JP2023088477A - Curable resin composition - Google Patents

Abstract

To provide a curable resin composition which enables production of a uniformly cured product and satisfies all of a sufficient Tg, low dielectric characteristics, copper foil adhesiveness, and a low linear expansion coefficient of the cured product.SOLUTION: A curable resin composition contains (A) modified polyphenylene ether having a vinylsilyl group represented by formula (1), and (B) an acrylic or methacrylic crosslinking assistant which has a molecular weight of 400 or less and three or less of the total number of acrylic groups or methacrylic groups in one molecule. In the formula (1), Z is an a-valent partial structure, a represents an integer of 2 to 6, Y is each independently a divalent connection group, n represents a repeating number of Y and is each independently an integer of 0 to 200, at least one n in a pieces of (-Yn-A) is an integer of 1 or more, and A represents a hydrogen atom, or a silyl group-containing derivative which can be bonded to a polyphenylene ether structure, except in the case where all of them are hydrogen atoms.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition.

Polyphenylene ether has excellent high-frequency characteristics, flame retardancy, and heat resistance, and is therefore widely used as a material in the fields of electrical/electronics, automobiles, and various other industrial materials. In recent years, it has been expected that polyphenylene ether, which has a much lower molecular weight than ordinary high-molecular-weight polyphenylene ether, is effective for electronic material applications such as substrate materials. For this reason, Patent Document 1 proposes a low-molecular-weight polyphenylene ether having a lower dielectric value than a general high-molecular-weight polyphenylene ether using 2,6-dimethylphenol as a raw material, and an efficient method for producing the same.

On the other hand, when polyphenylene ether is used as a molding material such as a substrate material, it is required not only to have excellent dielectric properties, but also to have excellent heat resistance, moldability, and the like. However, conventional polyphenylene ethers are thermoplastic, and in some cases sufficient heat resistance cannot be obtained. For this reason, it has been proposed to use a polyphenylene ether to which a thermosetting resin such as an epoxy resin is added, or to use a modified polyphenylene ether.

Patent Document 2 discloses a modified polyphenylene ether having a predetermined polyphenylene ether portion in its molecular structure and having at least one p-vinylbenzyl group, m-vinylbenzyl group or the like at the molecular end. Compounds are described.

Further, Patent Documents 3 and 4, for example, describe a modified polymer having a polyphenylene ether moiety in its molecular structure and a methacrylic group at the molecular end. In particular, methacrylic group modification has become a technique that is being widely used because the reactivity of the methacrylic group as a cross-linking group is moderately high and the introduction method to the terminal hydroxyl group is easy. Furthermore, an example in which a vinylsilyl group is introduced as a modifying group at the end of a molecule for the purpose of improving dielectric properties has been reported (for example, Patent Document 5).

Further, as disclosed in Patent Document 2, in order to easily ensure the heat resistance of the terminal-modified thermosetting polyphenylene ether, the thermosetting polyphenylene ether and other copolymerizable monomers (crosslinking It is effective to polymerize the auxiliary agent) to increase the crosslink density. As the cross-linking aid, as described in Patent Document 2, it is preferable to use trialkenyl isocyanurate from the viewpoint of compatibility, and among them, triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC) are preferred. It has been known.

JP-A-2004-99824 Japanese Patent Application Laid-Open No. 2004-339328 Japanese Patent Publication No. 2004-502849 Japanese Patent Publication No. 2010-538114 Chinese Patent Application Publication No. 106916293

Of the above polymers, methacrylic group modification is currently widely used, but since the modified polyphenylene ether has an ester bond at the terminal, the dipole moment of the bond increases, resulting in a decrease in the dielectric constant and the dielectric constant. Tangent tends to be higher. Furthermore, when polyphenylene ether is made to have a branched polymer structure in order to reduce the viscosity of the solution, the number of terminal groups per molecule increases compared to the linear polymer, which reduces the dielectric properties and leads to the next generation There are many problems as a low dielectric material.

On the other hand, a polymer having a vinylbenzyl group at its end has a problem that the reactivity of the vinyl group is too high, so that the final drying of the polymer after synthesis cannot be performed under normal conditions, and the polymer can only be handled in the form of a solution. be. In addition, although the polymer having a vinylbenzyl group has a smaller dipole moment at the bonding portion, there is also the problem that the adhesiveness to the copper foil is also lowered.

As a method of improving these, there is a method of introducing a vinylsilyl group or the like having low polarity and good metal adhesion into a polymer (for example, Patent Document 5). It was confirmed that when a cross-linking aid was used, the compatibility was poor, the reactivity was low, and it was difficult to obtain a uniform cured product.

As described above, a curable resin composition containing a terminally modified polyphenylene ether having a vinylsilyl group at the end and a cross-linking aid provides a uniform cured product, and the cured product has sufficient Tg, low dielectric properties, copper The current situation is that a curable resin composition that satisfies both foil adhesion and a low coefficient of linear expansion has not yet been obtained.

The present invention is a curable resin composition containing a terminal-modified polyphenylene ether having a vinylsilyl group at the end and a cross-linking aid, a uniform cured product can be obtained, the cured product has sufficient Tg, low dielectric properties, copper foil An object of the present invention is to provide a curable resin composition that satisfies both adhesiveness and a low coefficient of linear expansion.

｛式（１）中、Ｚは、下記式（２）で表されるａ価の部分構造であり、ａは２～６の整数を表し、Ｙは、各々独立に、下記式（４）で表される構造を有する２価の連結基であり、ｎは、Ｙの繰り返し数を表し、各々独立に、０～２００の整数であり、ａ個の（－Ｙ_ｎ－Ａ）中の少なくとも１つのｎは、１以上の整数であり、Ａは、全て水素原子の場合を除いて、水素原子、又はポリフェニレンエーテル構造と結合可能なシリル基含有誘導体を表し、

式（２）中、Ｘは、ａ価の任意の連結基であり、複数のＲ^５は、各々独立に、炭素数１～８の直鎖状アルキル基及び下記式（３）で表される部分構造のいずれかであり、ｋは、各々独立に、１～４の整数であり、

式（３）中、複数のＲ^１１は、各々独立に、置換されていてもよい炭素数１～８のアルキル基であり、複数のＲ^１２は、各々独立に、置換されていてもよい炭素数１～８のアルキレン基であり、ｂは、各々独立に、０又は１であり、Ｒ^１３は、水素原子、置換されていてもよい炭素数１～８のアルキル基、又は置換されていてもよいフェニル基のいずれかを表し、

式（４）中、複数のＲ^２１は、各々独立に、水素原子、置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基、及びハロゲン原子のいずれかであり、２つのＲ^２１は、同時に水素原子ではなく、２つのＲ^２１は、一方が上記式（３）で表される部分構造、もう一方が水素原子、メチル基又はエチル基のいずれかである組み合わせではなく、複数のＲ^２２は、各々独立に、水素原子、置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基、及びハロゲン原子のいずれかである｝
（Ｂ）分子量が４００以下であり、１分子内のアクリル基またはメタクリル基の合計数が３個以下のアクリル系またはメタクリル系架橋助剤
［２］
（Ｃ）開始剤をさらに含む、［１］に記載の硬化性樹脂組成物。
［３］
前記式（２）中、前記Ｒ^５のうち少なくとも１つは、前記式（３）で表される部分構造であり、前記式（２）中の－Ｏ－が結合するベンゼン環の炭素原子を１位としたとき、２位又は６位の一方の炭素原子に前記式（３）で表される部分構造を有するＲ^５が結合し、２位又は６位の他方の炭素原子に水素原子、メチル基又はエチル基が結合している、［１］又は［２］に記載の硬化性樹脂組成物。
［４］
前記式（３）で表される部分構造が、ｔｅｒｔ－ブチル基である、［３］に記載の硬化性樹脂組成物。
［５］
前記ポリフェニレンエーテル中に含まれるＯＨ末端数が、０～３，０００μｍｏｌ／ｇである、［１］～［４］のいずれかに記載の硬化性樹脂組成物。
［６］
前記式（４）のＲ^２１が、メチル基である、［１］～［５］のいずれかに記載の硬化性樹脂組成物。
［７］
前記式（１）のＡが、下記式（５）：

｛式（５）中、複数のＲ^３１、及びＲ^３４は、それぞれ独立に、Ｃ_１～３０の２価の炭化水素基であり、複数のＲ^３２、及びＲ^３３は、それぞれ独立に、Ｃ_１～３０の１価の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基、又はヒドロキシアルキル基であり、Ｂは、オレフィン系の炭素－炭素２重結合を含むＣ_１～３０の炭化水素系置換基であり、その一部が、水素原子、水酸基、アリール基、アルコキシ基、アリロキシ基、アミノ基、ヒドロキシアルキル基、ビニル基、イソプロペニル基、又はハロゲン基に置換されていてもよく、かつｔは、０～８の整数である｝
で表される、［１］～［６］のいずれかに記載の硬化性樹脂組成物。
［８］
前記式（１）のＡが、下記式（６）及び／又は（７）：

｛式（６）及び／又は式（７）中、複数のＲ^３１、及びＲ^３４は、それぞれ独立に、Ｃ_１～３０の２価の炭化水素基であり、複数のＲ^３２、及びＲ^３３は、それぞれ独立に、Ｃ_１～３０の１価の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基、又はヒドロキシアルキル基であり、Ｒ^３５は、それぞれ独立に、水素原子、水酸基、又はＣ_１～３０の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基、ヒドロキシアルキル基、ビニル基、イソプロペニル基、又はハロゲン基であり、Ｒ^３６は、Ｃ_１～３の２価の炭化水素基またはアミノ基、または酸素原子であり、炭化水素基の一部は、アリール基、アルコキシ基、アリロキシ基、アミノ基、ヒドロキシアルキル基、ビニル基、イソプロペニル基、又はハロゲン基に置換されていてよく、かつｓとｔとｕは、それぞれ独立に、０～８の整数である｝
で表される［１］～［７］のいずれかに記載の硬化性樹脂組成物。
［９］
前記（Ｂ）成分がメタクリル酸ジシクロペンタニルまたはアクリル酸ジシクロペンタニルである、［１］～［８］のいずれかに記載の硬化性樹脂組成物。
［１０］
前記（Ｂ）成分がメタクリル酸イソボルニルまたはアクリル酸イソボルニルである、［１］～［８］のいずれかに記載の硬化性樹脂組成物。
［１１］
前記（Ｂ）成分がメタクリル酸ステアリルまたはアクリル酸ステアリルである、［１］～［８］のいずれかに記載の硬化性樹脂組成物。
［１２］
（Ｄ）溶媒をさらに含む、［１］～［１１］のいずれかに記載の硬化性樹脂組成物。 In order to solve the above problems, the present inventors have made intensive studies and found that, in particular, a silicon-containing functional group is used as a modifying group in a branched polyphenylene ether skeleton having a specific structure, and an acrylic resin having a specific structure is used as a cross-linking aid. By adding a cross-linking aid or a methacrylic cross-linking aid, a curable resin composition capable of solving all of the above problems can be obtained, and the present invention has been completed. That is, the present invention is as follows.
[1]
A curable resin composition comprising the following components (A) and (B).
(A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1):

{In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, and each Y is independently represented by the following formula (4). a divalent linking group having the structure shown, n represents the number of repetitions of Y, each independently an integer of 0 to 200, and at least 1 in a (-Y _n -A) Each of n is an integer of 1 or more, and A represents a hydrogen atom or a silyl group-containing derivative capable of bonding with a polyphenylene ether structure, except when all are hydrogen atoms;

In formula (2), X is an a-valent linking group, and a plurality of R ⁵ are each independently represented by a linear alkyl group having 1 to 8 carbon atoms and the following formula (3) any of the partial structures, k is each independently an integer of 1 to 4,

In formula (3), a plurality of R ¹¹ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹² are each independently an optionally substituted carbon an alkylene group having a number of 1 to 8, b is each independently 0 or 1, R ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituted represents either a phenyl group,

In formula (4), a plurality of R ²¹ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom, and two R ²¹ are not hydrogen atoms at the same time, and two R ²¹ are, one of which is a partial structure represented by the above formula (3), and the other is a hydrogen atom, a methyl group, or A plurality of R ²² are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, or an optionally substituted C 6 to 12 aryl groups and halogen atoms}
(B) an acrylic or methacrylic cross-linking aid having a molecular weight of 400 or less and a total number of acrylic or methacrylic groups in one molecule of 3 or less [2]
(C) The curable resin composition according to [1], further comprising an initiator.
[3]
In the formula (2), at least one of the R ⁵ is a partial structure represented by the formula (3), and the carbon atom of the benzene ring to which -O- in the formula (2) is bonded is When the 1-position is used, R ⁵ having the partial structure represented by the formula (3) is bonded to one carbon atom at the 2- or 6-position, and a hydrogen atom is attached to the other carbon atom at the 2- or 6-position, The curable resin composition according to [1] or [2], wherein a methyl group or an ethyl group is bonded.
[4]
The curable resin composition according to [3], wherein the partial structure represented by formula (3) is a tert-butyl group.
[5]
The curable resin composition according to any one of [1] to [4], wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 μmol/g.
[6]
The curable resin composition according to any one of [1] to [5], wherein R ²¹ in formula (4) is a methyl group.
[7]
A in the formula (1) is represented by the following formula (5):

{In the formula (5), the plurality of R ³¹ and R ³⁴ are each independently a C _1-30 divalent hydrocarbon group, and the plurality of R ³² and R ³³ are each independently a C _{1 to 30} monovalent hydrocarbon groups, aryl groups, alkoxy groups, allyloxy groups, amino groups, or hydroxyalkyl groups, and B is a C _{1 to 30} carbon containing an olefinic carbon-carbon double bond a hydrogen-based substituent, a portion of which may be substituted with a hydrogen atom, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group; , and t is an integer from 0 to 8}
Represented by the curable resin composition according to any one of [1] to [6].
[8]
A in the formula (1) is represented by the following formulas (6) and/or (7):

{In formula (6) and/or formula (7), a plurality of R ³¹ and R ³⁴ are each independently a C _1-30 divalent hydrocarbon group, a plurality of R ³² and R ³³ are each independently a C _1-30 monovalent hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group, and each R ³⁵ is each independently a hydrogen atom, a hydroxyl group, or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and R ³⁶ is a C _1-3 divalent is a hydrocarbon group or amino group, or an oxygen atom, and part of the hydrocarbon group is substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. and s, t and u are each independently an integer from 0 to 8}
The curable resin composition according to any one of [1] to [7] represented by
[9]
The curable resin composition according to any one of [1] to [8], wherein the component (B) is dicyclopentanyl methacrylate or dicyclopentanyl acrylate.
[10]
The curable resin composition according to any one of [1] to [8], wherein the component (B) is isobornyl methacrylate or isobornyl acrylate.
[11]
The curable resin composition according to any one of [1] to [8], wherein the component (B) is stearyl methacrylate or stearyl acrylate.
[12]
(D) The curable resin composition according to any one of [1] to [11], further comprising a solvent.

