JP2024016043A - Curable composition, prepreg, resin sheet, metal foil-clad laminate, and printed wiring board - Google Patents

Abstract

To provide a curable composition that is superior in low thermal expansion and copper foil peel strength, and to also provide a prepreg, a resin sheet, a metal foil-clad laminate and a printed wiring board.SOLUTION: The present invention provides a curable composition that includes an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D, or a curable composition that includes a polymer having these as constituent units.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board.

In recent years, as semiconductor packages widely used in electronic devices, communication equipment, personal computers, etc. have become more sophisticated and smaller, the integration and density of each component for semiconductor packages has accelerated in recent years. are doing. Along with this, various characteristics required of printed wiring boards for semiconductor packages are becoming increasingly strict. Properties required of such a printed wiring board include, for example, low thermal expansion, chemical resistance, and peel strength.

Patent Document 1 states that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in its molecular structure, and a compound having a phenolic hydroxyl group has excellent heat resistance and low thermal expansion. , is disclosed to be suitably used for metal foil-clad laminates and multilayer printed wiring boards.

Patent Document 2 describes an addition polymer of polymaleimide, diglycidyl polysiloxane represented by the following formula (I), diallylbisphenols represented by the following formula (II), and an addition polymer of the following formula (III). A manufacturing method is disclosed in which a resin for semiconductor encapsulation is obtained by reacting the allylated phenol resin shown below in a predetermined ratio and under predetermined conditions. According to this document, the resin for semiconductor encapsulation obtained by the above production method has good compatibility between the polymaleimide and the above addition polymer, and furthermore, It is disclosed that the cured product has excellent properties (for example, high glass transition temperature, moisture resistance, and strength under heat) and is highly reliable as a resin composition for semiconductor encapsulation. This document discloses that in the following formula (III), component b is an important component that reacts with maleimide groups in the resin production reaction with polymaleimide and improves the compatibility between polymaleimide and polysiloxane. ing.

(In the formula, R ¹ represents an alkylene group or a phenylene group, R ² each independently represents an alkyl group or a phenyl group, and n represents an integer from 1 to 100.)

(In the formula, R ⁴ represents an ether bond, a methylene group, a propylidene group, or a direct bond (single bond).)

(In the above formula, a, b, and c each represent the percentage of each composition, and 0<a, b, c<100 and a+b+c=100.)

Japanese Patent Application Publication No. 2012-149154 Japanese Patent Application Publication No. 4-4213

As in Patent Document 1, a resin composition containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound has excellent low thermal expansion. However, the present inventors have found that the resin composition has a problem in moldability due to insufficient compatibility between the silicone compound and the thermosetting resin. Further, the present inventors have found that the above resin composition does not have sufficient metal foil peel strength (for example, copper foil peel strength) when used to form a metal foil-clad laminate.

On the other hand, the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and low thermal expansion and copper foil peel strength, which are required as characteristics of printed wiring boards, have not been studied.

The present invention has been made in view of the above problems, and provides a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board that have excellent low thermal expansion and copper foil peel strength. The purpose is to

The present inventors have made extensive studies to solve the above problems. As a result, a curable composition containing an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and an acid anhydride, or a curable composition containing a polymer having these as constituent units. Specifically, the inventors have discovered that the above problems can be solved, and have completed the present invention.

（式中、Ｒ¹は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ²は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。）
［６］
前記エポキシ化合物Ｃが、下記式（ｂ２）で表される化合物を含有する、上記［１］～［５］のいずれか記載の硬化性組成物。

（式中、Ｒ^aは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。）
［７］
前記エポキシ化合物Ｃの含有量が、前記エポキシ変性シリコーンＢ及び前記エポキシ化合物Ｃの合計量１００質量％に対して、２０～５０質量％である、上記［１］～［６］のいずれか記載の硬化性組成物。
［８］
前記酸無水物Ｄは、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上である、上記［１］～［７］のいずれか記載の硬化性組成物。
［９］
アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位と、を含有する重合体Ｅを含む、硬化性組成物。
［１０］
前記重合体Ｅの重量平均分子量が、３．０×１０³～５．０×１０⁴である、上記［９］に記載の硬化性組成物。
［１１］
前記重合体Ｅ中の前記エポキシ変性シリコーンＢに由来する構成単位の含有量が、前記重合体Ｅの総質量に対して、２０～６０質量％である、上記［９］又は［１０］に記載の硬化性組成物。
［１２］
前記重合体Ｅのアルケニル基当量が、３００～１５００ｇ／ｍｏｌである、上記［９］～［１１］のいずれか記載の硬化性組成物。
［１３］
前記重合体Ｅ中の前記酸無水物Ｄに由来する構成単位の含有量が、前記重合体Ｅの総質量に対して、３～２０質量％である、上記［９］～［１２］のいずれか記載の硬化性組成物。
［１４］
前記重合体Ｅの含有量が、樹脂固形分１００質量％に対して５～５０質量％である、上記［９］～［１３］のいずれか記載の硬化性組成物。
［１５］
前記アルケニルフェノールＡが、ジアリルビスフェノール及び／又はジプロペニルビスフェノールを含有する、上記［９］～［１４］のいずれか記載の硬化性組成物。
［１６］
前記エポキシ変性シリコーンＢが、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーンを含有する、上記［９］～［１５］のいずれか記載の硬化性組成物。
［１７］
前記エポキシ変性シリコーンＢが、下記式（１）で表されるエポキシ変性シリコーンを含有する、上記［９］～［１６］のいずれか記載の硬化性組成物。

（式中、Ｒ¹は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ²は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。）
［１８］
前記エポキシ化合物Ｃが、下記式（ｂ２）で表される化合物を含有する、上記［９］～［１７］のいずれか記載の硬化性組成物。

（式中、Ｒ^aは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。）
［１９］
前記酸無水物Ｄは、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上である、上記［９］～［１８］のいずれか記載の硬化性組成物。
［２０］
さらに、エポキシ化合物Ｃを含み、前記エポキシ化合物Ｃが、下記式（３－３）で表される化合物又は下記式（３－４）で表される化合物を含む、上記［９］～［１９］のいずれか記載の硬化性組成物。

（式中、Ｒ₁₃は、各々独立して、水素原子、炭素数１～３のアルキル基又は炭素数２～３のアルケニル基を表す。）

（式中、Ｒ₁₄は、各々独立して、水素原子、炭素数１～３のアルキル基又は炭素数２～３のアルケニル基を表す。）
［２１］
マレイミド化合物、シアン酸エステル化合物、アルケニルフェノールＡ以外のフェノール化合物Ａ’及びアルケニル置換ナジイミド化合物からなる群より選択される少なくとも１種の化合物Ｆを更に含む、上記［１］～［２０］のいずれか記載の硬化性組成物。
［２２］
前記マレイミド化合物が、ビス（４－マレイミドフェニル）メタン、２，２－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、下記式（３）で表されるマレイミド化合物及び下記式（３’）で表されるマレイミド化合物からなる群より選ばれる少なくとも１種を含む、上記［２１］に記載の硬化性組成物。

（式中、Ｒ₅は、各々独立して、水素原子又はメチル基を表し、ｎ₁は１以上の整数を表す。）

（式（３’）中、Ｒ¹³は各々独立に、水素原子、炭素数１～５のアルキル基、又はフェニル基を示し、ｎ⁴は１以上１０以下の整数を示す。）
［２３］
前記シアン酸エステル化合物が、下記式（４）で表される化合物及び／又は下記式（４）で表される化合物を除く下記式（５）で表される化合物を含む、上記［２１］又は［２２］に記載の硬化性組成物。

（式中、Ｒ₆は、各々独立して、水素原子又はメチル基を示し、ｎ₂は１以上の整数を表す。）

（式中、Ｒ_yaは、各々独立して、炭素数２～８のアルケニル基又は水素原子を表し、Ｒ_ybは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒ_ycは、各々独立して、炭素数４～１２の芳香環を表し、Ｒ_ycは、ベンゼン環と縮合構造を形成してもよく、Ｒ_ycは、存在していてもよく、存在していなくてもよく、Ａ^1aは、各々独立して、炭素数１～６のアルキレン基、炭素数７～１６のアラルキレン基、炭素数６～１０のアリーレン基、フルオレニリデン基、スルホニル基、酸素原子、硫黄原子又は単結合を表し、Ｒ_ycが存在しない場合は、１つのベンゼン環にＲ_ya及び／又はＲ_ybの基を２つ以上有してもよく、ｎは、１～２０の整数を表す。）
［２４］
前記フェノール化合物Ａ’が、下記式（８）で表される化合物を含む、上記［２１］～［２３］のいずれか記載の硬化性組成物。

（式中、Ｒ₇は、各々独立して、水素原子又はメチル基を示し、ｎ₃は１以上の整数を表す。）
［２５］
無機充填材を更に含有し、前記無機充填材の含有量が、樹脂固形分１００質量部に対し５０～１０００質量部である、上記［１］～［２４］のいずれか記載の硬化性組成物。
［２６］
前記無機充填材が、シリカ類、ベーマイト及びアルミナからなる群より選択される１種以上を含む、上記［２５］に記載の硬化性組成物。
［２７］
プリント配線板用である、上記［１］～［２６］のいずれか記載の硬化性組成物。
［２８］
基材と、前記基材に含浸又は塗布された上記［１］～［２７］のいずれか記載の硬化性組成物と、を含む、プリプレグ。
［２９］
支持体と、前記支持体の表面に配置された上記［１］～［２７］のいずれか記載の硬化性組成物と、を含む、レジンシート。
［３０］
上記［２８］に記載のプリプレグ及び上記［２９］に記載のレジンシートからなる群より選択される１種以上を用いて形成された積層体と、
前記積層体の片面又は両面に配置された金属箔と、
を含む、金属箔張積層板。
［３１］
上記［２８］に記載のプリプレグ及び上記［２９］に記載のレジンシートからなる群より選択される１種以上で形成された絶縁層と、
前記絶縁層の表面に形成された導体層と、
を有する、プリント配線板。
［３２］
アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃと、を重合して得られるプレポリマーを得る工程と、
前記プレポリマーに対して酸無水物Ｄを反応させる工程と、
を含む、上記［１］～［２７］のいずれかに記載の硬化性組成物の製造方法。 That is, the present invention is as follows.
[1]
A curable composition containing an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
[2]
The average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3, and the average number of phenol groups per molecule of the epoxy compound C is 1 or more and less than 3. The curable composition according to [1] above, having an average number of epoxy groups of 1 or more and less than 3.
[3]
The curable composition according to [1] or [2] above, wherein the alkenylphenol A contains diallylbisphenol and/or dipropenylbisphenol.
[4]
The curable composition according to any one of [1] to [3] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
[5]
The curable composition according to any one of [1] to [4] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group, R ² each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is , indicates an integer from 0 to 100.)
[6]
The curable composition according to any one of [1] to [5] above, wherein the epoxy compound C contains a compound represented by the following formula (b2).

