition for forming the insulating layer of a printed wiring board can be used suitably. The resin composition of the present invention can also be used in sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor packaging materials, filling resins, and parts embedding resins. The composition is used in a wide range of applications.

Also, for example, when manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as an insulating layer for forming a rewiring layer to form a rewiring formation layer Resin composition (resin composition for rewiring forming layer formation), and resin composition for encapsulating semiconductor chips (resin composition for semiconductor chip encapsulation). When manufacturing a semiconductor chip package, a redistribution layer may be further formed on the package layer. (1) The step of laminating the temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming an encapsulation layer on the semiconductor wafer, (4) A step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) A step of forming a rewiring formation layer as an insulating layer on the surface where the base material and temporary fixing film of the semiconductor wafer are peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer.

In addition, the resin composition of the present invention can form an insulating layer with good embedding properties of parts, so it can also be suitably used in the case where the printed wiring board is a circuit board with built-in parts.

＜Flake laminated materials＞ Although the resin composition of the present invention can be used by coating in a varnish state, it is generally industrially suitable to use it in the form of a sheet-like laminate containing the resin composition.

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

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm, from the viewpoint of thinning the printed wiring board and providing a cured product of the resin composition that is excellent in film insulation. the following. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be set to 5 μm or more, 10 μm or more, or the like.

The support may, for example, be a film made of a plastic material, a metal foil, or a release paper, and a film or metal foil made of a plastic material is 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"), polyethylene naphthalate (hereinafter sometimes Polyesters such as "PEN" for short), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic resins such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and low-priced polyethylene terephthalate is particularly preferred.

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

The support body can also be subjected to matte treatment, corona treatment, and antistatic treatment on the surface that is bonded to the resin composition layer.

Moreover, as a support body, the support body with a release layer which has a release layer on the surface bonded to a resin composition layer can also be used. As the release agent used in the release layer of the support with release layer, for example, one selected from the group consisting of alkyd resin, polyolefin resin, urethane resin and silicone resin More than one type of release agent. As the support body with a release layer, commercially available products can also be used, for example, "SK-1" manufactured by Lintec Co., Ltd., which has a PET film with a release layer having an alkyd resin release agent as a main component, "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by Unitika Corporation, etc.

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

In one embodiment, the resin sheet may further include an arbitrary layer if necessary. Such an arbitrary layer may, for example, be a support-based protective film provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust, etc. or scratches on the surface of the resin composition layer.

For the resin sheet, for example, a liquid resin composition is prepared directly or a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and this is coated on a support by using a die coater or the like, and then the It is manufactured by drying to form a resin composition layer.

As an organic solvent, the thing similar to the organic solvent demonstrated as a component of a resin composition is mentioned. An organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

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

Resin flakes that can be rolled into rolls for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention into a sheet-shaped fibrous base material.

The sheet-shaped fiber base material used in the prepreg is not particularly limited, and glass cloth, polyaramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc., which are commonly used as the base material for prepreg, can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-shaped fiber substrate is preferably at most 50 μm, more preferably at most 40 μm, further preferably at most 30 μm, particularly preferably at most 20 μm. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited. Usually 10 μm or more.

The prepreg can be produced by known methods such as a hot-melt method and a solvent method.

The thickness of the prepreg can be set within the same range as that of the resin composition layer in the above-mentioned resin sheet.

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

＜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 is manufactured by the method including the following (I) and (II) process using the said resin sheet, for example. (I) Step of laminating the resin sheet on the inner substrate in such a way that the resin composition layer of the resin sheet is bonded to the inner substrate (II) A step of hardening (for example, thermosetting) the resin composition layer to form an insulating layer

The so-called "inner layer substrate" used in step (I) is a component that becomes a substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting Type polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both surfaces, and the conductor layer may also be patterned. Inner substrates with conductive layers (circuits) formed on one or both sides of the substrate are sometimes referred to as "inner circuit substrates". In addition, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductive layer is to be formed is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner substrate with built-in parts can also be used.