By using a curable resin composition containing (A) a modified polyphenylene ether having a vinylsilyl group and (B) a cross-linking aid defined in the present invention, a uniform cured product is obtained, and the cured product is sufficiently cured. It is possible to provide a curable resin composition that satisfies all of a high Tg, low dielectric properties, copper foil adhesion, and a low coefficient of linear expansion.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The present embodiment is an illustration for explaining the present invention, and the present invention is not limited to only this embodiment, and the present invention can be practiced with appropriate modifications within the scope of the gist thereof.

｛式（１）中、Ｚは、下記式（２）で表されるａ価の部分構造であり、ａは２～６の整数を表し、Ｙは、各々独立に、下記式（４）で表される構造を有する２価の連結基であり、ｎは、Ｙの繰り返し数を表し、各々独立に、０～２００の整数であり、ａ個の（－Ｙ_ｎ－Ａ）中の少なくとも１つのｎは、１以上の整数であり、Ａは、全て水素原子の場合を除いて、水素原子、又はポリフェニレンエーテル構造と結合可能なシリル基含有誘導体を表し、

式（２）中、Ｘは、ａ価の任意の連結基であり、複数のＲ^５は、各々独立に、炭素数１～８の直鎖状アルキル基及び下記式（３）で表される部分構造のいずれかであり、ｋは、各々独立に、１～４の整数であり、

式（３）中、複数のＲ^１１は、各々独立に、置換されていてもよい炭素数１～８のアルキル基であり、複数のＲ^１２は、各々独立に、置換されていてもよい炭素数１～８のアルキレン基であり、ｂは、各々独立に、０又は１であり、Ｒ^１３は、水素原子、置換されていてもよい炭素数１～８のアルキル基、又は置換されていてもよいフェニル基のいずれかを表し、

式（４）中、複数のＲ^２１は、各々独立に、水素原子、置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基、及びハロゲン原子のいずれかであり、２つのＲ^２１は、同時に水素原子ではなく、２つのＲ^２１は、一方が上記式（３）で表される部分構造、もう一方が水素原子、メチル基又はエチル基のいずれかである組み合わせではなく、複数のＲ^２２は、各々独立に、水素原子、置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基、及びハロゲン原子のいずれかである｝
（Ｂ）分子量が４００以下であり、１分子内のアクリル基またはメタクリル基の合計数が３個以下のアクリル系またはメタクリル系架橋助剤 <Curable resin composition>
The curable resin composition of the present embodiment is characterized by containing the following components (A) and (B).
(A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1):

{In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, and each Y is independently represented by the following formula (4). a divalent linking group having the structure shown, n represents the number of repetitions of Y, each independently an integer of 0 to 200, and at least 1 in a (-Y _n -A) Each of n is an integer of 1 or more, and A represents a hydrogen atom or a silyl group-containing derivative capable of bonding with a polyphenylene ether structure, except when all are hydrogen atoms;

In formula (2), X is an a-valent linking group, and a plurality of R ⁵ are each independently represented by a linear alkyl group having 1 to 8 carbon atoms and the following formula (3) any of the partial structures, each k is independently an integer of 1 to 4,

In formula (3), a plurality of R ¹¹ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹² are each independently an optionally substituted carbon an alkylene group having a number of 1 to 8, b is each independently 0 or 1, R ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituted represents any of the phenyl groups,

In formula (4), a plurality of R ²¹ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom, and two R ²¹ are not hydrogen atoms at the same time, and two R ²¹ are, one of which is a partial structure represented by the above formula (3), and the other is a hydrogen atom, a methyl group, or A plurality of R ²² are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, or an optionally substituted C 6 to 12 aryl groups and halogen atoms}
(B) an acrylic or methacrylic cross-linking aid having a molecular weight of 400 or less and a total number of acrylic or methacrylic groups in one molecule of 3 or less;

In the present embodiment, by using a curable resin composition containing (A) a modified polyphenylene ether having a vinylsilyl group and (B) an acrylic cross-linking aid or a methacrylic cross-linking aid, a uniform cured product can be obtained. It is possible to provide a curable resin composition that satisfies all of the resulting cured product's sufficient Tg, low dielectric properties, copper foil adhesion, and low coefficient of linear expansion.
The components constituting the curable resin composition of this embodiment will be described in detail below.

式（１）中、Ｚは下記式（２）で表されるａ価の中心フェノール部位を有する部分構造であり、ａは３～６の整数である。 <(A) Modified polyphenylene ether>
The modified polyphenylene ether according to this embodiment has a structure represented by the following formula (1).

In formula (1), Z is a partial structure having an a-valent central phenol moiety represented by the following formula (2), and a is an integer of 3-6.

The above-mentioned "central phenol site" means a central skeleton that serves as a reaction starting point when polymerizing a polyfunctional polyphenylene ether, and a polyfunctional modified polyphenylene ether composition is analyzed by nuclear magnetic resonance (NMR), mass spectrometry, or the like. The structure can be identified by analysis. As a specific method for identifying the structure of the central phenol site from the polyfunctional modified polyphenylene ether composition, for example, only low molecular weight components are analyzed from the mass spectrometry results of the polyfunctional modified polyphenylene ether composition, and electric shock or electric ionization ( EI), in which the structure of the central phenol site is estimated from the fragment ion peak. Furthermore, there is a method of estimating the structure of the central phenol site by performing NMR measurement of the polyfunctional modified polyphenylene ether composition and comparing it with the NMR measurement results of known polyfunctional phenol compounds. By combining this mass spectrometry result and NMR measurement result, it becomes possible to more accurately identify the structure of the central phenol site.

式（２）中、ａとしては、式（１）と同様の２～６の整数が挙げられ、式（１）と同じ整数であることが好ましい。式（２）の中心フェノール部位において、ａ個の各部分構造は、同じ構造であってもよいし、異なっていてもよい。 In the modified polyphenylene ether, a partial structure (e.g., phenol optionally substituted with R ⁵ etc.) is bonded to the a-valent center X, and the a-valent partial structure (i.e., the following formula (2) It may be a structure in which (-Y _n -A) of formula (1) is bound to the central phenol site represented by ).

In formula (2), a is the same integer of 2 to 6 as in formula (1), preferably the same integer as in formula (1). In the central phenol site of formula (2), the a partial structures may have the same structure or different structures.

In formula (2), X is any a-valent linking group, which is not particularly limited, but is selected from, for example, hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; nitrogen, phosphorus, silicon and oxygen; atoms such as nitrogen, phosphorus, silicon, etc.; or groups combining these; and the like. X may be a linking group other than a single bond.

X in formula (2) may be a linking group that links the a-valent partial structures to each other.

In formula (2), X is an a-valent alkyl skeleton bonded to the benzene ring to ^which R ⁵ is bonded via a single bond, an ester bond, or the like; an a-valent aryl skeleton bonded to the benzene ring to which is bonded; an a-valent heterocyclic skeleton bonded to the benzene ring to which R ⁵ is bonded via a single bond or an ester bond;

Here, the alkyl skeleton is not particularly limited, but for example, a branched chain hydrocarbon having at least a carbon atoms of 1 to 6 (e.g., saturated chain hydrocarbon) branched to the benzene ring of the partial structure Skeletons directly bonded (a branched ends may be bonded with a benzene ring, and there may be branched ends to which no benzene ring is bonded), and the like. In addition, the aryl skeleton is not particularly limited, but for example, a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to R ⁵ via a single bond or an alkyl chain. Examples include a skeleton that bonds to a benzene ring that is attached. Furthermore, the heterocyclic skeleton is not particularly limited, but includes, for example, a skeleton in which a triazine ring is bonded to a benzene ring to which ^R5 is bonded via a single bond or an alkyl chain.

A plurality of R ⁵ in formula (2) is each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and k is each Independently an integer from 1 to 4.

式（３）中、
複数のＲ^１１は、各々独立に、置換されていてもよい炭素数１～８のアルキル基であり、
複数のＲ^１２は、各々独立に、置換されていてもよい炭素数１～８のアルキレン基であり、
ｂは、各々独立に、０又は１であり、
Ｒ^１３は、水素原子、置換されていてもよい炭素数１～８のアルキル基、又は置換されていてもよいフェニル基のいずれかを表す。
上記置換基としては、ハロゲン原子等が挙げられる。 R ⁵ in formula (2) is a linear alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, a group having a partial structure represented by the following formula (3), etc. At least one of R ⁵ may be a partial structure represented by the following formula (3).

In formula (3),
a plurality of R ¹¹ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms,
a plurality of R ¹² are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms,
b are each independently 0 or 1,
R ¹³ represents either a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group.
A halogen atom etc. are mentioned as said substituent.

The partial structure represented by formula (3) is preferably a group containing secondary and/or tertiary carbon atoms, such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and tert-amyl group. , 2-dimethylpropyl group, or a structure having a phenyl group at the end thereof, and the like, and more preferably a tert-butyl group.

In this embodiment, when the carbon atom of the benzene ring to which -O- in formula (2) is bonded is the 1st position, the partial structure represented by formula (3) is at one of the carbon atoms at the 2nd or 6th position. is bonded, and ^a hydrogen atom, a methyl group or an ethyl group is preferably bonded to the other carbon atom at the 2- or 6-position. Further, a hydrocarbon group or a partial structure represented by the above formula (3) may be bonded to the carbon atoms at the 2nd and 6th positions of the benzene ring to which -O- in formula (2) is bonded. In the benzene ring in the above formula (2), (Y _n -A) in the above formula (1) may be bound to a carbon atom other than the 2nd and 6th positions via the central portion X and an oxygen atom. , (Y _n -A) of the above formula (1) is bonded to the 1-position via an oxygen atom, and the central portion X is preferably bonded to the 4-position.

Examples of polyhydric phenol compounds for the partial structure represented by formula (2) are listed below.
Examples of polyhydric phenol compounds include 4,4′-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4′-[(3-hydroxyphenyl)methylene]bis(2 ,3,6-trimethylphenol), 4,4′-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4′-[(4-hydroxyphenyl)methylene]bis(2 , n3,6-trimethylphenol), 4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4′-[(4-hydroxy-3- ethoxyphenyl)methylene]bis(2,3,6-trimethylethylphenol), 4,4′-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4′-[ (3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 2,2′-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4, 4'-[4-(4-hydroxyphenyl)cyclohexylidene]bis(2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl)methylene]-bis(2,3,6-trimethyl phenol), 4,4′-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethylidene]bis(2,6-dimethylphenol), 4 , 4′-[1-[4-[1-(4-hydroxy-3-fluorophenyl)-1-methylethyl]phenyl]ethylidene]bis(2,6-dimethylphenol), 2,6-bis[( 4-hydroxy-3,5-dimethylphenyl)ethyl]-4-methylphenol, 2,6-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-4-methylphenol, 2,6 -bis[(4-hydroxy-3,5,6-trimethylphenyl)methyl]-4-ethylphenol, 2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-methylphenol, 2 ,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-methylphenol, 2,4-bis[(4-hydroxy-3-cyclohexylphenyl)methyl]-6-methylphenol, 2,4 -bis[(4-hydroxy-3-methylphenyl)methyl]-6-cyclohexylphenol, 2,4-bis[(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexylphenol, 2,4-bis [(4-hydroxy-2,3,6-trimethylphenyl)methyl]-6-cyclohexylphenol, 3,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2-benzenediol , 4,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzenediol, 2,4,6-tris[(4-hydroxy-3,5-dimethylphenyl)methyl ]-1,3-benzenediol, 2,4,6-tris[(2-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzenediol, 2,2′-methylenebis[6-[( 4/2-hydroxy-2,5/3,6-dimethylphenyl)methyl]-4-methylphenol], 2,2′-methylenebis[6-[(4-hydroxy-3,5-dimethylphenyl)methyl] -4-methylphenol], 2,2′-methylenebis[6-[(4/2-hydroxy-2,3,5/3,4,6-trimethylphenyl)methyl]-4-methylphenol], 2, 2′-methylenebis[6-[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-4-methylphenol], 4,4′-methylenebis[2-[(2,4-dihydroxyphenyl)methyl ]-6-methylphenol], 4,4′-methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-3,6-dimethylphenol], 4,4′-methylenebis[2-[(2, 4-dihydroxy-3-methylphenyl)methyl]-3,6-dimethylphenol], 4,4′-methylenebis[2-[(2,3,4-trihydroxyphenyl)methyl]-3,6-dimethylphenol ], 6,6′-methylenebis[4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2,3-benzenetriol], 1,1-bis(2-methyl-4-hydroxy -5-t-butylphenyl)butane, 4,4′-cyclohexylidenebis[2-cyclohexyl-6-[(2-hydroxy-5-methylphenyl)methyl]phenol], 4,4′-cyclohexylidene bis[2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl)methyl]phenol], 4,4′-cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-2- methyl-5-cyclohexylphenyl)methyl]phenol], 4,4′-cyclohexylidenebis[2-cyclohexyl-6-[(2,3,4-trihydroxyphenyl)methyl]phenol], 4,4′, 4'',4'''-(1,2-ethanediylidene)tetrakis(2,6-dimethylphenol), 4,4',4'',4'''-(1,4-phenylenedimethylidene)tetrakis (2,6-dimethylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane and the like, but are not limited thereto.