(In the formula, each R ^a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
[7]
According to any one of [1] to [6] above, the content of the epoxy compound C is 20 to 50% by mass with respect to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C. Curable composition.
[8]
The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of [1] to [7] above.
[9]
Contains a polymer E containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. , curable composition.
[10]
The curable composition according to [9] above, wherein the weight average molecular weight of the polymer E is 3.0×10 ³ to 5.0×10 ⁴ .
[11]
[9] or [10] above, wherein the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass based on the total mass of the polymer E. curable composition.
[12]
The curable composition according to any one of [9] to [11] above, wherein the alkenyl group equivalent of the polymer E is 300 to 1500 g/mol.
[13]
Any of the above [9] to [12], wherein the content of the structural unit derived from the acid anhydride D in the polymer E is 3 to 20% by mass based on the total mass of the polymer E. The curable composition according to.
[14]
The curable composition according to any one of [9] to [13] above, wherein the content of the polymer E is 5 to 50% by mass based on 100% by mass of the resin solid content.
[15]
The curable composition according to any one of [9] to [14] above, wherein the alkenylphenol A contains diallylbisphenol and/or dipropenylbisphenol.
[16]
The curable composition according to any one of [9] to [15] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
[17]
The curable composition according to any one of [9] to [16] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group, R ² each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is , indicates an integer from 0 to 100.)
[18]
The curable composition according to any one of [9] to [17] above, wherein the epoxy compound C contains a compound represented by the following formula (b2).

(In the formula, each R ^a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
[19]
The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of [9] to [18] above.
[20]
Furthermore, the above [9] to [19] contain an epoxy compound C, and the epoxy compound C contains a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4). The curable composition according to any one of the above.

(In the formula, each R ₁₃ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.)

(In the formula, each R ₁₄ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.)
[21]
Any of the above [1] to [20], further comprising at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A' other than alkenylphenol A, and an alkenyl-substituted nadimide compound. The curable composition described.
[22]
The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, The curable composition according to [21] above, containing at least one selected from the group consisting of a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3').

(In the formula, R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)

(In formula (3'), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.)
[23]
[21] above, wherein the cyanate ester compound includes a compound represented by the following formula (4) and/or a compound represented by the following formula (5) excluding the compound represented by the following formula (4); The curable composition according to [22].

(In the formula, R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)

(In the formula, R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R _yb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, R _yc each independently represents an aromatic ring having 4 to 12 carbon atoms, R _yc may form a fused structure with a benzene ring, and R _yc may or may not exist. A ^1a each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, represents a sulfur atom or a single bond; if R _yc is absent, one benzene ring may have two or more R _ya and/or R _yb groups; n represents an integer from 1 to 20; .)
[24]
The curable composition according to any one of [21] to [23] above, wherein the phenol compound A' contains a compound represented by the following formula (8).

(In the formula, R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.)
[25]
The curable composition according to any one of [1] to [24] above, which further contains an inorganic filler, and the content of the inorganic filler is 50 to 1000 parts by mass based on 100 parts by mass of resin solid content. .
[26]
The curable composition according to [25] above, wherein the inorganic filler contains one or more selected from the group consisting of silicas, boehmite, and alumina.
[27]
The curable composition according to any one of [1] to [26] above, which is used for printed wiring boards.
[28]
A prepreg comprising a base material and the curable composition according to any one of [1] to [27] above, which is impregnated or applied to the base material.
[29]
A resin sheet comprising a support and the curable composition according to any one of [1] to [27] above, disposed on the surface of the support.
[30]
A laminate formed using one or more selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above,
A metal foil disposed on one or both sides of the laminate;
including metal foil-clad laminates.
[31]
an insulating layer formed of one or more selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above;
a conductor layer formed on the surface of the insulating layer;
A printed wiring board.
[32]
A step of obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C;
a step of reacting acid anhydride D with the prepolymer;
The method for producing a curable composition according to any one of [1] to [27] above, comprising:

According to the present invention, it is possible to provide a curable composition, prepreg, resin sheet, metal foil-clad laminate, and printed wiring board that have excellent low thermal expansion and copper foil peel strength.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications may be made without departing from the gist thereof. It is possible.

Unless otherwise specified, "resin solid content" as used herein refers to the components of the curable composition of the present embodiment excluding the solvent and filler, and 100 parts by mass of resin solid content means: This means that the total of the components in the curable composition excluding the solvent and filler is 100 parts by mass. Moreover, 100 mass % of resin solid content means that the total of the components excluding the solvent and filler in the curable composition is 100 mass %.

In addition, in the curable composition of the first embodiment described below, "excellent compatibility" refers to a mixture containing alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D ( For example, in the state of varnish), liquid phase separation does not occur.
In addition, in the curable composition of the second embodiment described below, "excellent compatibility" means that liquid phase separation does not occur in a mixture (e.g., varnish) containing the polymer E and other components. Say something.
Due to its excellent compatibility, the curable composition of this embodiment suppresses liquid phase separation during the molding process, making it possible to obtain a molded article with excellent appearance and improve the physical properties of the obtained molded article. They also tend to have excellent directionality. In addition, in this specification, when referring to "the curable composition of the present embodiment", unless otherwise specified, "the curable composition of the first embodiment" and "the curable composition of the second embodiment" are used. It shall include both "things".

[First embodiment: Curable composition]
The curable composition of the first embodiment includes alkenylphenol A, epoxy-modified silicone B, epoxy compound C excluding epoxy-modified silicone B (hereinafter also simply referred to as "epoxy compound C"), and acid anhydride D. Contains. Curable compositions containing these components tend to have better compatibility with thermosetting resins (hereinafter also simply referred to as "thermosetting resins") that do not have sufficient compatibility with epoxy-modified silicone B. Due to this, the curable composition of the first embodiment can exhibit better compatibility and is excellent in low thermal expansion and copper foil peel strength. In addition, when the curable composition is used by reacting (polymerizing) a portion of each of these components, even better compatibility can be developed, and even better low thermal expansion and copper foil peel strength can be developed. (Curable composition of the second embodiment).

[Alkenylphenol A]
Alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. The curable composition of this embodiment can exhibit excellent compatibility by containing alkenylphenol A.

Examples of the alkenyl group include, but are not particularly limited to, alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among these, from the viewpoint of achieving the effects of the present invention more effectively and reliably, the alkenyl group is preferably an allyl group and/or a propenyl group, and more preferably an allyl group. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4. From the viewpoint of achieving the effects of the present invention more effectively and reliably, the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, and more preferably 1. Further, the bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, but it is preferably the ortho position (2, 6 position).

The phenolic aromatic ring refers to one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and examples thereof include a phenol ring and a naphthol ring. The number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, preferably 1.

The phenolic aromatic ring may have a substituent other than an alkenyl group. Examples of such substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, and straight chain alkyl groups having 1 to 10 carbon atoms. Examples include a chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of the substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2. Furthermore, the bonding position of the substituent to the phenolic aromatic ring is also not particularly limited.

Alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of achieving the effects of the present invention more effectively and reliably, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and has two structures. It is preferable.

Alkenylphenol A may be, for example, a compound represented by the following formula (1A) or the following formula (1B).

(In the formula, Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxb each independently represents an alkyl group or hydrogen atom having 1 to 10 carbon atoms, and Rxc each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. represents an aromatic ring having 4 to 12 carbon atoms, Rxc may form a fused structure with a benzene ring, Rxc may or may not be present, and A is Represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), and Rxc is If not present, one benzene ring may have two or more Rxa and/or Rxb groups.)

(In the formula, Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and Rxf represents a carbon number Represents 4 to 12 aromatic rings, Rxf may form a fused structure with a benzene ring, Rxf may or may not exist, and if Rxf does not exist, one The benzene ring may have two or more Rxd and/or Rxe groups.)

In formula (1A) and formula (1B), the alkenyl group having 2 to 8 carbon atoms represented as Rxa and Rxd is not particularly limited, but includes, for example, a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group. etc.

In formulas (1A) and (1B), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, examples include compounds containing a naphthol ring as a phenolic aromatic ring. . Further, in the formula (1A) and the formula (1B), when the groups represented by Rxc and Rxf are not present, examples of the phenolic aromatic ring include a compound containing a phenol ring.

In formula (1A) and formula (1B), the alkyl group having 1 to 10 carbon atoms represented as Rxb and Rxe is not particularly limited, but includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group. , linear alkyl groups such as hexyl group, branched alkyl groups such as isopropyl group, isobutyl group, and tert-butyl group.

In formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include a methylene group, an ethylene group, a trimethylene group, and a propylene group. The aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, but includes, for example, the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ - , or a group represented by the formula: -CH ₂ -Ar-CH ₂ -CH ₂ - (wherein, Ar represents a phenylene group, a naphthylene group, or a biphenylene group), represented as A. The arylene group having 6 to 10 carbon atoms is not particularly limited, but includes, for example, a phenylene ring.

In the compound represented by formula (1B), Rxf is preferably a benzene ring (a compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably achieving the effects of the present invention.

From the viewpoint of further improving compatibility, alkenylphenol A is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenol. From a similar point of view, alkenylbisphenols include diallylbisphenol, in which one allyl group is bonded to each of the two phenolic aromatic rings of bisphenols, and/or one propenyl group is bonded to each of the two phenolic aromatic rings of bisphenols. Dipropenyl bisphenol is preferred.

Diallylbisphenol is not particularly limited, but examples include o,o'-diallylbisphenol A (DABPA, a product of Daiwa Kasei Kogyo Co., Ltd.), o,o'-diallylbisphenol F, and o,o'-diallylbisphenol S. , o,o'-diallylbisphenolfluorene. Dipropenylbisphenol is not particularly limited, but examples include o,o'-dipropenylbisphenol A ("PBA01" manufactured by Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Examples include dipropenylbisphenol S, o,o'-dipropenylbisphenol fluorene.

The average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, and preferably 1.5 or more and 2.5 or less, from the viewpoint of achieving the effects of the present invention more effectively and reliably. More preferred. The average number of phenol groups is calculated by the following formula.

In the formula, Ai represents the number of phenol groups in the alkenylphenol having i phenol groups in the molecule, Xi represents the proportion of the alkenylphenol having i phenol groups in the molecule to the total alkenylphenols, and X ₁ +X ₂ +...X _n =1.

[Epoxy modified silicone B]
Epoxy-modified silicone B is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group. By containing the epoxy-modified silicone B, the curable composition of this embodiment can exhibit excellent low thermal expansion properties and copper foil peel strength.

The silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton in which siloxane bonds are repeatedly formed. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of achieving the effects of the present invention more effectively and reliably.

The epoxy group-containing group is not particularly limited, but includes, for example, a group represented by the following formula (a1).

(In the formula, R ⁰ represents an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms such as a methylene group, ethylene group, or propylene group), and X is a monovalent group represented by the following formula (a2). (represents a monovalent group represented by the following formula (a3))

Epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g/mol. Epoxy-modified silicone B has excellent compatibility with thermosetting resins by containing epoxy-modified silicone having an epoxy equivalent within the above range, and tends to further improve low thermal expansion and copper foil peel strength in a well-balanced manner. It is in. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g/mol, and even more preferably 150 to 240 g/mol.