The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by heat-compression bonding the resin sheet to the inner layer substrate from the side of the support. As the member for thermocompression-bonding the resin sheet to the inner layer substrate (hereinafter, also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller) can be exemplified. In addition, instead of directly pressing the thermocompression bonding member on the resin sheet, it is better to apply pressure through an elastic material such as heat-resistant rubber in order for the resin sheet to fully adhere to the surface unevenness of the inner substrate.

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

Lamination can be carried out by a commercially available vacuum lamination machine. As a commercially available vacuum lamination machine, the vacuum pressure lamination machine manufactured by Meiki Co., Ltd., the vacuum lamination machine manufactured by Nikko Materials, and the batch type vacuum pressure lamination machine etc. are mentioned, for example.

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

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

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

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

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

When manufacturing a printed wiring board, (III) the step of punching 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 implemented. These steps (III) to (V) can also be implemented according to various methods known to those in the industry for the manufacture of printed wiring boards. In addition, when removing the support body after step (II), the removal of the support body can be between step (II) and step (III), between step (III) and step (IV), or step (IV) Implement between step (V). In addition, the formation of the insulating layer and the conductor layer of step (II) to step (V) may be repeated as needed to form a multilayer wiring board.

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

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

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

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

The oxidizing agent used for the roughening treatment is not particularly limited, but for example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution is exemplified. The roughening treatment by an oxidizing agent such as alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Also, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As a commercially available oxidizing agent, the alkali permanganate solution, such as "Concentrates Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., can be mentioned, for example.

In addition, as the neutralizing solution used in the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited.

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

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

Step (V) is a step of forming a conductive layer, and the conductive layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a more suitable embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper ･Titanium alloy) layer. Among them, from the viewpoint of versatility, cost, and ease of patterning of conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel･ The alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy is better, the single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or the alloy layer of nickel-chromium alloy is better , a single metal layer of copper is even better.

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

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, although it varies depending on the desired design of the printed wiring board.

In one embodiment, the conductive layer can be formed by plating. For example, plating can be performed on the surface of the insulating layer by conventionally known techniques such as semi-additive method and full-additive method to form a conductor layer having a desired wiring pattern. Formation by a semi-additive method is preferable from the viewpoint of ease of production. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

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

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

Metal foil can be produced by known methods such as electrolysis and rolling, for example. Examples of commercially available metal foils include HLP foil, JXUT-III foil, and 3EC-III foil and TP-III foil manufactured by JX Nippon Oil & Metal Co., Ltd., respectively.

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

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

Hereinafter, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples. In addition, in the following, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise indicated. In particular, when the temperature and pressure are not specified, the temperature and pressure conditions are room temperature (23°C) and atmospheric pressure (1atm), respectively.

骨架之苯酚系硬化劑(DIC公司製「LA-3018-50P」，活性基當量約151g/eq.，不揮發成分率50%之2-甲氧基丙醇溶液)2份、碳二亞胺系硬化劑(日清紡化學公司製「V-03」，活性基當量約216g/eq.，不揮發成分率50%之甲苯溶液)5份、咪唑系硬化促進劑(四國化成工業公司製「1B2PZ」，1-苄基-2-苯基咪唑)0.1份、苯氧基樹脂(三菱化學公司製「YX7553BH30」，不揮發分30質量%之MEK與環己酮之1：1溶液)2份混合，以高速旋轉混合器均勻地分散，調製樹脂組成物(樹脂清漆)。 <Example 1> Bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a 1:1 mixture of bisphenol A and bisphenol F, epoxy equivalent about 169g/eq.) 2 8 parts, and 8 parts of naphthol-type epoxy resin ("ESN475V" produced by Nippon Steel Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330g/eq.), heated and dissolved in 5 parts of solvent naphtha while stirring. It was cooled to room temperature to prepare a dissolved composition of epoxy resin. In this dissolved epoxy resin composition, an allyl compound having an alicyclic structure ("FATC-809" produced by Qunyei Chemical Industry Co., Ltd., with a weight average molecular weight of about 10,000 and an allyl equivalent of about 400g/eq. ) 4 parts of 50% MEK solution, 4 parts of acrylate ("A-DOG" manufactured by Shin-Nakamura Chemical Co. 8000-65T", active ester group equivalent about 223g/eq., toluene solution with a non-volatile content rate of 65%) 30 parts, spherical carbon dioxide surface-treated with silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) 90 parts of silicon ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² /g) containing three