The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 3 or more, but if the number of polyphenylene ether terminals increases, the molecular weight change during polymerization may increase, so preferably 3 to 6. , more preferably 3 to 4.

Particularly preferred polyhydric phenol compounds are 4,4′-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4′-[(3-hydroxyphenyl)methylene]bis(2, 6-dimethylphenol), 4,4′-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4′-[(3-hydroxyphenyl)methylene]bis(2, 3,6-trimethylphenol), 4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol), 1,1,3-tris-( 2-methyl-4-hydroxy-5-t-butylphenyl)butane and 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane.

In the above formula (1), a plurality of Y are each independently a divalent linking group having a structure represented by the following formula (4) (i.e., a phenol unit having a substituent), and n is Y each independently an integer of 0 to 200, and at least one n in a (-Y _n -A) is an integer of 1 or more.

In formula (4), a plurality of R ²¹ are each independently a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; represents at least one selected from the group consisting of; R ²¹ is preferably an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, a vinyl group, an aryl group, an ethynyl group. , or a propargyl group, more preferably a methyl group or an ethyl group, particularly preferably a methyl group. A halogen atom etc. are mentioned as said substituent.

In formula (4), two R ²¹ are simultaneously hydrogen from the viewpoint of having all of low dielectric properties, adequate metal exfoliation, low solution viscosity, sufficient Tg upon curing, etc. for the modified polyphenylene ether-containing composition. It is preferably not an atom, and/or preferably not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group.

In formula (4), a plurality of R ²² are each independently a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; represents at least one selected from the group consisting of, preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom , a methyl group, an ethyl group or an n-propyl group, more preferably a hydrogen atom or a methyl group. A halogen atom etc. are mentioned as said substituent.

Examples of monohydric phenol compounds for the structure represented by the above formula (4) include o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2, 6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propyl phenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis-(4-fluorophenyl)phenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, 2,5-dimethylphenol, 2,3,6-trimethylphenol, 2,5-diethylphenol, 2-methyl-5-ethylphenol, 2-ethyl-5-methylphenol, 2-allyl-5-methylphenol, 2,5-diallylphenol, 2,3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromophenol, 2-methyl-5-isopropylphenol, 2-methyl-5-n-propylphenol , 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2,5-di-n-propylphenol, 2-ethyl-5-chlorophenol, 2-methyl-5-phenylphenol, 2 ,5-diphenylphenol, 2,5-bis-(4-fluorophenyl)phenol, 2-methyl-5-tolylphenol, 2,5-ditolylphenol, 2,6-dimethyl-3-allylphenol, 2, 3,6-triallylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6-dimethyl- 3-t-butylphenol and the like.

Among the above monohydric phenol compounds, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol and 2,3,6-trimethylphenol are particularly inexpensive and readily available. , or 2,5-dimethylphenol are preferred, and 2,6-dimethylphenol or 2,3,6-trimethylphenol are more preferred.

In addition, the said phenol compound may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the monohydric phenol compound include a method of using 2,6-dimethylphenol and 2,6-diethylphenol in combination, and a method of using 2,6-dimethylphenol and 2,6-diphenylphenol in combination. a method of using 2,3,6-trimethylphenol and 2,5-dimethylphenol in combination, a method of using 2,6-dimethylphenol and 2,3,6-trimethylphenol in combination, and the like. mentioned. At this time, the mixing ratio of the phenol compounds to be combined can be arbitrarily selected.

In addition, the phenol compounds used contain small amounts of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which may be contained as by-products during production. good too.

The phenol compound for the a-valent partial structure as represented by the above formula (2) includes a corresponding monohydric phenol compound, aldehydes (e.g., formaldehyde), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, etc.), or by reaction with a dihalogenated aliphatic hydrocarbon, reaction between corresponding monohydric phenol compounds, or the like.

In the above formula (1), A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except for the case where all of A are hydrogen atoms.

式（５）中、Ｒ^３１、及びＲ^３４は、それぞれ独立に、炭素数Ｃ_１～３０の２価の炭化水素基であり、複数のＲ^３２、及びＲ^３３は、それぞれ独立に、Ｃ_１～３０の１価の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基、又はヒドロキシアルキル基である。式（５）中、Ｂは、オレフィン系の炭素－炭素２重結合を含むＣ_１～３０の炭化水素系置換基で、その一部が、水素、水酸基、アリール基、アルコキシ基、アリロキシ基、アミノ基、ヒドロキシアルキル基、ビニル基、イソプロペニル基、又はハロゲン基に置換されていてもよい。式（５）中、ｔは、０～８の整数であり、０～５の整数であることが好ましい。 Here, A in formula (1) is represented by the following formula (5) from the viewpoint of obtaining low dielectric properties, appropriate metal peelability, low solution viscosity, and sufficient Tg properties during curing. Substituents are preferred.

In formula (5), R ³¹ and R ³⁴ are each independently a divalent hydrocarbon group having _{1 to 30} carbon atoms, and a plurality of R ³² and R ³³ are each independently C _{1 ∼30} monovalent hydrocarbon groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, or hydroxyalkyl groups. In formula (5), B is a C _1-30 hydrocarbon substituent containing an olefinic carbon-carbon double bond, a portion of which is hydrogen, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, It may be substituted with an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. In formula (5), t is an integer of 0-8, preferably an integer of 0-5.

In formula (5), the hydrocarbon groups of R ³² and R ³³ preferably have a large number of carbon atoms from the viewpoint of dielectric properties or solubility in solvents. On the other hand, if ^the number of carbon atoms is excessively large, a decrease in Tg, a decrease in metal peelability, or a decrease in olefinic carbon-carbon ^double bonds occurs _. It is preferably about ₃₀ , more preferably about C _1-20 , and even more preferably about C _1-12 .

Specific examples of monovalent hydrocarbon groups for R ³² and/or R ³³ in formula (5) include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n -pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2 -ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5 -methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1, 2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl , 1-methyl-3,3-dimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl , 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4 -ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl , 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2 ,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1- Ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2-ethyl-3-methyl Pentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methylpentyl, 1-( 2-methylpropyl)butyl, 1-(2-methylpropyl)-2-methylbutyl, 1,1-(2-methylpropyl)ethyl, 1,1-(2-methylpropyl)ethylpropyl, 1,1-diethyl propyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2, 3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl , 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2- phenylethyl and the like.

The monovalent hydrocarbon group for R ³² and/or R ³³ is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl. , 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl , 4-methylpentyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl , 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, and benzyl Yes, more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl , cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl and benzyl, more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3 -octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, and benzyl.

Specific examples of aryl groups for R ³² and/or R ³³ include phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4- n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2- n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2-t-butylphenyl, 2,6-dimethylphenyl, 2, 4-dimethylphenyl, 2,5-dimethylphenyl, 2,3-dimethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5 -diethylphenyl, 2,3-diethylphenyl, 3,5-diethylphenyl, 3,4-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 2,3,6-trimethyl phenyl, 3,4,5-trimethylphenyl, 2,4,6-triethylphenyl, 2,3,4-triethylphenyl, 2,3,6-triethylphenyl, 3,4,5-triethylphenyl and the like. .

The aryl group for R ³² and/or R ³³ is preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4- n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2- n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2, 5-dimethylphenyl, 2,3-dimethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3 -diethylphenyl, 3,5-diethylphenyl, 3,4-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5 -trimethylphenyl and 2,4,6-triethylphenyl, more preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl and 2-ethyl Phenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butyl phenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5 -dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,6-trimethylphenyl, and 2,4,6-triethylphenyl, more preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 4-isopropylphenyl, 3- isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-t-butylphenyl, 2,6-dimethylphenyl, 2,4- dimethylphenyl, 2,5-dimethylphenyl, and 2,4,6-trimethylphenyl.

Specific examples of alkoxy groups for R ³² and/or R ³³ include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy. , 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 4-methylpen thoxy, 3-methylpentoxy, 2-methylpentoxy, 1,1-dimethyl-1-butoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, 4,4-dimethyl- 1-butoxy, 1,2-dimethyl-1-butoxy, 1,3-dimethyl-1-butoxy, 2-ethyl-1-butoxy, 3-ethyl-1-butoxy, 3,3-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethyl-1-hexoxy, phenylmethoxy and the like.

Alkoxy groups for R ³² and/or R ³³ are preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 1-pentoxy, 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1,1-dimethyl-1-butoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, 2-ethyl-1-butoxy, 3-ethyl-1-butoxy , 3,3-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethyl-1-hexoxy and phenylmethoxy, more preferably methoxy , ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 2,2-dimethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-to xoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, cyclohexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy, more preferably methoxy, ethoxy, propoxy, iso propoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 2,2-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy.

Specific examples of aryloxy groups for R ³² and/or R ³³ include phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,3 -dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 3-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 3-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 3-t-butylphenoxy, 2,6-di-t-butylphenoxy, 2,4-di-t-butylphenoxy, 2,3-di-t-butylphenoxy, 2-methyl -4-t-butylphenoxy, 2-methyl-6-t-butylphenoxy, 4-methyl-2-t-butylphenoxy and the like.

The aryloxy group for R ³² and/or R ³³ is preferably phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4 ,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 3-t-butylphenoxy, 2,4 -di-t-butylphenoxy, 2,3-di-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, 2-methyl-6-t-butylphenoxy, and 4-methyl-2-t- butylphenoxy, more preferably phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4 -isopropylphenoxy, 2-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, and 2-methyl-6 -t-butylphenoxy, more preferably phenoxy, 4-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-t -butylphenoxy, 2-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, and 2-methyl-6-t-butylphenoxy.

Specific examples of amino groups for R ³² and/or R ³³ include dimethylamino, ethylmethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-t-butylamino, dicyclohexylamino and the like.

In formula (5), the hydrocarbon groups of R ³¹ and R ³⁴ are carbon from the viewpoint of dielectric properties or solubility in solvents, and from the viewpoint of increasing the degree of freedom of terminal functional groups and improving reactivity. A larger number is more preferable. On the ^other hand, if the number of carbon atoms is excessively large, a decrease in Tg, a decrease in metal peelability, or a decrease in olefinic carbon-carbon ^double bonds occurs _. C 1 to about ₃₀ is preferable, C _{1 to about 20} is more preferable, and C _{1 to about 12} is even more preferable.

Specific examples of the divalent hydrocarbon group for R ³¹ and/or R ³⁴ in formula (5) include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene , 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene , 2,2-dimethyl-1,3-propylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3 -propylene, 3,3-dimethyl-1,3-propylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2 -ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4 -methylpentylene, 1,1-dimethyl-1,4-butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4 -butylene, 1,3-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene , 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene , 3-ethyl-1,5-pentylene, 1,1-dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4 -dimethyl-1,5-pentylene, 1,2-dimethyl-1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl -1,5-pentylene, 2,4-dimethyl-1,5-pentylene, 3,4-dimethyl-1,5-pentylene and the like.

Specific examples of the divalent hydrocarbon group for R ³¹ and/or R ³⁴ include 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl-3,3-dimethyl-1, 4-butylene, 1,2,3-trimethyl-1,4-butylene, 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene , 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene Lene, 2,3-dimethyl-1,3-cyclopentylene, 2,4-dimethyl-1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene , octamethylene, 1-methyl-1,7-heptylene, 1-ethyl-1,6-hexylene, 1-propyl-1,5-pentylene, 2-methyl-1,7-heptylene, 3-methyl-1,7 -heptylene, 4-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6 -hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3 -dimethyl-1,6-hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl -1,6-hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1 ,6-hexylene, 2,5-dimethyl-1,6-hexylene and the like.

Specific examples of the divalent hydrocarbon group for R ³¹ and/or R ³⁴ include 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3, 3-ethylmethyl-1,5-pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5- Pentylene, 1-ethyl-4-methyl-1,5-pentylene, 2-ethyl-1-methyl-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1- methyl-1,5-pentylene, 2-ethyl-3-methyl-1,5-pentylene, 2-ethyl-4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 3-ethyl-4-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 1-(2-methylpropyl) -1,4-butylene, 1-(2-methylpropyl)-2-methyl-1,4-butylene, 1,1-(2-methylpropyl)ethylene, 1,1-(2-methylpropyl)ethyl- 1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3-propylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2 , 2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3 -dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl-1,4-cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2 -methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4-methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexyl sylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1 ,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene -methylene, methylene-1,4-phenylene, ethylene-1,4-phenylene, ethylene-1,4-phenylene-ethylene and the like.

The divalent hydrocarbon group for R ³¹ and/or R ³⁴ is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene , pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl- 1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3- ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylene , 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene , 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4- Cyclohexylene, 4-methyl-1,4-cyclohexylene, octamethylene, 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl -1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl -1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene.

The divalent hydrocarbon group for R ³¹ and/or R ³⁴ is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethyl Ethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl —1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, octamethylene, 1-methyl-1,7-heptylene, 3-methyl-1 ,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1 ,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene. .