Epoxy-modified silicone B preferably contains two or more types of epoxy-modified silicone from the viewpoint of having better compatibility with the thermosetting resin and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. In this case, the two or more types of epoxy-modified silicones preferably have different epoxy equivalents, and the epoxy-modified silicone has an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low-equivalent epoxy-modified silicone B1"). and an epoxy modified silicone having an epoxy equivalent of 400 to 4000 g/mol (hereinafter also referred to as "high equivalent epoxy modified silicone B2"), and an epoxy modified silicone having an epoxy equivalent of 140 to 250 g/mol. It is more preferable to contain a modified silicone (low equivalent epoxy modified silicone B1') and an epoxy modified silicone (high equivalent epoxy modified silicone B2') having an epoxy equivalent of 450 to 3000 g/mol.

When epoxy-modified silicone B contains two or more types of epoxy-modified silicone, the average epoxy equivalent of epoxy-modified silicone B is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol, More preferably, it is 300 to 1000 g/mol. The average epoxy equivalent weight is calculated by the following formula.

(In the formula, Ei represents the epoxy equivalent of one type of epoxy-modified silicone among two or more types of epoxy-modified silicone, Wi represents the proportion of the above-mentioned epoxy-modified silicone in epoxy-modified silicone B, and W ₁ +W ₂ +...W _n = 1.)

Epoxy-modified silicone B should contain an epoxy-modified silicone represented by the following formula (1) from the viewpoint of being superior in compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. is preferred.

In formula (1), R ¹ each independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group; R ² each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, n represents an integer from 0 to 100.

In formula (1), the alkylene group represented by R ¹ may be linear, branched, or cyclic. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. Among these, R ¹ is preferably a propylene group.

In formula (1), the arylene group represented by R ¹ may have a substituent. The number of carbon atoms in the arylene group is preferably 6 to 40, more preferably 6 to 20. Examples of the arylene group include a phenylene group, a cyclohexylphenylene group, a hydroxyphenylene group, a cyanophenylene group, a nitrophenylene group, a naphtylene group, a biphenylene group, an anthrylene group, a pyrenylene group, and a fluorenylene group. These groups may contain ether bonds, ketone bonds, or ester bonds.

（式（Ｘ－Ｉ）中、＊は、結合手を表す。） In formula (1), the number of carbon atoms in the aralkylene group represented by R ¹ is preferably 7 to 30, more preferably 7 to 13. Examples of the aralkylene group include a group represented by the following formula (X-I).

(In formula (X-I), * represents a bond.)

In formula (1), the group represented by R ¹ may further have a substituent, and examples of the substituent include a linear alkyl group having 1 to 10 carbon atoms, and a linear alkyl group having 3 to 10 carbon atoms. Branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkoxy groups having 1 to 10 carbon atoms, branched alkoxy groups having 3 to 10 carbon atoms, and cyclic alkoxy groups having 3 to 10 carbon atoms. It will be done. Among these, R ¹ is particularly preferably a propylene group.

In formula (1), each R ² independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. The above alkyl group and phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group. Among these, R ² is preferably a methyl group or a phenyl group.

In formula (1), n represents an integer greater than or equal to 0, and is, for example, 0 to 100. From the viewpoint of having better compatibility with the thermosetting resin and further improving low thermal expansion and copper foil peel strength in a well-balanced manner, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20. It is as follows.

Epoxy-modified silicone B contains two or more types of epoxy-modified silicone represented by formula (1) from the viewpoint of having better compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. It is preferable to contain. In this case, the epoxy-modified silicones containing two or more types preferably have different n values, such as an epoxy-modified silicone in which n is 1 to 2 in formula (1), and an epoxy-modified silicone in which n is 5 to 20 in formula (1). It is more preferable to contain a certain epoxy-modified silicone.

The average number of epoxy groups per molecule of epoxy-modified silicone B is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of achieving the effects of the present invention more effectively and reliably. is more preferable. The average number of epoxy groups is calculated by the following formula.

(In the formula, Bi represents the number of epoxy groups in the epoxy-modified silicone having i epoxy groups in the molecule, and Yi represents the proportion of the epoxy-modified silicone having i epoxy groups in the molecule to the entire epoxy-modified silicone. , and Y ₁ +Y ₂ +...Y _n =1.)

The content of epoxy-modified silicone B should be 5 to 95% by mass based on the total of 100% by mass of epoxy-modified silicone B and epoxy compound C, from the viewpoint of achieving even better low thermal expansion and chemical resistance. The amount is preferably 10 to 90% by weight, more preferably 40 to 85% by weight, and even more preferably 50 to 80% by weight.

As the epoxy-modified silicone B, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "X-22-163" and "KF-105" manufactured by Shin-Etsu Chemical Co., Ltd.

[Epoxy compound C]
Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, and more specifically, it is an epoxy compound that does not have a polysiloxane skeleton. By containing the epoxy compound C, the curable composition of this embodiment can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

The epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy modified silicone B. The epoxy compound C in the curable composition of the present embodiment is typically a bifunctional epoxy compound having two epoxy groups in one molecule or a polyfunctional epoxy compound having three or more epoxy groups in one molecule. can be used. It is preferable that the epoxy compound C contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of exhibiting even more excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

（式（３ａ）中、Ａｒ³は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ⁴は、ベンゼン環、ナフタレン環又はビフェニル環を表し、Ｒ^3aは、各々独立して、水素原子又はメチル基を表し、ｋは１～５０の整数を表し、
ここで、Ａｒ³におけるベンゼン環又はナフタレン環は、さらに一又は複数の置換基を有してもよく、当該置換基は、図示しないグリシジルオキシ基であってもよく、その他の置換基、例えば、炭素数１～５のアルキル基、フェニル基等であってもよく、
Ａｒ⁴におけるベンゼン環、ナフタレン環又はビフェニル環は、さらに一又は複数の置換基を有してもよく、当該置換基は、グリシジルオキシ基であってもよく、その他の置換基、例えば、炭素数１～５のアルキル基、フェニル基等であってもよい。） The epoxy compound C in the curable composition of this embodiment is not particularly limited, but a compound represented by the following formula (3a) can be used.

(In formula (3a), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, and R ^3a each independently represents a hydrogen atom. or represents a methyl group, k represents an integer from 1 to 50,
Here, the benzene ring or naphthalene ring in Ar ³ may further have one or more substituents, and the substituent may be a glycidyloxy group (not shown), and other substituents, such as It may be an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.
The benzene ring, naphthalene ring, or biphenyl ring in Ar ⁴ may further have one or more substituents, and the substituent may be a glycidyloxy group, and other substituents, such as carbon number It may be 1 to 5 alkyl groups, phenyl groups, etc. )

（式（ｂ１）中、Ａｒ³は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ⁴は、ベンゼン環、ナフタレン環又はビフェニル環を表し、Ｒ^3aは、各々独立して、水素原子又はメチル基を表し、
ここで、Ａｒ³におけるベンゼン環又はナフタレン環は、さらに一又は複数の置換基を有してもよく、当該置換基は、例えば、炭素数１～５のアルキル基やフェニル基等のグリシジルオキシ基以外の置換基であってもよく、
Ａｒ⁴におけるベンゼン環、ナフタレン環又はビフェニル環は、さらに一又は複数の置換基を有してもよく、当該置換基は、例えば、炭素数１～５のアルキル基やフェニル基等のグリシジルオキシ基以外の置換基であってもよい。） Among the compounds represented by the above formula (3a), examples of the bifunctional epoxy compound include the compound represented by the following formula (b1).

(In formula (b1), Ar ³ each independently represents a benzene ring or naphthalene ring, Ar ⁴ represents a benzene ring, naphthalene ring or biphenyl ring, and R ^3a each independently represents a hydrogen atom or represents a methyl group,
Here, the benzene ring or naphthalene ring in Ar ³ may further have one or more substituents, such as a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. Substituents other than
The benzene ring, naphthalene ring, or biphenyl ring in Ar ⁴ may further have one or more substituents, and the substituent may be, for example, an alkyl group having 1 to 5 carbon atoms or a glycidyloxy group such as a phenyl group. Substituents other than the above may also be used. )

The compound represented by formula (3a) is preferably a phenolic novolac type epoxy resin in which Ar ⁴ in formula (3a) is substituted with at least a glycidyloxy group. Examples of the phenolic novolac type epoxy resin include, but are not particularly limited to, compounds having a structure represented by the following formula (3-1) (naphthalene skeleton-containing polyfunctional epoxy resin having a naphthalene skeleton), and naphthalene cresol novolac type. Examples include epoxy resins.

（式中、Ａｒ³¹は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ⁴¹は、各々独立して、ベンゼン環、ナフタレン環又はビフェニル環を表し、Ｒ^31aは、各々独立して、水素原子又はメチル基を表し、ｐは１を表し、ｋｚは１～５０の整数を表し、各環は、グリシジルオキシ基以外の置換基（例えば、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基又はフェニル基）を有してもよく、Ａｒ³¹及びＡｒ⁴¹の少なくとも一方はナフタレン環を表す。）

(In the formula, each Ar ³¹ independently represents a benzene ring or a naphthalene ring; each Ar ⁴¹ independently represents a benzene ring, a naphthalene ring, or a biphenyl ring; each R ^31a independently represents a benzene ring, a naphthalene ring, or a biphenyl ring; represents a hydrogen atom or a methyl group, p represents 1, kz represents an integer from 1 to 50, and each ring represents a substituent other than the glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms, a carbon number 1 ~5 alkoxy groups or phenyl groups), and at least one of Ar ³¹ and Ar ⁴¹ represents a naphthalene ring.)

（式中、Ｒは、メチル基を表し、ｋｚは、上記式（３－１）中のｋｚと同義である。） Examples of the compound having the structure represented by formula (3-1) include compounds having the structure represented by formula (3-2).

(In the formula, R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).)

The naphthalene cresol novolac type epoxy resin is not particularly limited, but for example, a cresol/naphthol novolac type epoxy resin represented by the following formula (NE) is preferable. The compound represented by the following formula (NE) is a random copolymer of a constitutional unit of cresol novolac epoxy and a constitutional unit of naphthol novolak epoxy, and both cresol epoxy and naphthol epoxy can be terminal.

m and n in the formula (NE) each represent an integer of 1 or more. The upper limits of m and n and the ratio thereof are not particularly limited, but from the viewpoint of low thermal expansion, m:n (here, m+n=100) is preferably 30 to 50: 70 to 50, and 45 to 55:55-45 is more preferred.

As the naphthalene cresol novolac type epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "NC-7000", "NC-7300", and "NC-7300L" manufactured by Nippon Kayaku Co., Ltd., and "HP-9540" and "HP-9500" manufactured by DIC Corporation. "HP-9540" is particularly preferred.

The compound represented by formula (3a) may be a compound that does not correspond to the above-mentioned phenolic novolac type epoxy resin (hereinafter also referred to as "aralkyl type epoxy resin").
Aralkyl-type epoxy resins include compounds in which Ar ³ is a naphthalene ring and Ar ⁴ is a benzene ring in formula (3a) (also referred to as "naphthol aralkyl-type epoxy resin"), and compounds in which Ar 3 in formula (3a) is a naphthalene ring and Ar ⁴ is a benzene ring. A compound in which Ar ⁴ is a benzene ring and Ar 4 is a biphenyl ring (also referred to as a "biphenylaralkyl epoxy resin") is preferred, and a biphenylaralkyl epoxy resin is more preferred.