Skeleton phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, active group equivalent of about 151g/eq., 2-methoxy propanol solution with 50% non-volatile content) 2 parts, carbodiimide 5 parts of hardening agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution with an active group equivalent of about 216 g/eq. and a non-volatile content rate of 50%), imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd. ", 0.1 part of 1-benzyl-2-phenylimidazole), 2 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK with 30% by mass non-volatile matter and cyclohexanone) were mixed , and uniformly disperse with a high-speed rotary mixer to prepare a resin composition (resin varnish).

<Example 2> Except using 4 parts of acrylate ("DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryl equivalent weight about 152g/eq.) instead of 4 parts of acrylate ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) , Use 30 parts of active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with active ester group equivalent of about 220g/eq., non-volatile content rate 62% by mass) instead of active ester compound ("HPC-8150-62T" manufactured by DIC Corporation) -8000-65T") 30 parts, except not using the phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), it carried out similarly to Example 1, and prepared the resin composition (resin varnish).

<Example 3> In addition to changing the amount of 50% MEK solution of an allyl compound having an alicyclic structure ("FATC-809" manufactured by Qunei Chemical Industry Co., Ltd.) from 4 parts to 8 parts, using an active ester compound ("FATC-809" manufactured by DIC Corporation) HPC-8150-62T", active ester group equivalent of about 220g/eq., toluene solution with a non-volatile content rate of 62% by mass) 30 parts instead of active ester compound ("HPC-8000-65T" manufactured by DIC Corporation) 30 parts, the The amount of acrylate ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 4 parts to 2 parts, and the same procedure as in Example 1 was carried out except that no phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation) was used. , to prepare a resin composition (resin varnish).

<Example 4> In addition to changing 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.) from 90 parts to 92 parts, an alicyclic 4 parts of 50% MEK solution of an allyl compound ("FTC-809AE" produced by Qunyei Chemical Industry Co., Ltd., about 1000 g/eq.) with the formula structure replaces the allyl compound with an alicyclic structure (group Sakae Chemical Industry Co., Ltd. "FATC-809") 50% MEK solution 4 parts, use active ester compound (DIC company "HPC-8150-62T", active ester group equivalent of about 220g/eq., non-volatile component rate 62 mass % toluene solution) in place of 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation), a resin composition (resin varnish) was prepared in the same manner as in Example 1.

<Example 5> Except that 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, no acrylate was used. ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) 4 parts, using active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, active ester group equivalent of about 220g/eq., non-volatile content of 62% by mass of toluene A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation) was replaced with 30 parts.

<Example 6> In addition to changing 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.) from 90 parts to 93 parts, and using biphenyl Aralkyl novolak-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with 70% non-volatile content) 2 parts, using active ester compound ("MIR-3000-70MT" manufactured by DIC Corporation) HPC-8150-62T", active ester group equivalent of about 220g/eq., non-volatile content rate 62 mass% toluene solution) 30 parts instead of active ester compound (DIC company "HPC-8000-65T") 30 parts , It carried out similarly to Example 1, and prepared the resin composition (resin varnish).

<Example 7> In addition, 2 parts of methacrylic modified polyphenylene ether ("SA9000-111" manufactured by SABIC INNOVATIVE PLASTICS Co., Ltd.) -70MT") except 2 parts, it carried out similarly to Example 6, and prepared the resin composition (resin varnish).