The divalent hydrocarbon group for R ³¹ and/or R ³⁴ is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethyl ethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, octamethylene, 1-methyl-1 ,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1 ,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene , undecyl methylene, and dodecyl methylene.

In formula (5), specific examples of substituents containing a carbon-carbon double bond for B include vinyl, allyl, isopropenyl, 5-norbornene-2yl, 1-butenyl, and 1-pentenyl. group, 3-cyclopentenyl, 4-cyclopentenyl, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group , p-vinylbenzyl group, p-isopropenylbenzyl group, m-vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p- vinylphenylpropenyl group, p-vinylphenylbutenyl group, m-vinylphenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group , o-vinylphenylbutenyl group, methacryl group, acryl group, 2-ethyl acryl group, 2-hydroxymethyl acryl group and the like.

式（６）及び／又は式（７）中、複数のＲ^３１、及びＲ^３４は、それぞれ独立に、Ｃ_１～３０の２価の炭化水素基であり、複数のＲ^３２、及びＲ^３３は、それぞれ独立に、Ｃ_１～３０の１価の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基、又はヒドロキシアルキル基である。これらの基の具体例、及び好ましい基としては、上記式（５）で説明された対応する基の具体例、及び好ましい基が挙げられる。 More specific examples of A in formula (1) or more specific examples of substituents represented by formula (5) include structures represented by the following formulas (6) and/or (7) is mentioned.

In formula (6) and/or formula (7), multiple R ³¹ and R ³⁴ are each independently a C _1-30 divalent hydrocarbon group, and multiple R ³² and R ³³ are , each independently a C _1-30 monovalent hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group. Specific examples and preferred groups of these groups include specific examples and preferred groups corresponding to the above formula (5).

In formula (6) and/or formula (7), a plurality of R ³⁵ are each independently a hydrogen atom, a hydroxyl group, or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, A hydroxyalkyl group, a vinyl group, an isopropenyl group, and a halogen group.

In formula (7), R ³⁶ is a C _1-3 hydrocarbon group, an amino group, or oxygen, and part of the hydrocarbon group is an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl preferably substituted with a group, a vinyl group, an isopropenyl group, or a halogen group. A part of the amino group may be substituted with a C _1-5 alkyl group. The number of carbon atoms in the hydrocarbon group for R ³⁶ is preferably 1-3.
In formula (6) and/or formula (7), s, t and u are each independently an integer of 0-8.

In formula (6) and/or formula (7), the hydrocarbon group of R ³⁵ preferably has a large number of carbon atoms from the viewpoint of dielectric properties or solubility in solvents. On the other hand, if the number of carbon atoms is excessively large, the Tg is lowered, the metal peelability is lowered, or the ^olefinic carbon-carbon double bond is _lowered . Preferably, about C _1-20 is more preferable, and about C _1-12 is even more preferable.

Specific examples of hydrocarbon groups for R ³⁵ include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl. , 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4 -dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2 ,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl , 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methyl heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl and the like.

Specific examples of hydrocarbon groups for R ³⁵ include 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2- to dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethyl xyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methyl Pentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl -3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methylpentyl, 1-(2-methylpropyl)butyl, 1-(2-methylpropyl)-2-methylbutyl, 1,1 -(2-methylpropyl)ethyl, 1,1-(2-methylpropyl)ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6- dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1- Cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl and the like.

Hydrocarbon groups for R ³⁵ are preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl , 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl , 3-methylcyclohexyl, 4-methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl and benzyl, more preferably methyl and ethyl , n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl , n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethyl xyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl and benzyl, more preferably methyl, ethyl, n-propyl, 2 -propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2- methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl , decyl, isodecyl, undecyl, dodecyl, and benzyl.

Specific examples of hydrocarbon groups for R ³⁶ include methylene, 1,1-dimethylmethylene, 1,1-diethylmethylene, ethylene, trimethylene, 1,2-propylene, 2-methyl-1,3-trimethylene, 1, 1-dimethylethylene, 1-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene and the like, and specific examples of groups partially substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group include: -phenylmethylene, 1,1-diphenylmethylene, 1-benzylmethylene, 1,1-dibenzylmethylene, 1-methoxymethylene, 1,1-dimethoxymethylene, 1-ethoxymethylene, 1,1-diethoxymethylene, 1 -vinylmethylene, 1,1-divinylmethylene, 1-allylmethylene, 1,1-diallylmethylene, 1-isopropenylmethylene, 1,1-diisopropenylmethylene, 1-chloromethylene, 1,1-dichloromethylene, 1-bromomethylene, 1,1-dibromomethylene, 1-phenylethylene, 1,1-diphenylethylene, 1,2-diphenylethylene, 1,1,2-triphenylethylene, 1,1,2,2-tetra Phenylethylene, 1-benzylethylene, 1,1-dibenzylethylene, 1,2-dibenzylethylene, 1,1,2-tribenzylethylene, 1,1,2,2-tetrabenzylethylene, 1-vinylethylene , 1,1-divinylethylene, 1,2-divinylethylene, 1,1,2-trivinylethylene, 1,1,2,2-tetravinylethylene, 1-allylethylene, 1,1-diallylethylene, 1 ,2-diallylethylene, 1,1,2-triallylethylene, 1,1,2,2-tetraallylethylene, 1-chloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, 1,1,2 -trichloroethylene, 1,1,2,2-tetrachloroethylene, 1-bromoethylene, 1,1-dibromoethylene, 1,2-dibromoethylene, 1,1,2-tribromoethylene, 1,1,2,2- Tetrabromoethylene is mentioned.

The number of OH terminals contained in the polyphenylene ether having the structure represented by the above formula (1) is such that the modified polyphenylene ether-containing composition has low dielectric properties, moderate metal peelability, low solution viscosity, and sufficient Tg during curing. 0 to 3,000 μmol/g from the viewpoint of having all of the above.

式（８）中、Ｚは、下記式（９）と（１１）で表されるａ価の部分構造であり、ａは、全てが２の場合を除いた、２または３～６の整数を表す。 <Modified polyphenylene ether composition>
The curable resin composition according to the present embodiment includes, for example, a modified polyphenylene ether composition, and the modified polyphenylene ether composition has a structure represented by the above formula (1) (wherein a is all shall represent an integer of 2 or 3 to 6, except when is 2), more specifically, modified polyphenylene ether having a structure represented by the following formula (8) .

In formula (8), Z is an a-valent partial structure represented by the following formulas (9) and (11), and a is an integer of 2 or 3 to 6, except when all are 2. show.

In formula (8), a (-Y _n -A) bonded to Z may be the same or different. Here, Y is a substituted phenylene monomer unit, and Y _n represents a polyphenylene ether structure in which n substituted phenylene monomer units are continuously bonded. Moreover, Z is based on a polyhydric phenol compound having a phenol structure to which a polyphenylene ether unit structures can be bonded. Further, in formula (8), A represents a hydrogen atom or a silyl group-containing derivative capable of bonding with the polyphenylene ether structure, and contains the silicon atom (Si) defined in formulas (5), (6) and (7) above. A functional group is preferred.

The modified polyphenylene ether composition includes a modified polyphenylene ether having a structure represented by the above formula (8), and at least one (-Y _n -A) in the structure represented by the above formula (8) is (-Y 7.6 to 8.3 ppm with respect to the integrated value of the peak derived from the structure represented by the following formula (9) in the ¹ H-NMR measurement result containing 60 mol% or more of the modified or unmodified polyphenylene ether that is n- _H ) is 1 or less, and the polystyrene-equivalent number-average molecular weight is 500 to 15,000 g/mol.

The modified polyphenylene ether having the structure represented by the above formula (8) contained in the modified polyphenylene ether composition of the present embodiment may be of one type or plural types. In addition, in the modified polyphenylene ether composition of the present embodiment, one or more (-Y _n -A) in the structure of the above formula (8) is (Y _n -H), and all (-Y _n - Including modified polyphenylene ethers in which A) is not (Y _n —H), and polyphenylene ethers in which all (—Y _n —A) are (Y _n —H) in the structure represented by the above formula (8). You can Here, Y and n are preferably the same in ( _-Yn -A) of the modified polyphenylene ether and ( _Yn -H) of the unmodified polyphenylene ether.

The polyfunctional modified polyphenylene ether composition of the present embodiment may further contain additives such as solvents, polymerization catalysts and surfactants. The polyfunctional polyphenylene ether composition of this embodiment may be solid.

Z in formula (8) may be a structure having an a-valent central phenol site represented by the following formula (9), and a in formula (8) or (9) is an integer of 3 to 6 Preferably.

The central phenol site is as described in the above item <Modified Polyphenylene Ether>.

式（９）中、ａとしては、式（８）と同様の整数が挙げられ、式（８）と同じ整数であることが好ましい。式（９）の中心フェノール部位において、ａ個の各部分構造は、同じ構造であってもよいし、異なっていてもよい。 In the modified polyphenylene ether, a partial structure (e.g., phenol optionally substituted with R ⁵ etc.) is bonded to the a-valent center X, and the a-valent partial structure (i.e., the formula (9) It may be a structure in which (-Y _n -A) of formula (8) is bound to the central phenol site represented).

In formula (9), a is the same integer as in formula (8), preferably the same integer as in formula (8). In the central phenol site of formula (9), the a partial structures may have the same structure or different structures.

In formula (9), X is any a-valent linking group, which is not particularly limited, but is selected from, for example, hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; nitrogen, phosphorus, silicon and oxygen; atoms such as nitrogen, phosphorus, silicon, etc.; or groups combining these; and the like. Also, X may be a linking group other than a single bond. Furthermore, X may be a linking group that links the a-valent partial structures to each other.

X in the above formula (9) is an a-valent alkyl skeleton bonded to the benzene ring to which R ⁵ is bonded via a single bond or an ester bond; a-valent aryl skeleton bonded to the benzene ring to which ⁵ is bonded; a-valent heterocyclic skeleton bonded to the benzene ring to which R ⁵ is bonded via a single bond or an ester bond; .

Here, the alkyl skeleton is not particularly limited. Skeletons that are directly bonded (a branched terminals may be bonded with a benzene ring, and there may be branched terminals to which no benzene ring is bonded), and the like. The aryl skeleton is not particularly limited, but for example, a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to R ⁵ via a single bond or an alkyl chain. Examples include a skeleton that bonds to a benzene ring that is attached. Furthermore, the heterocyclic skeleton is not particularly limited, but includes, for example, a skeleton in which a triazine ring is bonded to a benzene ring to which ^R5 is bonded via a single bond or an alkyl chain.

A plurality of R ⁵ in formula (9) is each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and k is each It is independently an integer from 1 to 4.

式（１０）中、
複数のＲ^１１は、各々独立に、置換されていてもよい炭素数１～８のアルキル基であり；
複数のＲ^１２は、各々独立に、置換されていてもよい炭素数１～８のアルキレン基であり；ｂは、各々独立に０又は１であり；かつ
Ｒ^１３は、水素原子、置換されていてもよい炭素数１～８のアルキル基、又はフェニル基のいずれかを表す。
上記置換基としては、ハロゲン原子等が挙げられる。 Examples of R ⁵ in the above formula (9) include linear alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, and an n-propyl group, groups having a partial structure of the following formula (10), and the like. mentioned. At least one of R ⁵ may be a partial structure of the following formula (10).

In formula (10),
a plurality of R ¹¹ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms;
A plurality of R ¹² are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms; b is each independently 0 or 1; and R ¹³ is a hydrogen atom, substituted represents either an alkyl group having 1 to 8 carbon atoms, which may be substituted, or a phenyl group.
A halogen atom etc. are mentioned as said substituent.

The above formula (10) is preferably a group containing secondary and/or tertiary carbon, such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2-dimethylpropyl or a structure having a phenyl group at the end thereof, and more preferably a tert-butyl group.

When the carbon atom of the benzene ring to which -O- in formula (9) is bonded is the 1st position, R ⁵ having a partial structure represented by formula (10) is bonded to one carbon atom at the 2nd or 6th position. and a hydrogen atom, a methyl group or an ethyl group is bonded to the other carbon atom at the 2- or 6-position. It may be a structure in which a hydrocarbon group or a partial structure represented by the above formula (10) is bonded to the carbon atoms at the 2nd and 6th positions of the benzene ring to which —O— of formula (9) is bonded. In the benzene ring in the above formula (9), (Y _n -A) in the above formula (1) or (8) is bonded to a carbon atom other than the 2-position and the 6-position via the center X and an oxygen atom. It is preferable that (Y _n -A) of the above formula (8) is bonded to the 1-position via an oxygen atom, and the central portion X is bonded to the 4-position.

式（１１）中の複数のＲ^５は、各々独立に、任意の置換基であり、そしてｋは、各々独立に、１～４の整数である。
上記式（１１）中のＲ^５としては、例えば、メチル基、エチル基、ｎ－プロピル基等の炭素数１～８の直鎖状アルキル基等が挙げられる。 When a=2 in formula (8), Z may be, for example, a structure represented by formula (11) below.

Each of the plurality of R ⁵ in formula (11) is independently an optional substituent, and each k is independently an integer of 1-4.
Examples of R ⁵ in the above formula (11) include linear alkyl groups having 1 to 8 carbon atoms such as methyl group, ethyl group and n-propyl group.

When a≧3 in formula (8), Z may be based on or derived from a polyhydric phenolic compound for the structure represented by formula (9) above. Specific polyhydric phenols include compounds defined for the structure represented by formula (2) above.

In the above formula (8), each Y is independently a divalent linking group (a phenol unit having a substituent) having a structure derived from a monovalent phenol compound represented by the following formula (12), n represents the number of repetitions of Y, each independently being an integer of 0 to 200, and at least one n being an integer of 1 or more.