As the naphthol aralkyl epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Examples of commercially available products include "HP-5000" and "HP-9900" manufactured by DIC Corporation, and "ESN-375" and "ESN-475" manufactured by Nippon Steel Chemical Corporation.

（式中、ｋａは、１以上の整数を表し、１～２０が好ましく、１～６がより好ましい。） The biphenylaralkyl epoxy resin is preferably a compound represented by the following formula (3b).

(In the formula, ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.)

Among the compounds represented by the above formula (3b), examples of the bifunctional epoxy compound include a compound in which ka is 1 in the formula (3b).

As the biphenylaralkyl epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Examples of commercially available products include "NC-3000", "NC-3000L", and "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.

Further, as the epoxy compound C in the curable composition of the present embodiment, it is preferable to use a naphthalene type epoxy resin (excluding those corresponding to the compound represented by formula (3a)). As the naphthalene type epoxy resin, a naphthylene ether type epoxy resin is preferable from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

（式中、Ｒ₁₃は、各々独立して、水素原子、炭素数１～３のアルキル基（例えば、メチル基又はエチル基）、又は炭素数２～３のアルケニル基（例えば、ビニル基、アリル基又はプロペニル基）を表す。）

（式中、Ｒ₁₄は、各々独立して、水素原子、炭素数１～３のアルキル基（例えば、メチル基又はエチル基）、又は炭素数２～３のアルケニル基（例えば、ビニル基、アリル基又はプロペニル基）を表す。） Naphthylene ether type epoxy resin is a bifunctional epoxy compound represented by the following formula (3-3) or the following formula (3) from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. A polyfunctional epoxy compound represented by -4) or a mixture thereof is preferred.

(In the formula, R ₁₃ is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (for example, a vinyl group, an allyl group). or propenyl group).

(In the formula, R ₁₄ is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (for example, a vinyl group, an allyl group). or propenyl group).

As the naphthylene ether type epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available naphthylene ether type epoxy resins include, for example, "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L", and "EXA-7311L" manufactured by DIC Corporation. EXA7311-G3,” “EXA7311-G4,” “EXA-7311G4S,” and “EXA-7311G5,” with HP-6000 being particularly preferred.

（式（ｂ３）中、Ｒ^3bは、各々独立して、水素原子、炭素数１～５のアルキル基（例えば、メチル基又はエチル基）、アラルキル基、ベンジル基、ナフチル基、少なくとも１つのグリシジルオキシ基を含有するナフチル基又は少なくとも１つのグリシジルオキシ基を含有するナフチルメチル基を表し、ｎは、０以上の整数（例えば、０～２）を表す。） Examples of naphthalene type epoxy resins other than those mentioned above include, but are not limited to, compounds represented by the following formula (b3).

(In formula (b3), R ^3b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or at least one glycidyl group. Represents a naphthyl group containing an oxy group or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer of 0 or more (for example, 0 to 2).)

Commercial products of the compound represented by the above formula (b3) include, for example, "HP-4032" (n=0 in the above formula (b3)), "HP-4710" (n = 0 in the above formula (b3)) manufactured by DIC Corporation; ), n=0 and R ^3b is a naphthylmethyl group containing at least one glycidyloxy group).

（式（ｂ２）中、Ｒａは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。） Moreover, as the epoxy compound C in the curable composition of the present embodiment, it is preferable to use a biphenyl type epoxy compound (excluding those corresponding to the above-mentioned epoxy compound C).
The biphenyl-type epoxy compound is not particularly limited, but includes, for example, a compound represented by the following formula (b2) (compound b2).

(In formula (b2), each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

In formula (b2), the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group.

When the biphenyl-type epoxy compound is compound b2, the biphenyl-type epoxy compound may be in the form of a mixture of compounds b2 having different numbers of Ra, which are alkyl groups. Specifically, it is preferable to use a mixture of biphenyl-type epoxy compounds having different numbers of Ra, which are alkyl groups, and a compound b2 in which the number of Ra, which is an alkyl group, is 0, and a compound b2, in which the number of Ra, which is an alkyl group, is 4. More preferably, it is a mixture of compound b2.

（式中、Ｒ^3cは、各々独立し、水素原子又は炭素数１～５のアルキル基を表し、ｋ２は、０～１０の整数を表す。） Further, as the epoxy compound C in the curable composition of the present embodiment, a dicyclopentadiene type epoxy resin (excluding those corresponding to the above-mentioned epoxy compound C) can be used.
The dicyclopentadiene type epoxy resin is not particularly limited, but includes, for example, a compound represented by the following formula (3-5).

(In the formula, R ^3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.)

（式（ｂ４）中、Ｒ^3cは、各々独立し、水素原子又は炭素数１～５のアルキル基（例えば、メチル基又はエチル基）を表す。） The compound represented by the above formula (3-5) is not particularly limited, but may be, for example, a compound represented by the following formula (b4).

(In formula (b4), each R ^3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).)

As the dicyclopentadiene type epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available dicyclopentadiene type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", and "EPICRON HP-7000HH" manufactured by Dainippon Ink and Chemicals Co., Ltd. Can be mentioned.

Among these, epoxy compound C is suitable for the epoxy compound represented by formula (3a), naphthalene type epoxy resin, and biphenyl from the viewpoint of achieving even better heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. It is preferable that the epoxy compound represented by formula (3a) is one or more selected from the group consisting of naphthalene-type epoxy compounds; It is preferable that an ether type epoxy resin is included.

The epoxy compound C may contain other epoxy compounds that do not correspond to the epoxy compounds described above.
Examples of other epoxy compounds include, but are not limited to, bisphenol-type epoxy resins, trisphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, and fluorene-type epoxy resins. Examples include resins, epoxy resins consisting of bisphenol A type structural units and hydrocarbon structural units, and the like.
Among the other epoxy compounds mentioned above, from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, bisphenol-type epoxy resins can be included; as bisphenol-type epoxy resins, For example, diallyl bisphenol type epoxy resins (eg, diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.) can be used.

As the epoxy compound C, one type of the above-mentioned epoxy compounds and epoxy resins may be used alone or two or more types may be used in combination.

（上記式中、Ｃｉは、分子中にｉ個のエポキシ基を有するエポキシ化合物のエポキシ基数を表し、Ｚｉは、分子中にｉ個のエポキシ基を有するエポキシ化合物のエポキシ化合物全体に占める割合を表し、Ｚ₁＋Ｚ₂＋…Ｚ_n＝１である。） The average number of epoxy groups per molecule of the epoxy compound C is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of achieving the effects of this embodiment more effectively and reliably. is more preferable. The average number of epoxy groups is calculated by the following formula.

(In the above formula, Ci represents the number of epoxy groups in the epoxy compound having i epoxy groups in the molecule, and Zi represents the proportion of the epoxy compound having i epoxy groups in the molecule to the total epoxy compound. , Z ₁ +Z ₂ +...Z _n =1.)

The content of epoxy compound C is determined based on 100% by mass of the total amount of epoxy-modified silicone B and epoxy compound C, from the viewpoint of achieving even better heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. It is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 15 to 60% by weight, and particularly preferably 20 to 50% by weight.

[Acid anhydride D]
The curable composition of this embodiment contains acid anhydride D. The acid anhydride D reacts with the terminal hydroxyl group or epoxy group generated by the reaction of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C other than the epoxy-modified silicone B, and generates a terminal carboxyl group. This results in the presence of a large number of carboxyl groups that are highly reactive with the thermosetting resin, improving compatibility and crosslinking density, and improving low thermal expansion.

The acid anhydride D is not particularly limited, as long as it has a cyclic structure, and preferably has 4 to 20 carbon atoms, since it tends to have better compatibility with thermosetting resins. acid anhydrides, more preferably acid anhydrides having 4 to 16 carbon atoms, still more preferably acid anhydrides having 4 to 10 carbon atoms.

As the acid anhydride D, for example, one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. Among them, phthalic anhydride and succinic anhydride are more preferable from the viewpoint of having better compatibility with the thermosetting resin and further improving low thermal expansion and copper foil peel strength in a well-balanced manner.

The content of acid anhydride D is set to 0.0% based on 100% by mass of the resin solid content, from the viewpoint of having better compatibility with the thermosetting resin and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. It is preferably 8 to 15% by weight, more preferably 0.9 to 10% by weight, and even more preferably 1 to 5% by weight.

[Compound F]
The curable composition of this embodiment contains a maleimide compound, a cyanate ester compound, and a phenol compound A other than the alkenylphenol A from the viewpoint of further improving heat resistance, chemical resistance, low thermal expansion property, and copper foil peel strength. ' and alkenyl-substituted nadimide compounds. Compound F is not particularly limited, but is preferably bifunctional or more, and may be trifunctional or more polyfunctional.

The content of compound F in the curable composition of the present embodiment is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on 100% by mass of the resin solid content. It is preferably 30 to 50% by mass, and more preferably 30 to 50% by mass.

（式（３）中、Ｒ₅は、各々独立して、水素原子又はメチル基を表し、ｎ₁は１以上の整数を表す。） (maleimide compound)
As compound F, it is preferable to contain a maleimide compound from the viewpoint of further improving low thermal expansion property and copper foil peel strength. Maleimide compounds are not particularly limited as long as they have one or more maleimide groups in one molecule, but examples include monomaleimide compounds having one maleimide group in one molecule (for example, N-phenylmaleimide, N-phenylmaleimide, -hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}) propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, maleimide compound represented by the following formula (3), the following Examples include maleimide compounds represented by formula (3'), prepolymers of these maleimide compounds and amine compounds, and the like.

(In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)

n ₁ is 1 or more, preferably 1-100, more preferably 1-10.

(式（３’）中、Ｒ¹³は各々独立に、水素原子、炭素数１～５のアルキル基、又はフェニル基を示し、ｎ⁴は１以上１０以下の整数を示す。）

(In formula (3'), each R ¹³ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.)

These maleimide compounds may be used alone or in combination of two or more. Among these, maleimide compounds include bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}, from the viewpoint of further improving low thermal expansion and copper foil peel strength. At least one member selected from the group consisting of propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by formula (3), and a maleimide compound represented by formula (3') It is preferable to include.

As the maleimide compound, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" manufactured by K.I. Kasei Co., Ltd.; "BMI-3000" and "BMI -4000'', ``BMI-5100'', ``BMI-7000'', ``BMI-2300'', ``MIR-3000-70MT'' manufactured by Nippon Kayaku Co., Ltd. (all R ¹³ in formula (3') are hydrogen atoms) and n ⁴ is a mixture of 1 to 10).

The content of the maleimide compound is preferably 1 to 50 parts by mass, and 5 to 40 parts by mass, based on 100 parts by mass of resin solid content, from the viewpoint of further improving low thermal expansion and copper foil peel strength. is more preferable, and even more preferably 10 to 40 parts by mass.