<Example 8> In addition, 2 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile content rate of 65%) was used instead of biphenyl aralkyl novolac type maleimide In addition to 2 parts of amine ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.), the amount of imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.5 parts, and the implementation In the same manner as in Example 6, a resin composition (resin varnish) was prepared.

＜Comparative example 1＞ In addition to changing 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.) from 90 parts to 85 parts, no grease was used. 4 parts of a 50% MEK solution of an allyl compound with a ring structure ("FATC-809" manufactured by Qunyei Chemical Industry Co., Ltd.), without using acrylate ("DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., (methyl ) acryl group equivalent of about 152g/eq.) 4 parts, the use amount of imidazole hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.5 part, the same as in Example 1 Then, a resin composition (resin varnish) is prepared.

＜Comparative example 2＞ In addition to using 30 parts of an active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution with an active ester group equivalent of about 220 g/eq. and a non-volatile content rate of 62% by mass) instead of the active ester compound ("HPC-8150-62T" manufactured by DIC Corporation) -8000-65T") except 30 parts, it carried out similarly to the comparative example 1, and prepared the resin composition (resin varnish).

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

<Test Example 1: Evaluation of Smudge Removal> (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 body, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying became 40 μm. Afterwards, the resin composition is dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support body and a resin composition layer.

(2) Substrate treatment of built-in substrates As an inner layer substrate, a glass cloth substrate epoxy resin double-sided copper-clad laminate with copper foil on the surface was prepared (thickness of copper foil: 18 μm, thickness of substrate: 0.8 mm, “R1515A” manufactured by Panasonic Corporation). The copper foil on the surface of the inner layer substrate was etched with a copper etching amount of 1 μm using a microetchant ("CZ8101" manufactured by MEC Corporation) to perform roughening treatment. Thereafter, drying was performed at 190° C. for 30 minutes.

(3) Lamination and hardening of resin sheets The resin sheet obtained in the above (1) was bonded to the inner substrate by bonding the resin composition layer using a batch type vacuum pressure laminating machine (two-stage build-up laminating machine "CVP700" manufactured by Nikko Materials Co., Ltd.), Laminated on both sides of the inner substrate. This lamination was carried out by pressure-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds after the pressure was reduced to 13 hPa or less for 30 seconds.

Next, the laminated resin sheets were heat-pressed for 60 seconds at 100° C. and a pressure of 0.5 MPa under atmospheric pressure to smooth them. Then put it into an oven at 130° C. and heat it for 30 minutes, then switch to an oven at 170° C. and heat it for 30 minutes.

(4) The formation of the through hole uses a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Machinery Co., Ltd. to process the insulating layer under the conditions of a frequency of 2000 Hz, a pulse width of 3 μ seconds, an output of 0.95 W, and a number of shots of 3. A via hole with a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 40 μm on the bottom of the insulating layer is formed. Furthermore, the PET film was peeled off afterwards.

(5) Roughening treatment The inner layer substrate was immersed in Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. in a swelling liquid at 60° C. for 10 minutes. Next, it was immersed in Concentrates Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Co., Ltd. of the roughening liquid at 80° C. for 20 minutes. Finally, it was immersed in Reduction solution Securiganth P manufactured by Atotech Japan Co., Ltd. of the neutralizing solution at 40° C. for 5 minutes. The obtained board|substrate was made into evaluation board|substrate A.

(6) Evaluation of Smear Removal Observe and evaluate the periphery of the through-hole bottom of substrate A with a scanning electron microscope (SEM), and measure the maximum smear length from the bottom wall of the through-hole from the obtained image, and evaluate according to the following criteria. ◯: The maximum size of smear is less than 5 μm. ×: The maximum smear length is 5 μm or more.

<Test Example 2: Determination of Arithmetic Mean Roughness (Ra)> The value obtained from the evaluation substrate A obtained in (5) of Test Example 1, using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments Co., Ltd.), using VSI mode and a 50x lens to set the measurement range to 121μm×92μm. Calculate the arithmetic mean roughness (Ra) value. Each was determined by obtaining the average value of 10 randomly selected points.