式（１２）中、Ｒ^２１、及びＲ^２２としては、上記式（４）において定義された基と同様の基が挙げられ、上記式（４）で定義されたＲ^２１及びＲ^２２と同じであることが好ましい。 The modified polyphenylene ether and / or the modified polyphenylene ether composition corresponds to, for example, a monohydric phenol compound represented by the following formula (12) and the central part X in the structure represented by the above formula (9) It is obtained by copolymerizing with an a-valent phenol compound (central phenol) and subjecting it to a modification reaction.

In formula (12), R ²¹ and R ²² include the same groups as defined in formula (4) above, and are the same as R ²¹ and R ²² defined in formula (4) above. Preferably.

Specific examples of the monovalent phenol compound represented by the above formula (12) include the monovalent phenol compounds defined for the structure represented by the above formula (4).

Examples of dihydric phenols represented by the above formula (11) are listed below.
Examples of dihydric phenols include (1,1′-biphenyl)-4,4′-diol, 3,3′-dimethyl(1,1′-biphenyl)-4,4′-diol, 3,3 ',5,5'-tetramethyl(1,1'-biphenyl)-4,4'-diol, 2,2',3,3',5,5'-hexamethyl(1,1'-biphenyl)- 4,4-diol, 2,3,3′,5,5′-pentamethyl(1,1′-biphenyl)-4,4-diol, 2,3′,5,5′-tetramethyl(1,1 '-biphenyl)-4,4-diol, 2,2',5,5'-tetramethyl(1,1'-biphenyl)-4,4-diol, 2,2',3,5,5'- pentamethyl(1,1'-biphenyl)-4,4-diol, 5,5'-di-t-butyl-2,2'-dimethyl(1,1'-biphenyl)-4,4-diol, 3, 3′-di-t-butyl-5,5′-dimethyl(1,1′-biphenyl)-4,4-diol and the like, but are not limited thereto.

The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more, but if the number of polyphenylene ether terminals increases, the molecular weight change during polymerization may increase, so preferably 2 to 6. , more preferably 2 to 4.

式（１３）中、ｃは、１～１００の任意の整数であり、そしてＲ^２１及びＲ^２２としては、上記式（１２）について説明された基と同様のものが挙げられる。 The modified polyphenylene ether composition of the present embodiment may contain a monofunctional polyphenylene ether represented by the following formula (13) and/or a modified monofunctional polyphenylene ether represented by the following formula (13). do not have.

In formula (13), c is an arbitrary integer of 1 to 100, and R ²¹ and R ²² include the same groups as those described for formula (12) above.

In the modified polyphenylene ether and / or modified polyphenylene ether composition (hereinafter referred to as modified polyphenylene ether (composition)) of the present embodiment, a polyfunctional raw material for a polyfunctional modified polyphenylene ether having the structure of the above formula (1) Polyphenylene ethers may be prepared by a redistribution reaction in which monofunctional polyphenylene ethers are equilibrated with polyhydric phenols in the presence of an oxidizing agent. Redistribution reactions are known in the art and are described, for example, in US Pat. No. 3,496,236 to Cooper et al. and US Pat. No. 5,880,221 to Liska et al.

The modified polyphenylene ether (composition) of the present embodiment is a modified polyphenylene ether having the structure of the above formula (1) in the ¹ H-NMR measurement results, and one or more (-Y _n - A) is (Y _n —H) and not all (—Y _n —A) are (Y _n —H), and all (—Y _n in the structure of formula (1) above Appears in the region of 7.6 to 8.3 ppm with respect to the integrated value of the peak derived from the central phenol site represented by the above formula (2) contained in the polyphenylene ether in which -A) is (Y _n -H) The ratio of the integrated value of peaks derived from peroxide is 1 or less, preferably 0.8 or less, and more preferably 0.5 or less. The fact that the integrated value of the peak derived from the peroxide is 1 or less with respect to the integrated value of the peak derived from the central phenol site indicates that the modified polyphenylene ether composition does not contain a peroxide adduct as a by-product. However, it means that the target polyfunctional modified polyphenylene ether or the like has a high purity. As a result, the glass transition temperature (Tg) of the modified polyphenylene ether composition can be increased.
The ratio can be measured by the method described in Examples below.

The modified polyphenylene ether (composition) in the present embodiment has a number average molecular weight (Mn) of 500 to 15,000 g/mol, preferably 1,000 to 10,000 g/mol, more preferably 2,000. ~8,000 g/mol. When the number average molecular weight (Mn) is within the above range, the fluidity when dissolved in a solvent for preparing the varnish in the process of applying to the substrate material is further improved, and the workability when applying to the substrate material is ensured. be able to.
The number average molecular weight can be measured by the method described in Examples below.

The number of A substituents (meaning A defined by formula (1), hereinafter the same) contained in the polyfunctional modified polyphenylene ether (composition) in the present embodiment is not particularly limited, but A The number of substituents excludes the case where A=hydrogen atom (H). Among them, the number of A substituents in the composition is preferably 700 to 3,000 μmol/g, more preferably 700 to 2,000 μmol/g. When the number of A substituents in the composition is 700 μmol / g or more, the crosslink density can be increased during curing, and a cured product having a high glass transition temperature and excellent dielectric properties tends to be obtained. It is in. When the number of A substituents in the composition is 3,000 μmol/g or less, the viscosity of the varnish obtained by dissolving the polyphenylene ether composition in a solvent can be lowered, and the workability tends to be good when applied to the substrate material.

As a method for evaluating the number of A substituents, a known method such as a titration method, a spectroscopic method, or a quantitative NMR method can be used depending on the type of functional group. For example, in the quantitative NMR method, when ¹ H-NMR is used, a standard sample with a known structure and a polyfunctional polyphenylene ether composition are allowed to coexist for measurement. A polyfunctional polyphenylene ether composition with a known weight and a standard sample are dissolved in a deuterated solvent to measure ¹ H-NMR, and the ratio of the integrated value of the peak derived from the A substituent and the peak of the standard sample, the polyfunctional polyphenylene ether The number of A substituents can be calculated from the weight of the composition, the weight of the standard sample, and the molecular weight of the standard sample. The standard sample is not particularly limited as long as it dissolves in a deuterated solvent, does not react with the polyfunctional polyphenylene ether composition, and the peaks in ¹ H-NMR do not interfere with the peaks derived from the polyfunctional polyphenylene ether composition. For a specific method for evaluating the number of A substituents, the description in Examples can be referred to.

The modified polyphenylene ether-containing composition according to the present embodiment is represented by the above formula (8) from the viewpoint of having all of low dielectric properties, appropriate metal peeling properties, low solution viscosity, sufficient Tg during curing, etc. It preferably contains 0.5 to 95% by mass of modified polyphenylene ether having a structure.

式（１）’中、Ｚ、Ｙ、ｎ、及びａとしては、上記式（１）と同様のものが挙げられ、そして上記式（１）で定義されたものと同じであることが好ましい。 <Method for producing polyfunctional modified polyphenylene ether (composition)>
The method for producing the polyfunctional modified polyphenylene ether (composition) of the present embodiment is, for example, a polyfunctional modified polyphenylene ether (composition) having a hydroxyl group at the molecular end represented by the following formula (1)′ by a polymerization method ( Hereinafter, it can be produced by synthesizing an unmodified polyfunctional polyphenylene ether (composition), and introducing the A substituent in the formula (1) to its terminal, that is, modifying it.

In formula (1)′, Z, Y, n and a are the same as defined in formula (1) above, and are preferably the same as defined in formula (1) above.

(Polymerization process)
Here, in the method for producing the unmodified polyfunctional polyphenylene ether (composition), it is preferable to use an aromatic solvent that is a good solvent for the unmodified polyfunctional polyphenylene ether (composition) as the polymerization solvent in the polymerization step.

Here, the good solvent for the unmodified polyfunctional polyphenylene ether composition is a solvent capable of dissolving the polyfunctional polyphenylene ether. Examples of such solvents include benzene, toluene, xylene (o-, m- , p- isomers), aromatic hydrocarbons such as ethylbenzene and styrene, or halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; nitro compounds such as nitrobenzene;

As the polymerization catalyst used in the present embodiment, a known catalyst system that can be generally used for the production of polyphenylene ether can be used. As a generally known catalyst system, one comprising a transition metal ion having oxidation-reduction ability and an amine compound capable of forming a complex with the transition metal ion is known. For example, it comprises a copper compound and an amine compound. a catalyst system, a catalyst system comprising a manganese compound and an amine compound, a catalyst system comprising a cobalt compound and an amine compound, and the like. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, some alkali or additional amine compounds may be added here.

式（ＤＡ１）中、Ｒ^１４、Ｒ^１５、Ｒ^１６、及びＲ^１７は、それぞれ独立に、水素原子、炭素数１～６の直鎖状又は分岐状アルキル基であり、全てが同時に水素原子ではなく、そしてＲ^１８は、炭素数２～５の直鎖状又はメチル分岐を持つアルキレン基である。 A polymerization catalyst preferably used in the present embodiment is a catalyst comprising a copper compound, a halogen compound and an amine compound as constituent components of the catalyst, and more preferably a diamine compound represented by the general formula (DA1) as the amine compound. is a catalyst containing

In formula (DA1), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; and R ¹⁸ is a linear or methyl-branched alkylene group having 2 to 5 carbon atoms.

Examples of copper compounds for the catalyst components described herein are listed. Suitable copper compounds may be cuprous compounds, cupric compounds or mixtures thereof. Examples of cupric compounds include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, particularly preferred metal compounds are cuprous chloride, cupric chloride, cuprous bromide and cupric bromide. These copper salts may also be synthesized at the time of use from oxides (eg, cuprous oxide), carbonates, hydroxides, etc. and the corresponding halogens or acids. A frequently used method is a method of mixing cuprous oxide and hydrogen halide (or a solution of hydrogen halide) as exemplified above.

Examples of halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, and tetramethylammonium bromide. , tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and the like. Also, they can be used as an aqueous solution or a solution using a suitable solvent. These halogen compounds may be used alone as a component, or may be used in combination of two or more. A preferred halogen compound is an aqueous solution of hydrogen chloride or an aqueous solution of hydrogen bromide.

The amount of these compounds to be used is not particularly limited, but is preferably 2 to 20 times as halogen atoms relative to the molar amount of copper atoms, and the use of copper atoms is preferable for 100 mol of the phenol compound added to the polymerization reaction. Amounts range from 0.02 mol to 0.6 mol.

Next, examples of diamine compounds as catalyst components are listed. For example, N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N, N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N-diethylethylenediamine, N-ethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine , N,N'-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N,N'-n-propylethylenediamine, Ni-propylethylenediamine, N,N'-i-propylethylenediamine, Nn -butylethylenediamine, N,N'-n-butylethylenediamine, Ni-butylethylenediamine, N,N'-i-butylethylenediamine, Nt-butylethylenediamine, N,N'-t-butylethylenediamine, N, N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N'-trimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N- methyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,3-diamino-1-methylpropane, N,N,N',N'-tetramethyl-1,3- diamino-2-methylpropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetramethyl-1,5-diaminopentane and the like. . A preferred diamine compound for this embodiment is one in which the alkylene group connecting two nitrogen atoms has 2 or 3 carbon atoms. The amount of these diamine compounds to be used is not particularly limited, but is preferably in the range of 0.01 mol to 10 mol per 100 mol of the phenol compound added to the polymerization reaction.

In this embodiment, a primary amine and a secondary monoamine can be included as components of the polymerization catalyst. Examples of secondary monoamines include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, Di-t-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine , N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2′,6′-dimethylphenyl)ethanolamine, N-(p-chlorophenyl ) ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine and the like.

A tertiary monoamine compound can also be included as a constituent component of the polymerization catalyst in the present embodiment. Tertiary monoamine compounds are aliphatic tertiary amines including alicyclic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine and the like. These tertiary monoamines may be used alone or in combination of two or more. The amount of these used is not particularly limited, but is preferably in the range of 15 mol or less per 100 mol of the phenol compound added to the polymerization reaction.

In the present embodiment, there is no restriction on the addition of a surfactant that is conventionally known to have an effect of improving polymerization activity. Such surfactants include, for example, trioctylmethylammonium chloride known under the trade names Aliquat 336 or Capriquat. The amount used is preferably within a range not exceeding 0.1% by mass with respect to 100% by mass of the total amount of the polymerization reaction mixture.

As the oxygen-containing gas in the polymerization step of the present embodiment, in addition to pure oxygen, a mixture of oxygen and an inert gas such as nitrogen at an arbitrary ratio, air, and further air and an inert gas such as nitrogen. A mixture in any proportion can be used. Normal pressure is sufficient for the system internal pressure during the polymerization reaction, but if necessary, either reduced pressure or increased pressure can be used.

The polymerization temperature is not particularly limited, but if it is too low, the reaction will not progress easily, and if it is too high, there is a risk of a decrease in reaction selectivity or the formation of high molecular weight components. is in the range of 10°C to 50°C.

In the method for producing an unmodified polyfunctional polyphenylene ether (composition) of the present embodiment, it is preferable that the polyphenylene ether is polymerized in a solution state (also referred to herein as “solution polymerization”). By producing an unmodified polyfunctional polyphenylene ether (composition) by solution polymerization, even when using a central phenol having a bulky structure, the above when producing an unmodified polyfunctional polyphenylene ether (composition) A polyphenylene ether component that does not contain the structure of formula (1)′ can be produced with high purity, or the proportion of by-products generated by peroxides can be reduced, and the target product contains the structure of the above formula (1) Polyfunctional modified polyphenylene ether and the like can be produced with high purity.