（式（４）中、Ｒ₆は、各々独立して、水素原子又はメチル基を示し、ｎ₂は１以上の整数を表す。）

（式（５）中、Ｒｙａは、各々独立して、炭素数２～８のアルケニル基又は水素原子を表し、Ｒｙｂは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒｙｃは、各々独立して、炭素数４～１２の芳香環を表し、Ｒｙｃは、ベンゼン環と縮合構造を形成してもよく、Ｒｙｃは、存在していてもよく、存在していなくてもよく、Ａ^1aは、各々独立して、炭素数１～６のアルキレン基、炭素数７～１６のアラルキレン基、炭素数６～１０のアリーレン基、フルオレニリデン基、スルホニル基、酸素原子、硫黄原子又は直接結合（単結合）を表し、Ｒｙｃが存在しない場合は、１つのベンゼン環にＲｙａ及び／又はＲｙｂの基を２つ以上有してもよい。ｎは、１～２０の整数を表す。） (Cyanate ester compound)
The compound F preferably contains a cyanate ester compound from the viewpoint of further improving low thermal expansion and copper foil peel strength. The cyanate ester compound is not particularly limited as long as it has two or more cyanate groups (cyanate ester groups) in one molecule, but for example, naphthol aralkyl compounds such as the compound represented by the following formula (4) type cyanate ester compounds, novolak type cyanate ester compounds such as compounds represented by the following formula (5) excluding compounds represented by formula (4), biphenylaralkyl type cyanate esters, diallylbisphere type cyanate esters Compound, bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5- Tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanato Naphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone , 2,2-bis(4-cyanatophenyl)propane. These cyanate ester compounds may be used alone or in combination of two or more. In this embodiment, from the viewpoint of heat resistance, low thermal expansion property, and copper foil peel strength, the cyanate ester compound is a polyfunctional cyanate ester such as a naphthol aralkyl cyanate ester compound and/or a novolac type cyanate ester compound. Preferably, it contains a compound.

(In formula (4), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)

(In formula (5), Rya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and Ryb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. , Ryc each independently represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a fused structure with a benzene ring, and Ryc may be present or absent. Each A ^1a independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom. Alternatively, it represents a direct bond (single bond), and if Ryc is not present, one benzene ring may have two or more Rya and/or Ryb groups. n represents an integer of 1 to 20. )

Among these, the cyanate ester compound preferably contains a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion property, and copper foil peel strength.

In formula (4), n ₂ represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.

In formula (5), the alkenyl group having 2 to 8 carbon atoms represented as Rya is not particularly limited, and examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and the like.

In formula (5), the alkyl group having 1 to 10 carbon atoms represented as Ryb is not particularly limited, but includes straight chain groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. branched alkyl groups; examples include branched alkyl groups such as isopropyl, isobutyl, and tert-butyl groups.

In formula (5), the alkylene group having 1 to 6 carbon atoms represented by A ^1a is not particularly limited, but includes a methylene group, an ethylene group, a trimethylene group, and a propylene group. Further, in formula (5), the aralkylene group having 7 to 16 carbon atoms represented as A ^1a is not particularly limited, but includes, for example, the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or a group represented by the formula: -CH ₂ -Ar-CH ₂ -CH ₂ - (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group) can be mentioned. Further, the arylene group having 6 to 10 carbon atoms represented by A ^1a is not particularly limited, but includes, for example, a phenylene ring.

In formula (5), n represents an integer of 1 to 20, preferably an integer of 1 to 15, and more preferably an integer of 1 to 10.

（式（ｃ１）中、Ｒｘは、各々独立して、水素原子又はメチル基を表し、Ｒは、各々独立して、炭素数２～８のアルケニル基、炭素数１～１０のアルキル基又は水素原子を表し、ｎは、１～１０の整数を表す。） The compound represented by formula (5) is preferably a compound represented by formula (c1) below.

(In formula (c1), Rx each independently represents a hydrogen atom or a methyl group, and R each independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or hydrogen represents an atom, and n represents an integer from 1 to 10.)

These cyanate ester compounds may be produced according to known methods. Specific manufacturing methods include, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052 to 0057).

The content of the cyanate ester compound as compound F is preferably 10 to 70 parts by mass based on 100 parts by mass of the resin solid content, from the viewpoint of further improving low thermal expansion and copper foil peel strength. , more preferably 10 to 60 parts by weight, and even more preferably 10 to 40 parts by weight.

(Phenol compound A' other than alkenylphenol A)
As the compound F, a phenol compound A' other than alkenylphenol A can be contained from the viewpoint of developing even more excellent copper foil peel strength. The phenol compound A' is not particularly limited, but includes bisphenol type phenol resins (e.g., bisphenol A type resin, bisphenol E type resin, bisphenol F type resin, bisphenol S type resin, etc.), phenolic novolak resins (e.g., phenol (novolac resin, naphthol novolac resin, cresol novolac resin, etc.), glycidyl ester type phenolic resin, naphthalene type phenolic resin, anthracene type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenol resin, aralkyl type phenol resin, phenol-modified aromatic hydrocarbon formaldehyde resin, fluorene type phenol resin and the like. These phenol compounds may be used alone or in combination of two or more.

Among these, the phenol compound A' preferably contains a bifunctional phenol compound having two phenolic hydroxyl groups in one molecule, from the viewpoint of achieving even better compatibility and copper foil peel strength.

Examples of bifunctional phenol compounds include, but are not limited to, bisphenol, biscresol, bisphenols having a fluorene skeleton (for example, bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton, etc.), biphenols (for example, p, p'- biphenol, etc.), dihydroxydiphenyl ether (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (e.g., 4,4'-dihydroxydiphenylketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide) etc.), dihydroxyarenes (eg, hydroquinone, etc.). These bifunctional phenol compounds may be used alone or in combination of two or more. Among these, it is preferable that the bifunctional phenol compound contains at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton, from the viewpoint of achieving even better copper foil peel strength. . From the same viewpoint as above, biscresol fluorene is preferable as the bisphenol having a fluorene skeleton.

Examples of the aralkyl-type phenol resin include a compound represented by the following formula (c2).

(In the formula, Ar ¹ each independently represents a benzene ring or a naphthalene ring, Ar ² represents a benzene ring, a naphthalene ring, or a biphenyl ring, and R ^2a each independently represents a hydrogen atom or a methyl (m represents an integer of 1 to 50, and each ring may have a substituent other than a hydroxyl group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group, etc.)

From the viewpoint of further improving copper foil peel strength, the compound represented by formula (c2) is a compound in which Ar ¹ is a naphthalene ring and Ar ² is a benzene ring (hereinafter referred to as "naphthol aralkyl"). ), and a compound in formula (c2), in which Ar ¹ is a benzene ring and Ar ² is a biphenyl ring (hereinafter also referred to as a "biphenylaralkyl phenol resin"). preferable.

The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (8).

(In the formula, R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.)

In formula (8), n ₃ represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 6.

The biphenylaralkyl phenol resin is preferably a compound represented by the following formula (2c).

(In the formula, R ^2b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group (preferably a hydrogen atom), and m1 is an integer of 1 to 20 (preferably 1 to 6 ).

The phenolic compound A' preferably contains a compound represented by the above formula (8) from the viewpoint of further improving low thermal expansion and copper foil peel strength.

As the aralkyl type phenol resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercial products of aralkyl-type phenolic resin include "KAYAHARD GPH-65", "KAYAHARD GPH-78", and "KAYAHARD GPH-103" (biphenylaralkyl-type phenolic resin) manufactured by Nippon Kayaku Co., Ltd., Nippon Steel Chemical Co., Ltd. One example is the company's product "SN-495" (naphthol aralkyl phenolic resin).

The content of alkenylphenol A as compound F is 1 part by mass based on 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A' from the viewpoint of achieving even better compatibility. The amount is preferably 50 parts by weight, more preferably 3 to 30 parts by weight, and even more preferably 5 to 20 parts by weight.

The content of epoxy-modified silicone B in the curable composition of this embodiment is determined from the viewpoint of achieving even better low thermal expansion and copper foil peel strength in a well-balanced manner. The amount is preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight, and even more preferably 20 to 55 parts by weight, based on 100 parts by weight of the total amount of the phenol compound A'.

The content of epoxy compound C in the curable composition of the present embodiment is determined from the viewpoint of achieving even better compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. The amount is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, and 15 to 25 parts by weight based on 100 parts by weight of the total amount of silicone B, epoxy compound C, and phenol compound A'. Parts by weight are more preferably parts by weight.

The content of phenolic compound A' in the curable composition of this embodiment is determined by the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A' from the viewpoint of developing even more excellent copper foil peel strength. Based on 100 parts by weight, the amount is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, and even more preferably 15 to 20 parts by weight.

In addition, when the curable composition does not contain phenolic compound A', the respective contents of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C mentioned above are the same as those of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C. The content is expressed based on 100 parts by mass of the total amount.

（式（２ｄ）中、Ｒ₁は、各々独立して、水素原子、又は炭素数１～６のアルキル基（例えば、メチル基又はエチル基）を表し、Ｒ₂は、炭素数１～６のアルキレン基、フェニレン基、ビフェニレン基、ナフチレン基、又は下記式（６）若しくは下記式（７）で表される基を表す。）

（式（６）中、Ｒ₃は、メチレン基、イソプロピリデン基、ＣＯ、Ｏ、Ｓ又はＳＯ₂を表す。）

（式（７）中、Ｒ₄は、各々独立して、炭素数１～４のアルキレン基、又は炭素数５～８のシクロアルキレン基を表す。） (Alkenyl-substituted nadimide compound)
From the viewpoint of further improving heat resistance, the compound F preferably contains an alkenyl-substituted nadimide compound. The alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in one molecule, and examples thereof include a compound represented by the following formula (2d).

(In formula (2d), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group or an ethyl group), and R ₂ represents a Represents an alkylene group, phenylene group, biphenylene group, naphthylene group, or a group represented by the following formula (6) or the following formula (7).)

(In formula (6), R ₃ represents a methylene group, an isopropylidene group, CO, O, S or SO _2. )

(In formula (7), each R ₄ independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

As the alkenyl-substituted nadimide compound represented by formula (2d), a commercially available product may be used, or a product manufactured according to a known method may be used. Commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

From the viewpoint of improving heat resistance, the content of the alkenyl-substituted nadimide compound as compound F is preferably 1 to 40 parts by mass, and preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content. The amount is more preferably 10 to 30 parts by mass.

[Second embodiment: curable composition]
The curable composition of the second embodiment includes a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C other than the epoxy-modified silicone B, and an acid Contains a polymer E containing a structural unit derived from anhydride D. Alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D are as described above. Hereinafter, a polymer E containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D will be described. The curable resin composition of the second embodiment containing the above is distinguished from the curable composition of the first embodiment described above, which does not contain the polymer E.

Polymer E can exhibit sufficient compatibility even when mixed with a thermosetting resin that has poor compatibility with silicone compounds. Thereby, the curable composition containing the polymer E and the thermosetting resin can provide a uniform varnish or cured product. In a cured product such as a prepreg obtained using the curable composition, each component is uniformly dissolved, and variations in physical properties due to non-uniformity of the components are suppressed.