<Test Example 3: Measurement of Copper Plating Peel Strength> The evaluation substrate 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 at 25°C In the electroless copper plating solution for 20 minutes. After annealing by heating at 150°C for 30 minutes, an etching resist was formed, and copper sulfate electrolytic plating was performed after patterning by etching to form a conductor layer with a thickness of 30 μm. Next, an annealing treatment was performed at 200° C. for 60 minutes, and the resulting substrate was used as an evaluation substrate B.

In the portion of the conductor layer of the evaluation substrate B that does not contain through holes, cut a 10mm wide and 150mm long incision, peel off one end and use a gripper (manufactured by T.S.E., AUTO COM type testing machine AC-50C-SL ) at room temperature (25°C), measure the load (kgf/cm) when peeling 100mm vertically at a speed of 50mm/min.

<Test Example 4: Measurement of Dielectric Loss Tangent> The resin sheet obtained in (1) of Test Example 1 was heated and cured at 190° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-shaped cured product. Cut the cured product into test pieces with a width of 2 mm and a length of 80 mm, and use the cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and the Network analyzer E8362B manufactured by Agilent Technologies, Inc. to borrow the cavity resonance method. The dielectric loss tangent (tan δ) was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. It measured about 2 test pieces, and calculated the average value.

The amount of raw materials used and the content of non-volatile components of the resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3, and the measurement results of Test Examples 1 to 4 are shown in Table 1 below.

As shown in Table 1, in Comparative Examples 1 and 2 using the active ester compound, the smear removability was low. In addition, in Comparative Example 3 in which a low-molecular-weight (meth)acrylate compound was used together with the active ester compound, although the smear removal property was excellent, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment was High, copper plating low 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 of the surface of the insulating layer after the roughening treatment can be reduced. Degree (Ra), and can achieve excellent copper peel strength and smear removal results.

骨架之苯酚系硬化劑(DIC公司製「LA-3018-50P」，活性基當量約151g/eq.，不揮發成分率50%之2-甲氧基丙醇溶液)2份、碳二亞胺系硬化劑(日清紡化學公司製「V-03」，活性基當量約216g/eq.，不揮發成分率50%之甲苯溶液)5份、咪唑系硬化促進劑(四國化成工業公司製「1B2PZ」，1-苄基-2-苯基咪唑)0.1份、苯氧基樹脂(三菱化學公司製「YX7553BH30」，不揮發分30質量%之MEK與環己酮之1：1溶液)2份混合，以高速旋轉混合器均勻地分散，調製樹脂組成物(樹脂清漆)。 <Example 1'> 2 parts of an allyl compound having an alicyclic structure ("FATC-809" manufactured by Qunei Chemical Industry Co., Ltd., weight average molecular weight about 10000, allyl equivalent weight about 400g/eq.), naphthalene Type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, 1,6-bis(glycidoxy)naphthalene, epoxy equivalent about 145g/eq.) Dissolve 10 parts in MEK20 while stirring . Cool it to room temperature, and in this dissolved composition, add an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active ester equivalent of about 223 g/eq. and a non-volatile content rate of 65%) 30 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) 90 servings, containing three

Skeleton phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, active group equivalent of about 151g/eq., 2-methoxy propanol solution with 50% non-volatile content) 2 parts, carbodiimide 5 parts of hardening agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution with an active group equivalent of about 216 g/eq. and a non-volatile content rate of 50%), imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd. ", 0.1 part of 1-benzyl-2-phenylimidazole), 2 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK with 30% by mass non-volatile matter and cyclohexanone) were mixed , and uniformly disperse with a high-speed rotary mixer to prepare a resin composition (resin varnish).

<Example 2'> In addition to using an allyl compound with an alicyclic structure ("FTC-809AE" manufactured by Qunei Chemical Industry Co., Ltd., the allyl equivalent is about 1000g/eq.) instead of an allyl compound with an alicyclic structure (group Sakae Chemical Industry Co., Ltd. "FATC-809") 2 parts, active ester compound (DIC Corporation "HPC-8150-62T", active ester group equivalent of about 220g/eq., non-volatile content of 62% by mass toluene solution ) 30 parts instead of 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation), it carried out similarly to Example 1', and prepared the resin composition (resin varnish).