(Copper extraction and by-product removal step)
In the present embodiment, there are no particular restrictions on the post-treatment method after the completion of the polymerization reaction. Generally, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc. are added to the reaction solution to deactivate the catalyst. A conventionally known method can also be used to remove dihydric phenol by-products produced by polymerization of polyphenylene ether. If the catalyst metal ions described above are substantially deactivated, the mixture is decolorized or post-treated simply by heating. Alternatively, a method of adding a required amount of a known reducing agent to the system is also possible. Known reducing agents include hydroquinone, sodium dithionite, and the like.

(Liquid-liquid separation step)
In the method for producing the unmodified polyfunctional polyphenylene ether (composition) of the present embodiment, water is added to extract the compound in which the copper catalyst is deactivated, and the organic phase and the aqueous phase are subjected to liquid-liquid separation. The copper catalyst may then be removed from the substrate by removing the aqueous phase. This liquid-liquid separation step is not particularly limited, but methods such as static separation and separation using a centrifugal separator can be used. A known surfactant or the like may be used to promote the liquid-liquid separation.

(concentration/drying process)
Subsequently, in the method for producing a polyfunctional modified polyphenylene ether (composition) of the present embodiment, the organic phase containing the unmodified polyphenylene ether (composition) after liquid-liquid separation is volatilized with a solvent. It may be concentrated and dried by This step may be omitted when a subsequent modification reaction (for example, a reaction for introducing the substituent A in the formula (1) to the terminal of the unmodified polyfunctional polyphenylene ether (composition)) is performed.

The method for volatilizing the solvent contained in the organic phase is not particularly limited, but the organic phase is transferred to a high-temperature (for example, drying temperature described later) concentration tank, and the solvent is distilled off to concentrate. method, or a method of concentrating by distilling off toluene using an apparatus such as a rotary evaporator.

The temperature of the drying treatment in the drying step is preferably at least 60° C. or higher, more preferably 80° C. or higher, still more preferably 120° C. or higher, and most preferably 140° C. or higher. Drying the polyfunctional polyphenylene ether composition at a temperature of 60° C. or higher can efficiently reduce the content of high-boiling volatile components in the polyphenylene ether powder.

In order to obtain an unmodified polyfunctional polyphenylene ether (composition) with high efficiency, a method of increasing the drying temperature, a method of increasing the degree of vacuum in the drying atmosphere, a method of stirring during drying, etc. are effective. In particular, the method of increasing the drying temperature is preferable from the viewpoint of production efficiency. In the drying step, it is preferable to use a dryer with a mixing function. The mixing function includes a stirring type dryer, a tumbling type dryer, and the like. As a result, the throughput can be increased, and productivity can be maintained at a high level.

[Modification reaction step]
In the present embodiment, the method of introducing the substituent of A in formula (1) or (8) (for example, the functional group of formula (5) above) to the end of the resulting unmodified polyphenylene ether is halogenated A silyl compound, an aminosilyl compound, or an alkoxysilyl compound can be used for coupling with a functional group such as a hydroxyl group. As the silyl halide compounds, chlorides, bromides and the like are generally used, but other halogens may also be used.

Specific examples of halogenated silyl compounds include methylvinyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, diallyldichlorosilane, trichlorosilyl-2-norbornene, 6-methyldichlorosilyl-2-norbornene, and 6-dimethyldichlorosilyl. -2-norbornene, phenylvinyldichlorosilane, 3-methacryloxypropyldichloromethylsilane, 3-chloropropylmethyldivinylsilane, allylphenyldichlorosilane, diphenylvinylchlorosilane, dimethylvinylchlorosilane, chloromethyldimethylvinylsilane, allyldimethylchlorosilane, methyl Phenylvinylchlorosilane, 5-norbornen-2-yl(ethyl)chlorodimethylsilane, methylvinyldibromosilane, divinyldibromosilane, allylmethyldibromosilane, diallyldibromosilane, tribromosilyl-2-norbornene, 6-methyldibromosilyl- 2-norbornene, 6-dimethyldibromosilyl-2-norbornene, phenylvinyldibromosilane, 3-methacryloxypropyldibromomethylsilane, 3-bromopropylmethyldivinylsilane, allylphenyldibromosilane, diphenylvinylbromosilane, dimethylvinylchlorosilane, bromomethyldimethylvinylsilane, allyldimethylbromosilane, methylphenylvinylbromosilane, 5-norbornen-2-yl(ethyl)bromodimethylsilane, 5-norbornen-2-ylchlorodibromosilane, and the like.

Aminosilyl compounds include methylvinylsilyl-tris(1,2,4-triazole), divinylsilylbis(1,2,4-triazole), allylmethylsilylbis(1,2,4-triazole), diallylsilylbis (1,2,4-triazole), tris(1,2,4-triazolyl)silyl-2-norbornene, 6-methylbis(1,2,4-triazolyl)silyl-2-norbornene, 6-dimethylbis(1 ,2,4-triazolyl)silyl-2-norbornene, phenylvinylsilylbis(1,2,4-triazole), 3-methacryloxypropylmethylsilylbis(1,2,4-triazole), allylphenylsilyl(1 ,2,4-triazole), diphenylvinylsilyl (1,2,4-triazole), dimethylvinylsilyl (1,2,4-triazole), allyldimethylsilyl (1,2,4-triazole), methylphenylvinyl Silyl (1,2,4-triazole), 5-norbornen-2-yl(ethyl)dimethylsilyl (1,2,4-triazole), methylvinylsilyl-triimidazole, divinylsilylbisimidazole, allylmethylsilylbisimidazole , diallylsilylbisimidazole, triimidazolylsilyl-2-norbornene, 6-methylbisimidazolylsilyl-2-norbornene, 6-dimethylbisimidazolylsilyl-2-norbornene, phenylvinylsilylbisimidazole, 3-methacryloxypropylmethylsilylbis imidazole, allylphenylsilylimidazole, diphenylvinylsilylimidazole, dimethylvinylsilylimidazole, allyldimethylsilylimidazole, methylphenylvinylsilylimidazole, 5-norbornen-2-yl(ethyl)dimethylsilylimidazole, 1,3-divinyl-1, 1,3,3-tetramethyldisilazane, bis(dimethylamino)methylvinylsilane, and the like.

Alkoxysilane compounds include trimethoxyvinylsilane, methoxydimethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, methacryloxypropyldimethoxymethylsilane, methacryloxypropyltrimethoxysilane, methacryloxypropyldiethoxymethylsilane, methacryloxypropyltriethoxysilane. , p-styryltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, and the like.

The reaction for introducing the above compound to the end of the unmodified polyphenylene ether is generally a direct reaction with a hydroxyl group, but a reaction with an alkali metal salt of a hydroxyl group may also be used. Alternatively, the silyl halide compound may be reacted with imidazole, triazole, pyrrolidine or piperidine to form an amine compound, which may then be reacted with a hydroxyl group. In the direct reaction between a silyl halide compound and a hydroxyl group, an acid such as hydrogen halide is generated. Therefore, a weak base such as an amine may be used together for the purpose of trapping the acid.

In order to prevent side reactions, the coexisting amines are preferably tertiary amines. Specific examples of coexisting amines include trimethylamine, diethylmethylamine, triethylamine, diethylamine, di-n-propylamine, tri-n-propylamine, triisopropylamine, di-n-butylamine, and di-n-butylmethyl. Amine, di-n-butylethylamine, di-n-propylmethylamine, diisopropylmethylamine, di-n-propylethylamine, diisopropylethylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, di-t -Butylamine, diisobutylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, dimethylaminopyridine and the like.

Amines to be coexisted are preferably trimethylamine, diethylmethylamine, triethylamine, tri-n-propylamine, triisopropylamine, di-n-butylmethylamine, di-n-butylethylamine, di-n-propylmethylamine. , di-n-propylethylamine, diisopropylethylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, and dimethyl aminopyridine, more preferably triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, tetramethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine , pyridine, dimethylaniline, and dimethylaminopyridine.

In addition, moisture causes not only unfavorable side reactions during the reaction, but also hydrolysis reactions after the reaction, which may reduce the reaction yield. It is preferable to keep A preferred amount of water in the reaction system is less than 200 ppm, more preferably less than 100 ppm.

Excess amines may be removed from the system after the reaction in order to prevent side reactions or formation of by-products during purification. Amines with a low boiling point can be removed from the reaction system by distillation or the like. The residual amine content before the purification step is less than 10,000 ppm.

As a preferred embodiment for achieving a high modification rate in the modification reaction step, the amount of the silyl halide used in the modification reaction is 1.00 times or more moles per 1 mole of hydroxyl groups in the polymer. And it is less than 4-fold mol, preferably 1.05-fold mol to 3-fold mol, more preferably 1.1-fold mol to 2.5-fold mol. If the amount of the silyl halide used is less than 1.00 moles per 1 mole of the hydroxyl group, a sufficient modification rate cannot be obtained. may occur, resulting in reduced purification yields. The amount of the amine coexisting for the purpose of trapping the acid during the reaction is preferably 1.00-fold mol or more and less than 6-fold mol, more preferably 1.05-fold mol to 4-fold mol, with respect to 1 mol of hydroxyl group. It is preferably 1.1-fold molar to 4-fold molar. When the amount of amine used is less than 1.00 times mole per mole of hydroxyl group, a sufficient modification rate cannot be obtained, and when the amount is 6 times mole or more, the effect on the conversion rate does not change, but a large amount of amine is used after the reaction. Not preferred because it requires removal.

Although the modification reaction temperature is not particularly limited, it is preferable that the unmodified polyphenylene ether is not precipitated from the unmodified polyphenylene ether and the unmodified polyphenylene ether solution consisting of its good solvent. Also, a combination of a plurality of temperature conditions may be used.

After the denaturation reaction, if there is an excess silyl halide compound, it may be reacted with an alcohol such as methanol or ethanol for treatment such as deactivation.

After the modification reaction, in order to remove by-products such as amine salts, etc., the object may be filtered or washed with water or an acidic or alkaline aqueous solution. The desired product may be collected by dropping it inside and reprecipitating. Alternatively, after washing the polymer solution, the solvent may be distilled off under reduced pressure to recover the desired polymer.

The method for producing the polyfunctionally modified polyphenylene ether (composition) of the present embodiment is not limited to the method for producing the polyfunctionally modified polyphenylene ether composition of the present embodiment described above. The order or number of the by-product removal step, the liquid-liquid separation step, and the concentration/drying step may be appropriately adjusted.

<(B) Cross-linking aid>
The curable resin composition of the present embodiment comprises (B) an acrylic or methacrylic cross-linking aid having a molecular weight of 400 or less and a total number of acrylic or methacrylic groups in one molecule of 3 or less. element.

Component (B) has a molecular weight of 400 or less. The smaller the molecular weight, the lower the viscosity in the resin solution and molten state, the higher the fluidity, and the better the moldability. In addition, the larger the molecular weight, the lower the dielectric loss tangent of the cured product, and the lower the vapor pressure. Therefore, for example, after uniformly dissolving the resin composition in an organic solvent, the organic solvent is evaporated by heating (also called a drying process). ), the amount of evaporation of component (B) tends to decrease. From such a viewpoint, the preferred molecular weight range is 50-400, more preferably 100-350, still more preferably 150-300, and particularly preferably 200-280.

The total number of acrylic or methacrylic groups in one molecule of component (B) is 3 or less. Tg, which is a measure of heat resistance, tends to increase as the total number of acrylic or methacrylic groups increases. On the other hand, the smaller the total number of acrylic or methacrylic groups, the lower the viscosity of the resin composition, the better the moldability, and the higher the toughness of the cured product.
From such a point of view, the total number of acryl groups or methacryl groups is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

<Reason for manifestation of effect of cross-linking aid>
Since the cross-linking aid of the component (B) has a low molecular weight, by blending it with the modified polyphenylene ether of the component (A), the viscosity in the resin solution and molten state is lowered, the fluidity is increased, and good molding is achieved. show gender. Furthermore, since the cross-linking aid has a highly reactive acrylic group or methacrylic group, it exhibits good reactivity with the vinylsilyl group, which is the terminal unsaturated group of the component (A).

In addition, when the crosslink density is excessively increased, the uniformity of the cured product is reduced, the dielectric loss tangent is high, and the cured product tends to be brittle. Since the number is limited to 3 or less, an excessive increase in the crosslink density of the cured product is suppressed, and a cured product with high uniformity is obtained, so that the cured product has high toughness and low dielectric loss tangent.

Specific examples of the (B) component cross-linking aid include:
isobornyl methacrylate, isobornyl acrylate, stearyl methacrylate, stearyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, benzyl methacrylate, benzyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl acrylates, 2-hydroxyethyl acrylate, isobutyl acrylate, isoamyl acrylate, 2,3-dibromopropyl acrylate, stearyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, 2-dimethylaminoethyl acrylate, hexyl acrylate, 1H , 1H,2H,2H-heptadecafluorodecyl acrylate, ter-butyl acrylate, 4-hydroxybutyl acrylate, 2-phenoxyethyl acrylate, 3-(trimethoxysilyl)propyl acrylate, adamantane-1-yl-acrylate, allyl acrylate, benzyl acrylates, 4-tert-butylcyclohexyl acrylate, 2-cyanoethyl acrylate, dicyclopentanyl acrylate, dodecyl acrylate, glycidyl acrylate, hexadecyl acrylate, isobornyl acrylate, isononyl acrylate, 3-(methoxydimethylsilyl)-propyl acrylate, 2-methyladamantan-2-yl acrylate, 1-methylcyclopentyl acrylate, nonafluorohexyl acrylate, octyl acrylate, pentabromobenzyl acrylate, phenyl acrylate, N-succinimidyl acrylate, tetrahydrofurfuryl acrylate, tetradecyl acrylate, trimethylsilyl acrylate,

Butyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, isobutyl methacrylate, isoamyl methacrylate, 2,3-dibromopropyl methacrylate, stearyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate , 2-dimethylaminoethyl methacrylate, hexyl methacrylate, 1H,1H,2H,2H-heptadecafluorodecyl methacrylate, ter-butyl methacrylate, 4-hydroxybutyl methacrylate, 2-phenoxyethyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, adamantane-1-yl-methacrylate, allyl methacrylate, benzyl methacrylate, 4-tert-butylcyclohexyl methacrylate, 2-cyanoethyl methacrylate, dicyclopentanyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, hexadecyl methacrylate, isobornyl methacrylate, isononyl methacrylate , 3-(methoxydimethylsilyl)-propyl methacrylate, 2-methyladamantan-2-yl methacrylate, 1-methylcyclopentyl methacrylate, nonafluorohexyl methacrylate, octyl methacrylate, pentabromobenzyl methacrylate, phenyl methacrylate, N-succinimidyl methacrylate, tetrahydrofurfuryl methacrylate, tetradecyl methacrylate, trimethylsilyl methacrylate,
etc.