The curable composition of the second embodiment contains, in addition to the polymer E, one or more selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D. Good too. In this case, alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D contained in the curable composition of the second embodiment may be unreacted components remaining after polymerization of polymer E. However, it may be a component newly added to the synthesized polymer E.

In addition to the polymer E, the curable composition of the second embodiment also contains, if necessary, the above-mentioned maleimide compound, cyanate ester compound, phenol compound A' other than the alkenylphenol A, and alkenyl-substituted nadimide. It may further contain Compound F, which is at least one selected from the group consisting of compounds. Compound F may be an unreacted component remaining after polymerization of polymer E, or may be a component newly added to synthesized polymer E.

[Polymer E]
Polymer E contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D, If necessary, it further contains a structural unit derived from at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A' other than the alkenylphenol A, and an alkenyl-substituted nadimide compound. You can. When polymer E has a structural unit derived from compound F, compound F is preferably a bifunctional compound. In addition, in this specification, "constituent unit derived from alkenylphenol A", "constituent unit derived from epoxy modified silicone B", "constituent unit derived from epoxy compound C", "constituent unit derived from acid anhydride D""unit" and "constituent unit derived from compound F" refer to a constituent unit obtained by polymerizing each component of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and compound F in polymer E. In addition to this, it also includes structural units formed by reactions etc. that can yield similar structural units. Hereinafter, each constituent unit will also be referred to as constituent units A, B, C, D, and F, respectively. By using Polymer E, the curable composition of the second embodiment has even better compatibility, and has better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. Excellent.

The weight average molecular weight of the polymer E is preferably 3.0×10 ³ to 5.0×10 ⁴ , and 3.0×10 ³ to 2.0×10 in terms of polystyrene in gel permeation chromatography. More preferably, it is ⁴ . By having a weight average molecular weight of 3.0×10 ³ or more, the curable composition of the second embodiment has even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. There is a tendency for this to occur. By having a weight average molecular weight of 5.0×10 ⁴ or less, the curable composition of the second embodiment tends to exhibit even better compatibility.

The content of the structural unit A in the polymer E is preferably 5 to 50% by mass based on the total mass of the polymer E. When the content of the structural unit A is within the above range, the curable composition of the second embodiment tends to exhibit even better compatibility. From the same viewpoint, the content of the structural unit A is more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass.

The content of the structural unit B in the polymer E is preferably 20 to 60% by mass based on the total mass of the polymer E. When the content of the structural unit B is within the above range, the curable composition of the second embodiment tends to be able to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner. From the same viewpoint, the content of structural unit B is more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.

Structural unit B consists of an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (low equivalent epoxy modified silicone B1) and an epoxy modified silicone having an epoxy equivalent of 400 to 4000 g/mol (high equivalent epoxy modified silicone B2). It is preferable that the structural unit derived from the Low equivalent epoxy modified silicone B1 and high equivalent epoxy modified silicone B2 are respectively epoxy modified silicone having an epoxy equivalent of 140 to 250 g/mol (low equivalent epoxy modified silicone B1') and epoxy modified silicone having an epoxy equivalent of 450 to 3000 g/mol. More preferably, it is an epoxy-modified silicone (high equivalent epoxy-modified silicone B2').

The content of the structural unit B1 derived from the low equivalent epoxy-modified silicone B1 in the polymer E is preferably 5 to 25% by mass, and 7.5 to 20% by mass, based on the total mass of the polymer E. More preferably, it is 10 to 17% by mass.

The content of the structural unit B2 derived from the high equivalent epoxy-modified silicone B2 in the polymer E is preferably 15 to 55% by mass, and 20 to 52.5% by mass, based on the total mass of the polymer E. It is more preferable that the amount is 25 to 50% by mass.

The mass ratio of the content of the structural unit B2 to the content of the structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and 1.9 to 3.1. It is more preferable that Since the contents of the structural unit B1 and the structural unit B2 have the above relationship, the curable composition of the second embodiment tends to have further improved low thermal expansion properties and copper foil peel strength.

The structural unit C in the polymer E includes a compound represented by the above formula (b1), a compound represented by the above formula (b2), a compound represented by the above formula (b3), and a compound represented by the above formula (b4). It is preferable that the unit is derived from at least one type selected from the group consisting of the represented compounds.

The content of the structural unit C in the polymer E is preferably 5 to 40% by mass based on the total mass of the polymer E. When the content of the structural unit C is within the above range, the curable composition of the second embodiment has even better compatibility, and has even better heat resistance, chemical resistance, low thermal expansion, and copper foil. It tends to be able to exhibit peel strength and insulation reliability. From the same viewpoint, the content of the structural unit C is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.

Further, the content of the structural unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 15 to 60% by mass, based on the total mass of the structural units B and C. It is more preferably 20 to 50% by weight, particularly preferably 20 to 50% by weight. Because the contents of the structural unit B and the structural unit C have the above relationship, the curable composition of the second embodiment has even better compatibility, has heat resistance, chemical resistance, low thermal expansion, and copper. There is a tendency for foil peel strength and insulation reliability to further improve.

The content of the structural unit D in the polymer E is preferably 3 to 20% by mass based on the total mass of the polymer E. When the content of the structural unit D is within the above range, the curable composition of the second embodiment tends to be able to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner. From the same viewpoint, the content of the structural unit D is more preferably 5 to 15% by mass, and even more preferably 5 to 10% by mass.

When polymer E has a structural unit derived from compound F, the content of structural unit F in polymer E is preferably 3 to 40% by mass based on the total mass of polymer E. By having the content of the structural unit F within the above range, the curable composition of the second embodiment exhibits even more excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. It tends to be possible. From the same viewpoint, the content of structural unit F is preferably 5 to 35% by mass, more preferably 10 to 30% by mass.

When the polymer E has a structural unit derived from a phenolic compound A' other than alkenylphenol A (hereinafter also referred to as "structural unit A'"), the content of the structural unit A' in the polymer E is The amount is preferably 5 to 30% by mass based on the total mass of E. By having the content of the structural unit A' within the above range, the curable composition of the second embodiment has even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. There is a tendency for this to occur. From the same viewpoint, the content of the structural unit A' is preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass.

The alkenyl group equivalent in polymer E is preferably 300 to 1500 g/mol. By having an alkenyl group equivalent of 300 g/mol or more, the cured product of the curable composition of the second embodiment tends to have a further lower elastic modulus, and as a result, the elasticity of the cured product tends to be lower. This tends to further reduce the coefficient of thermal expansion. When the alkenyl group equivalent is 1500 g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability of the curable composition of the second embodiment tend to be further improved. It is in. From the same viewpoint, the alkenyl group equivalent is preferably 350 to 1200 g/mol, more preferably 400 to 1000 g/mol.

The content of polymer E in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, based on 100% by mass of resin solids. , more preferably 15 to 40% by mass. When the content is within the above range, the curable composition has better compatibility and tends to exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.

Polymer E is produced by, for example, a step of reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and optionally compound F in the presence of polymerization catalyst G. can get. The reaction may be performed in the presence of an organic solvent.
More specifically, in the above step, an addition reaction between an epoxy group possessed by epoxy-modified silicone B and epoxy compound C and a hydroxyl group possessed by alkenylphenol A, and an addition reaction between the hydroxyl group possessed by the obtained addition reaction product and epoxy-modified silicone B and After the addition reaction with the epoxy group of the epoxy compound C proceeds, the addition reaction between the terminal hydroxyl group and the epoxy group and the acid anhydride D further proceeds, whereby the polymer E can be obtained.

The method for producing the curable composition of this embodiment (especially the curable composition of the second embodiment) is as follows:
obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C;
a step of reacting acid anhydride D with the prepolymer;
It is preferable to include.
After producing a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C, this prepolymer is reacted with acid anhydride D to improve low thermal expansion and copper foil. A curable composition with even better peel strength tends to be obtained.

[Polymerization catalyst G]
The polymerization catalyst G is not particularly limited, and examples include one or more of imidazole compounds and organic phosphorus compounds. These catalysts may be used alone or in combination of two or more. Among these, imidazole compounds are preferred.

The imidazole compound is not particularly limited, and examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] Imidazoles such as benzimidazole ("TBZ", a product of Shikoku Kasei Kogyo Co., Ltd.) and 2,4,5-triphenylimidazole ("TPIZ", a product of Tokyo Kasei Kogyo Co., Ltd.). Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferred from the viewpoint of preventing homopolymerization of the epoxy component.

The amount of polymerization catalyst G (preferably imidazole compound) used is not particularly limited, and for example, based on 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D and compound F, The amount is 0.1 to 10 parts by mass. From the viewpoint of increasing the weight average molecular weight of the polymer E, the amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.

[Organic solvent]
The organic solvent is not particularly limited, and for example, a polar solvent or a nonpolar solvent can be used. Polar solvents are not particularly limited, but include, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate, and acetic acid. Examples include ester solvents such as butyl, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide. Examples of the nonpolar solvent include, but are not particularly limited to, aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass based on 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and compound F. .

The reaction temperature is not particularly limited, and may be, for example, 100 to 170°C. The reaction time is also not particularly limited, and may be, for example, 3 to 8 hours.

After the reaction in this step is completed, polymer E may be separated and purified from the reaction mixture by a conventional method.

As described above, in addition to polymer E, the curable composition of the second embodiment may further contain compound F, if necessary. By further containing compound F in addition to polymer E, the curable composition of the second embodiment tends to further improve heat resistance, chemical resistance, low thermal expansion property, and copper foil peel strength. .

When the curable composition of the second embodiment contains the polymer E and the compound F, the content of the polymer E in the curable composition of the second embodiment is 100% by mass in total of the polymer E and the compound F. On the other hand, it is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass. When the content is within the above range, the curable composition has better compatibility and tends to exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.

When the curable composition of the second embodiment contains the polymer E and the compound F, the content of the compound F in the curable composition of the second embodiment is based on the total of 100% by mass of the polymer E and the compound F. The amount is preferably 20 to 80% by weight, more preferably 35 to 75% by weight, and even more preferably 45 to 65% by weight.

The curable composition in this embodiment may further contain other resins as long as they do not impede the effects of this embodiment. Examples of other resins include oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins may be used alone or in combination of two or more.

Examples of the oxetane resin include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3 '-Di(trifluoromethyl) perfluoroxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, "OXT-101" and "OXT-121" manufactured by Toagosei Co., Ltd. etc.

The term "benzoxazine compound" as used herein refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of the benzoxazine compound include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" manufactured by Konishi Chemical Co., Ltd.

Examples of compounds having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl ( Monovalent meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Or (meth)acrylates of polyhydric alcohols; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin, and the like.

[Inorganic filler]
The curable composition in this embodiment preferably further contains an inorganic filler from the viewpoint of further improving low thermal expansion. Inorganic fillers are not particularly limited, and include, for example, silicas, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), and metal nitrides. metal sulfides (e.g., barium sulfate, etc.), metal hydroxides (e.g., aluminum hydroxide, aluminum hydroxide heat-treated products (e.g., (aluminum hydroxide heat-treated to reduce some of the crystallization water), boehmite, magnesium hydroxide, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), zinc compounds (e.g., zinc borate, zinc stannate, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass , M-glass G20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass. These inorganic fillers may be used alone or in combination of two or more. Among these, the inorganic filler is preferably at least one selected from the group consisting of silicas, metal hydroxides, and metal oxides, from the viewpoint of further improving low thermal expansion properties, and silicas, boehmite, etc. and alumina, and more preferably silicas.