<Example 3'> In addition to using 10 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 269g/eq.) instead of 10 parts of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation) Except that, it carried out similarly to Example 1', and prepared the resin composition (resin varnish).

<Example 4'> The resin composition was prepared in the same manner as in Example 3', except that the amount of allyl compound having an alicyclic structure ("FATC-809" produced by Qunei Chemical Industry Co., Ltd.) was changed from 2 parts to 0.5 parts. material (resin varnish).

<Example 5'> In addition to using an allyl compound with an alicyclic structure ("FTC-809AE" manufactured by Qunei Chemical Industry Co., Ltd., weight average molecular weight is about (described later), allyl equivalent is about 1000g/eq.) instead of having an alicyclic A resin composition (resin varnish) was prepared in the same manner as in Example 3' except for 2 parts of an allyl compound having the structure of the formula ("FATC-809" manufactured by Qunei Chemical Industry Co., Ltd.).

<Example 6'> In addition to changing 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.) from 90 parts to 93 parts, and using biphenyl Aralkyl novolak-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with 70% non-volatile content) 2 parts, using active ester compound ("MIR-3000-70MT" manufactured by DIC Corporation) HPC-8150-62T", active ester group equivalent of about 220g/eq., non-volatile content rate 62 mass% toluene solution) 30 parts instead of active ester compound (DIC company "HPC-8000-65T") 30 parts , It carried out similarly to Example 1', and prepared the resin composition (resin varnish).

<Example 7'> In addition to using 2 parts of methacrylic modified polyphenylene ether ("SA9000-111" manufactured by SABIC INNOVATIVE PLASTICS Co., Ltd.) instead of biphenyl aralkyl novolak type maleimide ("MIR-3000- 70MT") except for 2 parts, it carried out similarly to Example 6', and prepared the resin composition (resin varnish).

<Example 8'> In addition to using 2 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content rate of 65%) instead of biphenyl aralkyl novolac-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.) 2 parts, and the amount of imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.5 parts. 6' In the same manner, a resin composition (resin varnish) was prepared.

＜Comparative example 1'＞ In addition to changing 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.) from 90 parts to 85 parts, no grease A resin composition (resin varnish) was prepared in the same manner as in Example 3' except for 2 parts of an allyl compound having a ring structure ("FATC-809" manufactured by Qunei Chemical Industry Co., Ltd.).

＜Comparative example 2'＞ In addition to changing 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.) from 90 parts to 85 parts, no grease A resin composition (resin varnish) was prepared in the same manner as in Example 2' except for 2 parts of an allyl compound having a ring structure ("FTC-809AE" manufactured by Qunei Chemical Industry Co., Ltd.).

＜Comparative example 3'＞ In addition to changing 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.) from 90 parts to 52 parts, the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation) was changed from 30 parts to 10 parts, and 2 parts of an allyl compound with an alicyclic structure ("FATC-809" manufactured by Qunei Chemical Industry Co., Ltd.) was not used Other than that, it carried out similarly to Example 1', and prepared the resin composition.

＜Comparative example 4'＞ In addition to changing 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.) from 90 parts to 40 parts, no grease A resin composition was prepared in the same manner as in Example 1' except for 2 parts of an allyl compound having a ring structure ("FATC-809" manufactured by Qunei Chemical Industry Co., Ltd.).

<Test example 1': Measurement of substrate copper adhesion strength (copper foil peel strength)> (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 became 40 μm. Afterwards, the resin composition is dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support body and a resin composition layer.

(2) Base treatment of copper foil The glossy surface of "3EC-III" (electrolytic copper foil, 35μm) manufactured by Mitsui Mining Co., Ltd. was etched 1 μm with "CZ8101" manufactured by MEC Co., Ltd. to roughen the copper surface, followed by antirust treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it heat-processed in the oven of 130 degreeC for 30 minutes, and obtained the CZ copper foil which has a process surface.