Among these, isobornyl methacrylate, isobornyl acrylate, stearyl methacrylate, stearyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and the like are used from the viewpoint of the balance between Tg, which is a measure of heat resistance, and the dielectric loss tangent. Preferred are isobornyl methacrylate, dicyclopentanyl methacrylate and stearyl acrylate.

As a result, the curable resin composition of the present embodiment provides a uniform cured product, and satisfies all of the sufficient Tg of the cured product, low dielectric properties, copper foil adhesion, and low coefficient of linear expansion. Become.

<Composition ratio of component (A) and component (B)>
The curable resin composition of the present embodiment is not limited by the composition ratio of the component (A) and the component (B), but the higher the composition ratio of the component (A), the higher the Tg of the resin tends to be. , the higher the composition ratio of the component (B), the lower the viscosity of the composition. From such a point of view, the composition ratio of component (A) and component (B) is preferably 10:90 to 99:1, more preferably 50:50 to 90:10, still more preferably 60:40 to 80:20.

<(C) Initiator>
The curable resin composition of this embodiment may contain an initiator. Although the initiator is not particularly limited, organic peroxides can be mentioned, and those having a 1-minute half-life temperature within the range of 155° C. to 180° C. are preferred from the viewpoint of stability and reactivity during storage of the composition. Preferably, for example, t-hexylperoxyisopropyl monocarbonate (1-minute half-life temperature, 155.0° C.), t-butylperoxy-3,5,5-trimethylhexanoate (166.0° C.), t -Butyl peroxylaurate (159.4°C), t-butylperoxyisopropyl monocarbonate (158.8°C), t-butylperoxy 2-ethylhexyl monocarbonate (161.4°C), t-hexylperoxy Benzoate (160.3°C), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (158.2°C), t-butylperoxyacetate (159.9°C), 2,2-di- (t-butylperoxy)butane (159.9°C), t-butylperoxybenzoate (166.8°C), n-butyl 4,4-di-(t-butylperoxy)valerate (172.5°C) , di(2-t-butylperoxyisopropyl)benzene (175.4°C), dicumyl peroxide (175.2°C), di-t-hexyl peroxide (176.7°C), 2,5-dimethyl -2,5-di(t-butylperoxy)hexane (179.8°C) and t-butylcumyl peroxide (173.3°C).

Among these, organic peroxides include t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxybenzoate, di(2-t-butyl At least one selected from the group consisting of peroxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and t-butylcumyl peroxide is preferred.

The blending amount of component (C) is preferably 0.001 to 10 phr based on the total amount of components (A) and (B). When the amount of the component (C) is 0.001 phr or more, the effect of the component (C) is sufficiently exhibited, and the progress of the curing reaction is accelerated, thereby tending to increase the Tg of the cured product. Further, when the content is 10 phr or less, the amount of the initiator and its decomposition products remaining in the cured product can be reduced, and there is a tendency to prevent an increase in the dielectric loss tangent of the cured product. From such a point of view, the amount of component (C) is more preferably 0.1 to 5 phr, more preferably 0.5 to 2 phr.

<Solvent>
An organic or inorganic solvent can be added to the curable resin composition of the present embodiment, if necessary. By adding an organic solvent, the viscosity of the composition can be reduced, and such a curable resin composition can improve the impregnation of glass fibers in the case of impregnating glass fibers to produce a laminated plate. There are things that can be improved.
Examples of such organic solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), ethyl acetate, etc., which have low boiling points and are removed by evaporation from the resin composition. Toluene and methyl ethyl ketone are preferred from the viewpoint of ease of use.

<Other ingredients>
Additives such as flame retardants, elastomers, and fillers can be added to the curable resin composition of the present embodiment within a range that does not impair its purpose.

Hereinafter, the present embodiment will be described in more detail based on Production Examples and Examples, but the present embodiment is not limited to the following Production Examples and Examples.

First, the measurement methods and evaluation criteria for each physical property and evaluation will be described below.

｛式（１４）中、複数のＲ^２１は、各々独立に、水素原子；置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基；及びハロゲン原子；から成る群から選択される少なくとも１つを表し、置換されていてもよい炭素数１～６の飽和又は不飽和の炭化水素基が好ましく、より好ましくは、メチル基、エチル基、ｎ－プロピル基、ビニル基、アリール基、エチニル基、又はプロパルギル基であり、さらに好ましくは、メチル基、又はエチル基であり、特に好ましくはメチル基である。上記置換基としては、ハロゲン原子等が挙げられる。
式（１４）中、２つのＲ^２１は、変性ポリフェニレンエーテル含有組成物について低誘電特性、適度な金属剥離性、低溶液粘度、硬化時の十分なＴｇなどの全てを有するという観点から、同時に水素原子ではないことが好ましく、かつ／又は、一方が上記式（３）で表される部分構造、もう一方が水素原子、メチル基又はエチル基のいずれかであるという組み合わせではないことが好ましい。
式（１４）中、複数のＲ^２２は、各々独立に、水素原子；置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基；及びハロゲン原子；から成る群から選択される少なくとも１つを表し、水素原子、又は置換されていてもよい炭素数１～６の飽和又は不飽和の炭化水素基が好ましく、より好ましくは、水素原子、メチル基、エチル基、又はｎ－プロピル基であり、さらに好ましくは、水素原子、又はメチル基である。上記置換基としては、ハロゲン原子等が挙げられる。
ｃは１～１００の任意の整数である｝
で表される副生成物に特有の末端フェノキシユニット、及び式（１５）：

｛式（１５）中、複数のＲ^２１は、各々独立に、水素原子；置換されていてもよい炭素数１～６の炭化水素基、置換されていてもよい炭素数６～１２のアリール基；及びハロゲン原子；から成る群から選択される少なくとも１つを表し、置換されていてもよい炭素数１～６の飽和又は不飽和の炭化水素基が好ましく、より好ましくは、メチル基、エチル基、ｎ－プロピル基、ビニル基、アリール基、エチニル基、又はプロパルギル基であり、さらに好ましくは、メチル基、又はエチル基であり、特に好ましくはメチル基である。上記置換基としては、ハロゲン原子等が挙げられる。 (1) polyphenylene ether (modified polyphenylene ether having the structure of formula (1), one or more (-Yn-A) in the structure of formula (1) is (-Yn-H), and all (- Yn-A) is not (-Yn-H), and a polyphenylene ether in which all (-Yn-A) are (-Yn-H) in the structure of formula (1) (main component polyphenylene ether) ) existence ratio (1-1)
The modified polyphenylene ether compositions obtained in Examples and Comparative Examples and the polyhydric phenol used as a raw material were dissolved in deuterated chloroform, and ¹ H-NMR measurement (500 MHz manufactured by JEOL) was performed using tetramethylsilane as an internal standard. rice field.
(1-2)
A polyhydric phenol peak contained in the product was identified from the peak position due to the central phenol site.
(1-3)
The central phenol unit of the main component polyphenylene ether represented by formula (2), and formula (14):

{In formula (14), a plurality of R ²¹ are each independently a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms and a halogen atom; represents at least one selected from the group consisting of, optionally substituted saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms, more preferably methyl group, ethyl group , n-propyl group, vinyl group, aryl group, ethynyl group or propargyl group, more preferably methyl group or ethyl group, particularly preferably methyl group. A halogen atom etc. are mentioned as said substituent.
In formula (14), two R ²¹ are simultaneously hydrogen from the viewpoint of having all of low dielectric properties, adequate metal stripping properties, low solution viscosity, sufficient Tg upon curing, etc. for the modified polyphenylene ether-containing composition. It is preferably not an atom, and/or preferably not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group.
In formula (14), a plurality of R ²² are each independently a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; represents at least one selected from the group consisting of, preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom , a methyl group, an ethyl group or an n-propyl group, more preferably a hydrogen atom or a methyl group. A halogen atom etc. are mentioned as said substituent.
c is any integer from 1 to 100}
and a terminal phenoxy unit specific to the by-product of formula (15):

{In formula (15), a plurality of R ²¹ are each independently a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms and a halogen atom; represents at least one selected from the group consisting of, optionally substituted saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms, more preferably methyl group, ethyl group , n-propyl group, vinyl group, aryl group, ethynyl group or propargyl group, more preferably methyl group or ethyl group, particularly preferably methyl group. A halogen atom etc. are mentioned as said substituent.

In formula (15), two R ²¹ are simultaneously hydrogen, from the standpoint of having all of low dielectric properties, adequate metal stripping properties, low solution viscosity, sufficient Tg upon curing, etc. for the modified polyphenylene ether-containing composition. It is preferably not an atom, and/or preferably not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group.

A plurality of R ²² each independently consists of a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; represents at least one selected from the group, preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group , or an n-propyl group, more preferably a hydrogen atom or a methyl group. A halogen atom etc. are mentioned as said substituent.

｛式中、
Ｃ：式（１４）で表される副生成物に特有の末端フェノキシユニットのＨ^１、及びＲ^２２’に起因するピーク面積の積算値；
Ｄ：式（１５）で表される副生成物に特有のジフェニルユニットの中心フェノール内部のＲ^２２”に起因するピーク面積の積算値；
Ｅ：式（２）で表される主成分ポリフェニレンエーテルの中心フェノール部位に起因するピーク面積の積算値；及び
Ｆ：積分値Ｃを求めたピークに該当する式（２）で表される中心フェノール部位由来のプロトン数；
である｝
に従って定量した。 d and e are each independently any integer from 1 to 100}
The diphenyl units peculiar to the by-product represented by are assigned to the peaks in the obtained NMR spectrum, respectively, and the abundance ratio of various polyphenylene ethers is calculated by the following formula (15):

{In the formula,
C: integrated value of peak areas resulting from H ¹ and R ²² ' of the terminal phenoxy unit specific to the by-product represented by formula (14);
D: Integrated value of the peak area due to R ²² ″ inside the central phenol of the diphenyl unit unique to the by-product represented by formula (15);
E: the integrated value of the peak area due to the central phenol site of the main component polyphenylene ether represented by formula (2); and F: the central phenol represented by formula (2) corresponding to the peak for which the integral value C was obtained number of protons from the site;
is}
quantified according to

In addition, H ¹ of the terminal phenol of the by-product represented by the peak due to the central phenolic site of the main component polyphenylene ether represented by the formula (2) and the formula (14) used in the examples and comparative examples, and The peak due to R ²² ′ and the peak due to R ²² ″ inside the central phenol of the by-product represented by formula (15) appear in the following regions.
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (1H): 2.8 to 3.2 ppm
1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane (1H): 4.0 to 4.3 ppm
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane (4H): 6.95-7.0ppm
Terminal phenoxy unit (3H) of the by-product represented by formula (14): 7.05 to 7.1 ppm
Diphenyl (4H) as a by-product represented by formula (15): 7.34 to 7.4 ppm

(2) The ratio of the integrated value of peaks appearing at 7.6 to 8.3 ppm to the integrated value of peaks derived from the structure of formula (2) (abundance ratio of peroxide peak)
In the above ¹ H-NMR measurement, the integrated value of the peak area due to the central phenolic site of the main component polyphenylene ether represented by formula (2) is E, and the peroxide that appears in the region of 7.6 to 8.3 ppm The abundance ratio of the peroxide peak was analyzed by calculating the integrated value G of the derived impurity peak (that is, the peroxide peak) area and substituting it into the following formula (17).

(3) number average molecular weight (Mn)
As a measuring device, Showa Denko KK gel permeation chromatography System 21 is used, a calibration curve is prepared with standard polystyrene and ethylbenzene, and the number average molecular weight (Mn ) was measured.

As standard polystyrene, molecular weights of 1,300 and 550 were used.

As the column, two K-805L columns manufactured by Showa Denko KK were connected in series. Chloroform was used as the solvent, the solvent flow rate was 1.0 mL/min, and the column temperature was 40°C. A 1 g/L chloroform solution of the modified polyphenylene ether composition was prepared and used as a measurement sample. The UV wavelength of the detector was 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

The number average molecular weight (Mn) (g/mol) was calculated from the peak area ratio based on the curve showing the molecular weight distribution obtained by GPC based on the above measurement data.

(4) Glass transition temperature (Tg)
The glass transition temperature of the modified polyphenylene ether composition was measured using a differential scanning calorimeter DSC (manufactured by PerkinElmer - Pyrisl). After heating from room temperature to 200° C. at a rate of 20° C./min in a nitrogen atmosphere, the temperature was lowered to 50° C. at a rate of 20° C./min, and then the glass transition temperature was measured at a rate of 20° C./min.