Examples of silicas include natural silica, fused silica, synthetic silica, Aerosil, hollow silica, and the like. These silicas may be used alone or in combination of two or more. Among these, from the viewpoint of dispersibility, fused silica is preferable, and from the viewpoint of filling property and fluidity, two or more types of fused silica having different particle sizes are more preferable.

The content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving low thermal expansion. , more preferably 100 to 300 parts by mass.

[Silane coupling agent]
The curable composition of this embodiment may further contain a silane coupling agent. By containing the silane coupling agent, the curable composition of this embodiment further improves the dispersibility of the inorganic filler, and the composition of the curable composition of this embodiment and the base material described below can be further improved. There is a tendency for adhesive strength to be further improved.

Silane coupling agents are not particularly limited, and include silane coupling agents that are generally used for surface treatment of inorganic materials, such as aminosilane compounds (for example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl) -γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (eg, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds, phenylsilane compounds, and the like. The silane coupling agents may be used alone or in combination of two or more. Among these, the silane coupling agent is preferably an epoxysilane compound. Examples of the epoxysilane compound include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by weight based on 100 parts by weight of the resin solid content.

[Wetting and dispersing agent]
The curable composition of this embodiment may further contain a wetting and dispersing agent. When the curable composition contains a wetting and dispersing agent, the dispersibility of the filler tends to be further improved.

The wetting and dispersing agent may be any known dispersing agent (dispersion stabilizer) used for dispersing fillers, such as DISPER BYK-110, 111, 118, 180 manufactured by BYK Chemie Japan Co., Ltd. 161, BYK-W996, W9010, W903, etc.

The content of the wetting and dispersing agent is not particularly limited, but it is preferably 0.5 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of resin solid content.

[solvent]
The curable composition of this embodiment may further contain a solvent. By including the solvent in the curable composition of this embodiment, the viscosity at the time of preparation of the curable composition is reduced, the handling property is further improved, and the impregnating property into the base material is further improved. There is a tendency to

The solvent is not particularly limited as long as it can dissolve some or all of the components in the curable composition, but examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), amides (for example, dimethyl formaldehyde, etc.), propylene glycol monomethyl ether, and its acetate. These solvents may be used alone or in combination of two or more.

The method for producing the curable composition of the present embodiment is not particularly limited, and includes, for example, a method of blending the above-mentioned components in a solvent all at once or sequentially and stirring the mixture. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading treatments are used.

[Application]
As described above, the curable composition of this embodiment has excellent compatibility and can exhibit even more excellent low thermal expansion and copper foil peel strength. Therefore, the curable composition of this embodiment is suitably used for metal foil-clad laminates and printed wiring boards. That is, the curable composition of this embodiment can be suitably used as a curable composition for printed wiring boards.

Note that, especially in the above-mentioned applications, the curable composition of the second embodiment includes at least an epoxy compound C (epoxy compound C existing separately from the structural unit C in the polymer E) in addition to the polymer E. is preferred.
In this case, the polymer E preferably has a unit derived from the above-mentioned bifunctional epoxy compound as a unit derived from the epoxy compound C, and more preferably has a unit derived from the above-mentioned biphenyl-type epoxy compound. , more preferably a compound b2 having a unit derived from the compound represented by the above formula (b2) (compound b2), and even more preferably the number of R ^a is 0, and the number of R ^a being an alkyl group is 4 (commercially available products include, for example, the trade name "YL-6121HA" manufactured by Mitsubishi Chemical Corporation).
In addition, as the epoxy compound C that exists separately from the structural unit C in the polymer E, the above-mentioned naphthylene ether type epoxy resin (commercially available products include, for example, "HP-6000" manufactured by DIC Corporation) and It is preferable to include/or a naphthalene cresol novolac type epoxy resin (commercially available products include, for example, "HP-9540" manufactured by DIC Corporation).

[Prepreg]
The prepreg of this embodiment includes a base material and the curable composition of this embodiment impregnated or applied to the base material. As mentioned above, the prepreg may be a prepreg obtained by a known method. Specifically, after impregnating or applying the curable composition of the present embodiment onto a base material, the prepreg is heated under conditions of 100 to 200°C. It is obtained by semi-curing (B-staged) by heating and drying.

The prepreg of this embodiment also includes the form of a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.

The content of the curable composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and even more preferably 40% by volume based on the total amount of prepreg. ~80% by volume. When the content of the curable composition is within the above range, moldability tends to be further improved. Note that the calculation of the content of the curable composition herein also includes the cured product of the curable composition of this embodiment. Furthermore, the solid content of the prepreg referred to herein refers to components obtained by removing the solvent from the prepreg, and for example, the filler is included in the solid content of the prepreg.

The base material is not particularly limited, and includes, for example, known base materials used as materials for various printed wiring boards. Specific examples of the base material include glass base materials, inorganic base materials other than glass (for example, inorganic base materials composed of inorganic fibers other than glass such as quartz), and organic base materials (for example, fully aromatic polyamides, polyesters, etc.). , polyparaphenylenebenzoxazole, an organic base material composed of organic fibers such as polyimide), and the like. These base materials may be used alone or in combination of two or more. Among these, glass substrates are preferred from the viewpoint of superior heating dimensional stability.

Examples of the fibers constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among these, the fibers constituting the glass base material are selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of superior strength and low water absorption. It is preferable that one or more types of fibers are selected from the above.

The form of the base material is not particularly limited, but examples include forms such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. The method of weaving the woven fabric is not particularly limited, but for example, plain weaving, Nanako weaving, twill weaving, etc. are known, and the weaving method can be appropriately selected from these known methods depending on the intended use and performance. . Furthermore, glass woven fabrics subjected to fiber opening treatment or surface treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but those having a thickness of about 0.01 to 0.1 mm are usually suitably used.

[Resin sheet]
The resin sheet of this embodiment includes a support and the curable composition of this embodiment disposed on the surface of the support. The resin sheet of this embodiment may be formed, for example, by applying the curable composition of this embodiment to one or both sides of a support. The resin sheet of this embodiment can be manufactured by, for example, directly applying a curable composition used for prepreg or the like onto a support such as a metal foil or a film, and drying the composition.

The support is not particularly limited, but for example, known supports used in various printed wiring board materials can be used, and a resin sheet or metal foil is preferable. Examples of the resin sheet and metal foil include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, and polyethylene (PE) film; and metal foils such as aluminum foil, copper foil, and gold foil. Among these, electrolytic copper foil and PET film are preferable for the support.

The resin sheet of this embodiment can be obtained, for example, by applying the curable composition of this embodiment onto a support and then semi-curing (B-staged). Generally, the method for manufacturing the resin sheet of this embodiment is preferably a method for manufacturing a composite of a B-stage resin and a support. Specifically, for example, the curable composition is applied to a support such as copper foil, and then semi-cured by heating for 1 to 60 minutes in a dryer at 100 to 200°C to form a resin sheet. Examples include manufacturing methods. The amount of the curable composition adhered to the support is preferably in the range of 1.0 μm or more and 300 μm or less in terms of the resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a build-up material for printed wiring boards.

[Metal foil laminate]
The metal foil-clad laminate of this embodiment includes a laminate formed using one or more selected from the group consisting of the prepreg and resin sheet of this embodiment, and a laminate disposed on one or both sides of the laminate. Including metal foil. The laminate may be formed from one prepreg or resin sheet, or may be formed from a plurality of prepregs and/or resin sheets.

The metal foil (conductor layer) may be any metal foil used for various printed wiring board materials, such as copper, aluminum, etc. metal foil, and examples of copper metal foil include rolled copper foil, electrolytic copper foil, etc. Examples include copper foil such as foil. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

The method and conditions for forming the metal foil-clad laminate are not particularly limited, and methods and conditions for general printed wiring board laminates and multilayer boards can be applied. For example, when forming a laminate (the above-mentioned laminate) or a metal foil-clad laminate, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used. In addition, when forming a laminate (the above-mentioned laminate) or a metal foil-clad laminate (laminate molding), the temperature is 100 to 300°C, the pressure is 2 to 100 kgf/cm ² , and the heating time is 0.05 to 5. Time ranges are common. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300°C. Particularly when using a multi-stage press machine, from the viewpoint of sufficiently accelerating the curing of the prepreg, the temperature is preferably 200°C to 250°C, the pressure 10 to 40 kgf/cm ² , the heating time 80 minutes to 130 minutes, and the temperature 215°C to More preferably, the temperature is 235° C., the pressure is 25 to 35 kgf/cm ² , and the heating time is 90 to 120 minutes. Moreover, it is also possible to form a multilayer board by laminating and molding a combination of the above-mentioned prepreg and a separately prepared inner layer wiring board.

[Printed wiring board]
The printed wiring board of this embodiment includes an insulating layer formed of one or more selected from the group consisting of the prepreg and resin sheet of this embodiment, and a conductor layer formed on the surface of the insulating layer. . The printed wiring board of this embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of this embodiment into a predetermined wiring pattern to form a conductor layer.

Specifically, the printed wiring board of this embodiment can be manufactured, for example, by the following method. First, the metal foil-clad laminate of this embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to create an inner layer board having a conductor layer (inner layer circuit). Next, a predetermined number of insulating layers and metal foil for the outer layer circuit are laminated in this order on the conductor layer (interior circuit) surface of the inner layer board, and are integrally formed (laminated) by heating and pressing. Obtain a laminate. The lamination molding method and the molding conditions are the same as the lamination molding method and molding conditions for the above-mentioned laminate plate and metal foil clad laminate. Next, the laminate is drilled for through holes and via holes, and a plating metal film is applied to the walls of the holes thus formed to provide electrical continuity between the conductor layer (inner circuit) and the metal foil for the outer layer circuit. form. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to create an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is manufactured in this way.

Furthermore, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductive layer that will become a circuit on the insulating layer. At this time, an electroless plating method can also be used to form the conductor layer.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
In a three-necked flask equipped with a thermometer and a Dimroth, 5.0 parts by mass of diallyl bisphenol A (DABPA, Daiwa Kasei Kogyo Co., Ltd.), 5.5 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), and epoxy. Modified silicone compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g/eq.) 4.1 parts by mass, epoxy-modified silicone compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional Base equivalent: 500 g/eq.) 8.4 parts by mass, 5.5 parts by mass of biphenyl-type epoxy compound A (YL-6121HA, Mitsubishi Chemical Corporation), propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan) as a solvent. 30.0 parts by mass of Co., Ltd. was added, and the mixture was heated and stirred at 120° C. in an oil bath. After confirming that the raw material was dissolved in the solvent, 0.3 parts by mass of imidazole catalyst A (TBZ, Shikoku Kasei Kogyo Co., Ltd.) was added and the temperature was raised to 140°C, stirred for 5 hours, and cooled to form a phenoxy polymer solution. (solid content 50% by mass) was obtained (polymer production step). Note that diallylbisphenol A corresponds to "alkenylphenol A," epoxy-modified silicone compound A and epoxy-modified silicone compound B correspond to "epoxy-modified silicone B," and biphenyl-type epoxy compound A corresponds to "epoxy compound C." ”. The phenoxy polymer solution contained a polymer containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C.