(3) Preparation of the inner substrate: The two sides of the glass cloth substrate epoxy resin double-sided copper-clad laminate (the thickness of the copper foil is 18 μm, the thickness of the substrate is 0.4 mm, “R1515A” manufactured by Panasonic Co., Ltd.) with the inner layer circuit formed are 1 μm with “CZ8101” manufactured by MEC Corporation. Etching is used to roughen the copper surface to obtain an inner substrate.

(4) Lamination of resin composition layers The protective film was peeled off from the resin sheet prepared in (1) above to expose the resin composition layer. Using a batch type vacuum pressure laminating machine (manufactured by Nikko Materials, two-stage stacking laminating machine "CVP700"), the resin composition layer was laminated on both sides of the inner substrate so that the resin composition layer was in contact with the inner substrate. This lamination was carried out by pressure-bonding at 120° C. and a pressure of 0.74 MPa for 30 seconds after adjusting the air pressure to 13 hPa or less by reducing the pressure for 30 seconds. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds. Thereafter, the support was peeled off to expose the resin composition layer.

(5) Lamination of copper foil and hardening of resin composition layer On the exposed resin composition layer, the treated surface of the CZ copper foil is laminated under the same conditions as in (4) above, and the resin composition layer is cured under the curing conditions of 200°C and 90 minutes to form a cured product (insulation Layer), the evaluation substrate A with CZ copper foil laminated on both sides was produced.

(6) Determination of substrate copper adhesion strength (copper foil peel strength) before HAST The evaluation substrate A produced in (5) above was cut into small pieces of 150mm×30mm. On the copper foil part of the small piece, use a cutter to cut out a part with a width of 10mm and a length of 100mm, peel off one end and clamp it with the gripper of the tensile testing machine described below, and use it at room temperature (23°C). Tensile testing machine (AUTO COM universal testing machine "AC-50C-SL" manufactured by T.S.E Co., Ltd.) measures the load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min according to JIS C6481.

(7) Determination of substrate copper adhesion strength (copper foil peel strength) after HAST The evaluation substrate A prepared in (5) above was subjected to an accelerated environmental test for 100 hours under high-temperature and high-humidity conditions of 130°C and 85%RH using a highly accelerated life tester ("PM422" manufactured by Kusumoto Kasei Co., Ltd.). After that, cut out the same incision as above on the evaluation substrate A after HAST, peel off one end of the incision in the same way as the measurement of (6) above, clamp it with the gripper of the above-mentioned tensile testing machine, and set it at room temperature (ordinary temperature) Next, the load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min was measured according to Japanese Industrial Standard JIS C6481.

<Test example 2': Measurement of dielectric loss tangent> Peel off the protective film from the resin sheet produced in (1) of Test Example 1', heat at 200°C for 90 minutes to thermally harden the resin composition layer, and then peel off the support to obtain a cured product of the resin composition. hardened film. The cured product film was cut out with a width of 2 mm and a length of 80 mm to obtain a cured product A for evaluation.

With regard to the obtained cured product A for evaluation, the value of the dielectric loss tangent (Df value) was measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using “HP8362B” manufactured by Agilent Technologies. The measurement was performed on three test pieces, and the average value was calculated.

<Test Example 3': Determination of elongation at breaking point> Regarding the hardened product A for evaluation obtained in Test Example 2', a tensile test was performed on a Tensilon universal testing machine ("RTC-1250A" manufactured by ORIENTEC) in accordance with Japanese Industrial Standards JIS K7127 at room temperature (23°C) , Determination of elongation at breaking point (%).

The amount of raw materials used and the content of non-volatile components of the resin compositions of Examples 1' to 8' and Comparative Examples 1' to 4', and the measurement results of Test Examples 1' to 3' are shown in Table 2 below.

As shown in Table 2, the dielectric loss tangent is relatively high in Comparative Example 3' in which (C) the content of the active ester compound is low and in Comparative Example 4' in (E) the content of the inorganic filler is low. (C) Comparative examples 1' and 2' in which the contents of (C) active ester compound and (E) inorganic filler were high, although the dielectric loss tangent was low, the breaking point elongation was low, and the accelerated environmental test (HAST ) After the base copper adhesion strength (copper foil peel strength) is also low. On the other hand, in the case of using the resin composition of the present invention containing (A) an allyl compound having an alicyclic structure, the dielectric loss tangent (Df) is low, the breaking point elongation is high, and the accelerated environment The base copper adhesion strength (copper foil peel strength) after the test (HAST) is also high.

Claims (26)

A resin composition comprising (A) an allyl compound with an alicyclic structure, (B) an epoxy resin and (C) an active ester compound. The resin composition according to claim 1, further comprising (D) a (meth)acrylate compound with a molecular weight of less than 1,000. The resin composition according to claim 2, wherein the mass ratio of (D) component to (A) component ((D) component/(A) component) is 0.1-10. The resin composition according to claim 1, wherein when the non-volatile components in the resin composition are defined as 100% by mass, the content of component (C) is 10% by mass or more. The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition according to claim 5, wherein when the non-volatile components in the resin composition are defined as 100% by mass, the content of the component (E) is 60% by mass or more. A resin composition comprising (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound and (E) an inorganic filler, Among them, when the non-volatile components in the resin composition are defined as 100% by mass, the content of component (C) is 10% by mass or more, The content of (E) component is 60 mass % or more when the non-volatile matter in a resin composition is made into 100 mass %. The resin composition as claimed in item 1 or 7, wherein component (A) has a group represented by formula (a-1):

[wherein, * represents a bonding site]. The resin composition as claimed in item 1 or 7, wherein (A) component has a group shown in formula (A3):

[In the formula, X represents a single bond, -C(R ⁵ ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -, R ² and R ⁵ are each independently representing a hydrogen atom Or hydrocarbon group, R ³ and R ⁴ are independent, representing a hydrocarbon group, at least one of R ² and b R ³ is an allyl group, b and c are independently representing an integer of 0 to 3, * represents a bond part]. The resin composition as claimed in item 1 or 7, wherein the weight average molecular weight of component (A) is 1000~20000. The resin composition as claimed in item 1 or 7, wherein the allyl equivalent of component (A) is 200g/eq.~2000g/eq. The resin composition according to claim 1 or 7, wherein the content of component (A) is 0.01% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition according to claim 1 or 7, wherein the content of component (A) is 5% by mass or less when the non-volatile components in the resin composition are defined as 100% by mass. The resin composition of claim 1 or 7, wherein when the non-volatile components in the resin composition are taken as 100% by mass, the content of component (B) is 1% by mass to 20% by mass. The resin composition according to claim 1 or 7, wherein the mass ratio of (B) component to (A) component ((B) component/(A) component) is 1.5-100. The resin composition according to claim 5 or 7, wherein the component (E) is silicon dioxide. The resin composition according to claim 5 or 7, wherein the content of component (E) is 70% by mass or more when the non-volatile components in the resin composition are defined as 100% by mass. The resin composition according to claim 1 or 7, further comprising an imidazole-based hardening accelerator. The resin composition according to claim 1 or 7, further comprising a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents. The resin composition according to claim 1 or 7, wherein the elongation at break of the cured product of the resin composition is 1.0% or more when measured at 23°C. The resin composition according to claim 1 or 7, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23°C. A cured product of the resin composition as claimed in claim 1 or 7. A sheet-like laminated material containing the resin composition according to claim 1 or 7. A resin sheet having a support and a resin composition layer disposed on the support, the resin composition layer being formed of the resin composition as claimed in claim 1 or 7. A printed wiring board having an insulating layer made of a hardened resin composition according to claim 1 or 7. A semiconductor device comprising the printed wiring board according to claim 25.