(5) Number of A substituents contained in the composition Modified polyphenylene ether composition, and 1,3,5-trimethoxybenzene standard product as an internal standard sample (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 168.19) A prescribed amount was taken, dissolved in deuterated chloroform containing trimethylsilane, and subjected to ¹ H-NMR measurement (500 MHz manufactured by JEOL).

Next, the integrated value of the proton peak derived from the methoxy group of 1,3,5-trimethoxybenzene (3.7 to 3.8 ppm: 9H) and the proton at the C=C bond terminal of the methacrylic group on the high magnetic field side Calculate the integrated value of the peak (5.5 ~ 5.9 ppm: 1H) appearing in the modified polyphenylene ether from these integrated values and the weight of the polyphenylene ether composition and 1,3,5-trimethoxybenzene used for measurement The number of methacrylic groups (unit μmol/g) per 1 g of the composition was calculated.

(6) Viscosity of toluene solution of modified polyphenylene ether composition (liquid viscosity)
2 g of the modified polyphenylene ether composition and 3 g of toluene were weighed. A 40 wt % toluene solution was prepared by stirring these for 1 hour using a stirrer and a magnetic stirrer and completely dissolving until the solution became clear. The liquid viscosity of this solution was measured using a Brookfield viscometer under conditions of 25° C. and 30 rpm.

(7) Modification rate The modification rate was calculated from the change in the amount of hydroxyl groups before and after the reaction by IR measurement in carbon disulfide according to the method described in Japanese Patent Publication No. 2004-502849 (Patent Document 3).

(8) Preparation of Cured Product A film-shaped test piece having a thickness of 0.1 to 0.3 mm was produced by a pressing method under the following conditions.
A polymer, a cross-linking aid, etc. were added to toluene and uniformly dissolved overnight at room temperature, and then Perbutyl P manufactured by NOF Corporation was added. This was applied to the shine side of copper foil, dried at 120° C. for 10 minutes, and the obtained solid resin composition was pulverized in an agate mortar.
A Teflon (registered trademark) sheet with a thickness of 100 μm is cut into a shape of 60×60 mm, the Teflon (registered trademark) sheet is placed on the shiny side of the copper foil, and about 1.5 times the theoretical value (specific gravity 6 × 6 × 0.01 × 1.5 = 0.54 g) of the above solid resin composition was added, and the shiny surface of copper foil was covered, press pressure 40 (kg / cm ² ), under constant vacuum conditions. , press hardened under the following temperature conditions.
Room temperature to 50°C, 4°C/min, 50°C Hold 1 min 50°C to 160°C 4°C/min, 160°C Hold 3 min 160°C to 220°C 4°C/min,
220°C Hold time: 60 minutes

(9) Measurement of Tg of cured product Using Hitachi High-Tech Science (DMS6100), the glass transition temperature (Tg) of the cured product was measured by DMA under the following conditions.
A dynamic viscoelasticity test was performed by cutting a test piece into a size that allows suitable measurement in the entire temperature range of the DMA device.
Test piece: Strip, Measurement mode: Tensile mode Test start temperature: Room temperature Heating rate: 4°C/min Test maximum temperature: 300°C
Maximum temperature retention time: 5 minutes Measurement frequency: 1 Hz
Analysis: The tan δ peak was taken as Tg. Furthermore, the storage elastic modulus at a temperature higher by 30° C. was read from the tan δ peak and used to calculate the crosslink density.

(10) Dielectric loss tangent measurement of cured product A cured product with a thickness of 0.1 to 0.3 mm is cut into a shape of 50 × 50 mm, and a network analyzer (KEYSIGHT TECHNOLOGIES PNA N5227B, cavity resonator method, using a split cylinder resonator) was used to measure the dielectric loss tangent at 10 GHz.

(11) Measurement of Coefficient of Linear Expansion The coefficient of linear expansion was obtained by measuring under the following conditions using a sample cut from a test piece for dielectric loss tangent measurement using Hitachi High-Tech Science TMA7100. Measurement mode: Tensile Size: width 2mm, length 10mm, thickness 0.2mm
Test start temperature: -50°C
Heating rate: 10°C/min Test maximum temperature: 250°C
Maximum temperature retention time: 5 minutes

(12) Measurement of Copper Foil Adhesive Strength Adhesive strength to copper foil was measured by a T-peel test. A small amount of glass beads (for spacer) with a particle size of about 40 μm (20-40 μm) are added to the varnish prepared in a predetermined ratio. A 35 μm thick copper foil, which is an adherend, is cut into 50×80 mm, and a polyimide tape (10 mm wide and 55 μm thick) is attached to the roughened surface of the copper foil. The prepared varnish is poured into the obtained frame, left overnight, dried at 120° C. for 10 minutes, and the polyimide tape is peeled off to obtain a test piece. Copper foils of the same size are overlapped so that the resin layer is sandwiched between the roughened surfaces, and a Teflon (registered trademark) sheet of about 20 mm is sandwiched at one end to secure a gripping margin. Form with a vacuum press under certain conditions. The obtained copper foil is cut to prepare a 10 mm*80 mm piece.
A T-peel test is performed using a tensile tester (Instron 59R5582 model) under the following conditions.
Assumed test piece: 10 mm x 80 mm n = 2 test and take the average value.
Measurement conditions: test temperature room temperature (about 23 ° C.),
Test speed: 50 mm/min, test length: about 30 mm.

Hereinafter, the method for producing the unmodified polyphenylene ether composition of each Production Example and Comparative Production Example, and the method for producing the modified polyphenylene ether composition of each Example and Comparative Example will be described.

(Production example 1)
0.1026 g preconditioned in a 1.5 liter jacketed reactor equipped with a sparger for oxygen-containing gas introduction at the bottom of the reactor, stirred turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor. of cuprous oxide and 0.7712 g of 47% hydrogen bromide, 0.2471 g of N,N'-di-t-butylethylenediamine, 3.6407 g of dimethyl-n-butylamine, 1.1962 g of di -n-butylamine, 894.04 g toluene, 73.72 g 2,6-dimethylphenol, 26.28 g 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (Manufactured by ADEKA: AO-30) was added. Next, while these components were vigorously stirred, air was introduced into the reactor at a rate of 1.05 L/min through a sparger, and at the same time, a heating medium was passed through the jacket so as to maintain the polymerization temperature at 40°C. After 160 minutes from the start of air introduction, the air was turned off and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (Dojindo Laboratories reagent) was added as 100 g of an aqueous solution to the polymerization mixture, Warmed to 70°C. After incubating at 70° C. for 2 hours, extracting the catalyst and removing the by-product diphenoquinone, the mixed solution was transferred to a centrifuge manufactured by Sharpless Co., and the unmodified polyphenylene ether composition solution (organic phase) and the catalyst It separated into an aqueous phase in which the metals were transferred. The resulting unmodified polyphenylene ether composition solution was transferred to a jacketed concentration tank, and concentrated by distilling off toluene until the solid content in the unmodified polyphenylene ether composition solution reached 55% by mass. Next, toluene was further distilled off from the concentrate using an oil bath and a rotary evaporator set at 230° C., and the solid content was dried to obtain an unmodified polyphenylene ether composition.

A stirrer was placed in a 300 ml three-necked flask, a Dimroth condenser equipped with a three-way cock was installed in the main tube, and a rubber stopper with a thermometer inserted was attached to one side tube. 20.0 g of the unmodified polyphenylene ether composition obtained in the above step was introduced from the other side tube, and a rubber stopper was attached. After the inside of the flask was replaced with nitrogen, 60.0 g of ultra-dehydrated toluene manufactured by Wako Pure Chemical Industries, Ltd. was used with a syringe while stirring the inside with a magnetic stirrer. Then 5.72 g of triethylamine was added into the system. After that, 3.38 g of dimethylvinylchlorosilane was collected in a syringe and dropped into the system through a rubber plug. Stirring was continued at 30° C. for 3 hours from the end of dropping, and then 0.86 g of super-dehydrated methanol manufactured by Wako Pure Chemical Industries was added to the system to stop the reaction.

Then, triethylamine was distilled off from the reaction solution together with toluene under reduced pressure. After that, super-dehydrated toluene manufactured by Wako Pure Chemical Industries, Ltd. was added to the reaction solution to adjust the solid content concentration to 20% by weight. After that, the polymer solution was added dropwise to methanol (5 times the weight of the organic layer) while stirring. Next, the precipitate was filtered, and the filter cake was vacuum-dried at 110° C. for 1 hour to obtain a modified polyphenylene ether composition. It was confirmed from the results of NMR measurement that the reaction proceeded. The resulting modified polyphenylene ether composition (PPE-1) had a molecular weight of Mw=4,810 and Mn=2,610. Also, the conversion rate of the obtained PPE-1 was 96%. The resulting polymer had a toluene 40 wt % solution viscosity of 23 mPa·s.

(Example 1-2, Comparative Example 1-2)
A curable resin composition solution was prepared according to the formulation shown in Table 1, and the cured product obtained by the above method was evaluated. Table 1 shows the results.

Abbreviations in Table 1 are as follows.

From the above results, in Examples, a uniform cured product is obtained, and a curable resin composition that satisfies all of the sufficient Tg of the cured product, low dielectric properties, copper foil adhesion, and a low coefficient of linear expansion is obtained. However, in Comparative Examples, a uniform cured product could not be obtained, or a curability that satisfies all of the sufficient Tg of the cured product, low dielectric properties, copper foil adhesion, and low coefficient of linear expansion A resin composition could not be obtained.

The curable resin composition of the present invention is obtained by blending a modified polyphenylene ether having a specific structure and a specific cross-linking aid, thereby obtaining a uniform cured product, sufficient Tg of the cured product, low dielectric properties, It is possible to provide a curable resin composition that satisfies both copper foil adhesion and a low coefficient of linear expansion and is useful as a substrate material.

Claims (12)

A curable resin composition comprising the following components (A) and (B).
(A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1):

{In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, and each Y is independently represented by the following formula (4). a divalent linking group having the structure shown, n represents the number of repetitions of Y, each independently an integer of 0 to 200, and at least 1 in a (-Y _n -A) Each of n is an integer of 1 or more, and A represents a hydrogen atom or a silyl group-containing derivative capable of bonding with a polyphenylene ether structure, except when all are hydrogen atoms;

In formula (2), X is an a-valent linking group, and a plurality of R ⁵ are each independently represented by a linear alkyl group having 1 to 8 carbon atoms and the following formula (3) any of the partial structures, each k is independently an integer of 1 to 4,

In formula (3), a plurality of R ¹¹ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹² are each independently an optionally substituted carbon an alkylene group having a number of 1 to 8, b is each independently 0 or 1, R ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituted represents any of the phenyl groups,

In formula (4), a plurality of R ²¹ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom, and two R ²¹ are not hydrogen atoms at the same time, and two R ²¹ are, one of which is a partial structure represented by the above formula (3), and the other is a hydrogen atom, a methyl group, or A plurality of R ²² are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, or an optionally substituted C 6 to 12 aryl groups and halogen atoms}
(B) an acrylic or methacrylic cross-linking aid having a molecular weight of 400 or less and a total number of acrylic or methacrylic groups in one molecule of 3 or less; 2. The curable resin composition according to claim 1, further comprising (C) an initiator. In the formula (2), at least one of the R ⁵ is a partial structure represented by the formula (3), and the carbon atom of the benzene ring to which -O- in the formula (2) is bonded is When the 1-position is used, R ⁵ having the partial structure represented by the formula (3) is bonded to one carbon atom at the 2- or 6-position, and a hydrogen atom is attached to the other carbon atom at the 2- or 6-position, 3. The curable resin composition according to claim 1, wherein a methyl group or an ethyl group is bonded. 4. The curable resin composition according to claim 3, wherein the partial structure represented by formula (3) is a tert-butyl group. The curable resin composition according to any one of claims 1 to 4, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 µmol/g. The curable resin composition according to any one of claims 1 to 5, wherein R ²¹ in formula (4) is a methyl group. A in the formula (1) is represented by the following formula (5):

{In the formula (5), the plurality of R ³¹ and R ³⁴ are each independently a C _1-30 divalent hydrocarbon group, and the plurality of R ³² and R ³³ are each independently a C _{1 to 30} monovalent hydrocarbon groups, aryl groups, alkoxy groups, allyloxy groups, amino groups, or hydroxyalkyl groups, and B is a C _{1 to 30} carbon containing an olefinic carbon-carbon double bond a hydrogen-based substituent, a portion of which may be substituted with a hydrogen atom, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group; , and t is an integer from 0 to 8}
Represented by the curable resin composition according to any one of claims 1 to 6. A in the formula (1) is represented by the following formulas (6) and/or (7):

{In formula (6) and/or formula (7), a plurality of R ³¹ and R ³⁴ are each independently a C _1-30 divalent hydrocarbon group, and a plurality of R ³² and R ³³ are each independently a C _1-30 monovalent hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group, and each R ³⁵ is each independently a hydrogen atom, a hydroxyl group, or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and R ³⁶ is a C _1-3 divalent is a hydrocarbon group or amino group, or an oxygen atom, and part of the hydrocarbon group is substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. and s, t and u are each independently an integer from 0 to 8}
The curable resin composition according to any one of claims 1 to 7, represented by. The curable resin composition according to any one of claims 1 to 8, wherein the component (B) is dicyclopentanyl methacrylate or dicyclopentanyl acrylate. The curable resin composition according to any one of claims 1 to 8, wherein the component (B) is isobornyl methacrylate or isobornyl acrylate. The curable resin composition according to any one of claims 1 to 8, wherein the component (B) is stearyl methacrylate or stearyl acrylate. (D) The curable resin composition according to any one of claims 1 to 11, further comprising a solvent.