After heating this phenoxy polymer solution to 100°C in an oil bath, 1.5 parts by mass of succinic anhydride was added as acid anhydride D, stirred for 2 hours, and after cooling, the modified phenoxy polymer solution (solid content 50 parts by mass) was added. %) was obtained (polymer modification step). The modified phenoxy polymer solution contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. It contained a polymer that The polymer modification step can also be performed continuously with the polymer production step.

[Method for measuring weight average molecular weight Mw]
The weight average molecular weight Mw of the modified phenoxy polymer obtained as described above was measured as follows. Analysis was performed by injecting 20 μL of a solution in which 0.5 g of the modified phenoxy polymer solution was dissolved in 2 g of THF into a high performance liquid chromatography device (manufactured by Shimadzu Corporation, pump: LC-20AD). The columns are Showa Denko's Shodex GPC KF-804 (length 30 cm x inner diameter 8 mm), Shodex GPC KF-803 (length 30 cm x inner diameter 8 mm), Shodex GPC KF-802 (length 30 cm x inner diameter 8 mm), Shodex GPC A total of four bottles of KF-801 (length 30 cm x inner diameter 8 mm) were used, THF (solvent) was used as the mobile phase, the flow rate was 1 mL/min, and RID-10A was used as the detector. The weight average molecular weight Mw was determined by GPC method using standard polystyrene as a standard substance.
The weight average molecular weight Mw of the modified phenoxy polymer measured as described above was 12,000.

To this modified phenoxy polymer solution, 25 parts by mass of a naphthol aralkyl type phenol compound (SN-495V, Nippon Steel Chemical & Materials Co., Ltd.), 9 parts by mass of a novolac type maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd.), Phenylene ether type maleimide compound (BMI-80, Daiwa Kasei Kogyo Co., Ltd.) 9 parts by weight, naphthylene ether type epoxy compound (HP-6000, DIC Corporation) 27 parts by weight, spherical silica (SC-2050MB, Admatex) Co., Ltd.), 1 part by weight of a wetting and dispersing agent (DISPERBYK-161, BYK Chemie Japan Co., Ltd.), and 5 parts by weight of a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.). A varnish was obtained (varnish production process). This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), and heated and dried at 150°C for 3 minutes to form a prepreg with a curable composition solid content (including filler) of 58.2% by volume. (prepreg manufacturing process).

(Example 2)
In the polymer production step, the amount of diallyl bisphenol A added is 5.0 parts by mass to 4.7 parts by mass, the amount of biscresol fluorene added is 5.5 parts by mass to 5.2 parts by mass, and the amount of epoxy-modified silicone A is The amount added was 4.1 parts by mass to 3.8 parts by mass, the amount of epoxy modified silicone B added was 8.4 parts by mass to 8.1 parts by mass, and the amount added of biphenyl type epoxy compound A was 5.5 parts by mass. In the same manner as in Example 1, except that the amount of acid anhydride D was changed to 3.0 parts by mass instead of 1.5 parts by mass in the polymer modification step. A prepreg with a curable composition solid content (including filler) of 58.2% by volume was obtained.
The modified phenoxy polymer solution contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. It contained a polymer that
Furthermore, the weight average molecular weight Mw of the modified phenoxy polymer in Example 2, measured by the method described above, was 12,000.

(Example 3)
In the polymer modification step, the solid content of the curable composition was prepared in the same manner as in Example 2, except that the acid anhydride D was replaced with 3.0 parts by mass of phthalic anhydride instead of 3.0 parts by mass of succinic anhydride. A prepreg with a content of 58.2% by volume (including filler) was obtained.
The modified phenoxy polymer solution contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. It contained a polymer that
Furthermore, the weight average molecular weight Mw of the modified phenoxy polymer in Example 3, measured by the method described above, was 12,000.

(Comparative example 1)
In the polymer production step, the amount of diallyl bisphenol A added is 5.0 parts by mass to 5.3 parts by mass, the amount of biscresol fluorene added is 5.5 parts by mass to 5.8 parts by mass, and the amount of epoxy-modified silicone A is The amount added was 4.1 parts by mass to 4.4 parts by mass, the amount of epoxy-modified silicone B added was 8.4 parts by mass to 8.7 parts by mass, and the amount added of biphenyl-type epoxy compound A was 5.5 parts by mass. The resin composition solid content ( A prepreg with a content of 58.2% by volume (including filler) was obtained.
The weight average molecular weight Mw of the phenoxy polymer in Comparative Example 1, measured by the method described above, was 12,000.

Two sheets of prepreg obtained in Examples 1 to 3 and Comparative Example 1 were stacked, and electrolytic copper foil (3EC-M2S-VLP, manufactured by Mitsui Mining & Mining Co., Ltd.) with a thickness of 12 μm was placed on top and bottom. Then, lamination molding was performed for 120 minutes at a pressure of 30 kgf/cm ² and a temperature of 220° C. to obtain a copper foil-clad laminate including an insulating layer having a thickness of 0.2 mm as a metal foil-clad laminate. The properties of the obtained copper foil-clad laminate were evaluated by the method shown below. The evaluation results are shown in Table 1.

[Copper foil peel strength]
Using the copper foil-clad laminate (10 mm x 150 mm x 0.2 m) obtained by the above method, the copper foil peel strength (unit: kN/m) was measured according to JIS C6481.

[Coefficient of linear thermal expansion (CTE)]
The longitudinal linear thermal expansion coefficient of the glass cloth was measured for the insulating layer of the laminate. Specifically, after removing the copper foil on both sides of the copper foil-clad laminate (10 mm x 6 mm x 0.2 mm) obtained by the above method by etching, it was heated in a constant temperature bath at 220 ° C. for 2 hours and molded. The stress caused by this was removed. Thereafter, the temperature was raised from 40°C to 320°C at a rate of 10°C per minute using a coefficient of thermal expansion measuring device (horizontal dilatometer manufactured by Linseis), and the coefficient of linear thermal expansion (CTE) from 60°C to 260°C (unit: ppm/°C) was measured.

As shown in Table 1 above, the copper foil-clad laminates (Examples 1 to 3) using the curable composition of the present embodiment had excellent low thermal expansion and copper foil peel strength.

This application is based on a Japanese patent application (Japanese Patent Application No. 2021-128743) filed with the Japan Patent Office on August 5, 2021, the contents of which are incorporated herein by reference.

Claims (34)

A curable composition containing an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D. The average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3, and the average number of phenol groups per molecule of the epoxy compound C is 1 or more and less than 3. The curable composition according to claim 1, wherein the average number of epoxy groups is 1 or more and less than 3. The curable composition according to claim 1 or 2, wherein the alkenylphenol A contains diallylbisphenol and/or dipropenylbisphenol. The curable composition according to claim 1 or 2, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. The curable composition according to claim 1 or 2, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group, R ² each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is , indicates an integer from 0 to 100.) The curable composition according to claim 1 or 2, wherein the epoxy compound C contains a compound represented by the following formula (b2).

(In the formula, each R ^a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.) The curable composition according to claim 1, wherein the content of the epoxy compound C is 20 to 50% by mass based on 100% by mass of the epoxy-modified silicone B and the epoxy compound C. The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , The curable composition according to claim 1 or 2. Contains a polymer E containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. , curable composition. The curable composition according to claim 9, wherein the weight average molecular weight of the polymer E is 3.0×10 ³ to 5.0×10 ⁴ . Curable according to claim 9 or 10, wherein the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass based on the total mass of the polymer E. Composition. The curable composition according to claim 9 or 10, wherein the alkenyl group equivalent of the polymer E is 300 to 1500 g/mol. Curable according to claim 9 or 10, wherein the content of the structural unit derived from the acid anhydride D in the polymer E is 3 to 20% by mass based on the total mass of the polymer E. Composition. The curable composition according to claim 9 or 10, wherein the content of the polymer E is 5 to 50% by mass based on 100% by mass of the resin solid content. The curable composition according to claim 9 or 10, wherein the alkenylphenol A contains diallylbisphenol and/or dipropenylbisphenol. The curable composition according to claim 9 or 10, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. The curable composition according to claim 9 or 10, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group, or an aralkylene group, R ² each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is , indicates an integer from 0 to 100.) The curable composition according to claim 9 or 10, wherein the epoxy compound C contains a compound represented by the following formula (b2).

(In the formula, each R ^a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.) The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , The curable composition according to claim 9 or 10. The epoxy compound C according to claim 9 or 10, further comprising an epoxy compound C, wherein the epoxy compound C includes a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4). Curable composition.

(In the formula, each R ₁₃ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.)

(In the formula, each R ₁₄ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.) The curable composition according to claim 1 or 9, further comprising at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A' other than alkenylphenol A, and an alkenyl-substituted nadimide compound. thing. The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, The curable composition according to claim 21, comprising at least one selected from the group consisting of a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3').

(In the formula, R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)

(In formula (3'), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.) 22. The cyanate ester compound includes a compound represented by the following formula (4) and/or a compound represented by the following formula (5) excluding the compound represented by the following formula (4). curable composition.

(In the formula, R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)

(In the formula, R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R _yb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, R _yc each independently represents an aromatic ring having 4 to 12 carbon atoms, R _yc may form a fused structure with a benzene ring, and R _yc may or may not exist. A ^1a each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, represents a sulfur atom or a single bond; if R _yc is absent, one benzene ring may have two or more R _ya and/or R _yb groups; n represents an integer from 1 to 20; .) The curable composition according to claim 21, wherein the phenol compound A' contains a compound represented by the following formula (8).

(In the formula, R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.) The curable composition according to claim 1, further comprising an inorganic filler, and the content of the inorganic filler is 50 to 1000 parts by mass based on 100 parts by mass of the resin solid content. The curable composition according to claim 25, wherein the inorganic filler contains one or more selected from the group consisting of silicas, boehmite, and alumina. The curable composition according to claim 1 or 9, which is used for printed wiring boards. A prepreg comprising a base material and the curable composition according to claim 1 or 9 impregnated or applied to the base material. A resin sheet comprising a support and the curable composition according to claim 1 disposed on the surface of the support. A laminate formed using the prepreg according to claim 28,
A metal foil disposed on one or both sides of the laminate;
including metal foil-clad laminates. A laminate formed using the resin sheet according to claim 29,
A metal foil disposed on one or both sides of the laminate;
including metal foil-clad laminates. An insulating layer formed using the prepreg according to claim 28,
a conductor layer formed on the surface of the insulating layer;
A printed wiring board. An insulating layer formed using the resin sheet according to claim 29,
a conductor layer formed on the surface of the insulating layer;
A printed wiring board. A step of obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C;
a step of reacting acid anhydride D with the prepolymer;
A method for producing a curable composition according to claim 1 or 9, comprising: