JP2022077400A - Modified polyphenylene ether, production method thereof, prepreg and laminate - Google Patents

Abstract

To provide modified polyphenylene ether having a high glass transition temperature after being hardened.SOLUTION: Modified polyphenylene ether of the present invention is represented by formula (1) and has a number average molecular weight of 500-15,000 in terms of polystyrene. The modified polyphenylene ether has a content of methacrylic acid of less than 200 ppm, a total content of methacrylic acid anhydride and vinyl methacrylate of less than 200 ppm, a content of an organic amine catalyst of less than 200 ppm, and a content of a chloride ion of less than 1,500 ppm based on the total amount of the modified polyphenylene ether.SELECTED DRAWING: None

Description

The present invention relates to a modified polyphenylene ether, a method for producing a modified polyphenylene ether, a prepreg, and a laminate.

Polyphenylene ether (hereinafter, also referred to as "PPE") has excellent high-frequency characteristics, flame retardancy, and heat resistance, and is therefore widely used as a material in the electric / electronic field, the automobile field, and various other industrial material fields. There is. In recent years, it is expected that polyphenylene ether, which has an extremely low molecular weight, is more effective for electronic material applications such as substrate materials than ordinary high molecular weight polyphenylene ether. Therefore, Patent Document 1 proposes a low molecular weight polyphenylene ether which uses 2,6-dimethylphenol as a raw material and has a lower dielectric weight than a general high molecular weight polyphenylene ether, and an efficient production method thereof.

On the other hand, when polyphenylene ether is used as a molding material for a substrate material or the like, it is required to have not only excellent dielectric properties but also excellent heat resistance and moldability. However, conventional polyphenylene ethers are thermoplastic and may not be able to obtain sufficient heat resistance. Therefore, 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 describes a modification having a predetermined polyphenylene ether moiety in the molecular structure and having at least one p-ethenylbenzyl group, m-ethenylbenzyl group, or the like at the end of the molecule. Polyphenylene ether compounds have been described.
Further, Patent Document 3 describes a modified polymer having a polyphenylene ether moiety in a molecular structure and having a methacrylic group at the end of the molecule.

In order to easily secure the heat resistance of the terminal-modified thermosetting polyphenylene ether as in the compounds disclosed in Patent Document 2 and Patent Document 3, cross-linking between the thermosetting polyphenylene ether and the thermosetting cross-linking agent A method of increasing the density is effective. Therefore, a polyfunctional polyphenylene ether having a plurality of terminals in one molecule is required. Therefore, low-molecular-weight polyfunctional polyphenylene ethers obtained by polymerizing in the presence of a polyfunctional phenol compound have been proposed in Patent Documents 4, 5 and 6. Since these polyfunctional polyphenylene ethers have a branched structure, the solution viscosity is lower than that of the linear polymer at the same molecular weight, and the fluidity is higher than that of the linear polymer even at the same molecular weight. A polymer having a high molecular weight can be used, and improvement in the physical properties of the cured product can be expected. In addition, since the number of cross-linking reaction points increases, it can be expected that the cross-linking reaction can be easily controlled in addition to contributing to the improvement of the above-mentioned physical properties.

Japanese Unexamined Patent Publication No. 2004-99824 Japanese Unexamined Patent Publication No. 2004-339328 Japanese Patent No. 5147397 US Pat. No. 9012572 Japanese Patent No. 5176336 Japanese Patent No. 5439700

Generally, a thermosetting composition for a substrate capable of high frequency is a support material such as a glass cloth made of a varnish in which a low-dielectric polymer material such as modified polyphenylene ether, a thermosetting cross-linking agent, a cross-linking initiator and the like are dissolved. It is obtained through a step of impregnating with and thermosetting. If a modified polyphenylene ether composition capable of exhibiting a high glass transition temperature after curing is used as a raw material, the addition rate of a crosslinking initiator or the like that causes deterioration of the dielectric properties can be reduced, and the substrate material has more excellent dielectric properties. ..

The present invention has been made in view of the above problems, and an object of the present invention is to provide a modified polyphenylene ether having a high glass transition temperature after curing.

・・・式（１）
（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（－Ｙｎ－Ａ）中少なくとも１つのｎは１以上の整数であり、Ａは、下記式（５）で表される基である。

・・・式（２）
式（２）中、Ｘはａ価の任意の連結基であり、Ｒ^４は炭素数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、－Ｏ－が結合するベンゼン環の炭素原子を１位とし、２位又は６位の少なくとも一方の炭素原子に結合しており、ｋは各々独立に１～４の整数である。

・・・式（３）
式（３）中、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、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のアルキル基及び置換されていてもよいフェニル基のいずれかである。

・・・式（４）
式（４）中、Ｒ^２１は各々独立に、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。

・・・式（５）
上記式（５）中、Ｒ^３１は各々独立に、水素原子、水酸基、炭素数１～３０の炭化水素基（例えば、鎖状炭化水素基、環状炭化水素基）、アリール基、アルコキシ基、アリロキシ基、アミノ基、及びヒドロキシアルキル基のいずれかであり、Ｒ^３２は各々独立に、炭素数１～３０の炭化水素基（例えば、アルキレン基）であり、ｓは０～５の整数である。）
［２］
下記式（８）で示される未変性ポリフェニレンエーテルと、下記式（１０）の不飽和化合物との反応工程を有する、ことを特徴とする変性ポリフェニレンエーテルの製造方法。

・・・式（８）
（式（８）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（－Ｙｎ－Ａ）中少なくとも１つのｎは１以上の整数である。

・・・式（２）
式（２）中、Ｘはａ価の任意の連結基であり、Ｒ^４は炭素数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、－Ｏ－が結合するベンゼン環の炭素原子を１位とし、２位又は６位の少なくとも一方の炭素原子に結合しており、ｋは各々独立に１～４の整数である。

・・・式（３）
式（３）中、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、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のアルキル基及び置換されていてもよいフェニル基のいずれかである。

・・・式（４）
式（４）中、Ｒ^２１は各々独立に、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。

・・・式（１０）
上記式（１０）中、Ｒ^３１は各々独立に、水素原子、水酸基、炭素数１～３０の炭化水素基（例えば、鎖状炭化水素基、環状炭化水素基）、アリール基、アルコキシ基、アリロキシ基、アミノ基、及びヒドロキシアルキル基のいずれかであり、Ｒ^３２は各々独立に、炭素数１～３０の炭化水素基（例えば、アルキレン基）であり、ｓは０～５の整数である。）
［３］
前記式（８）で示される未変性ポリフェニレンエーテルと、前記式（１０）の不飽和化合物との反応が、有機アミン触媒又はルイス酸触媒の存在化で実施される、［２］に記載の製造方法。
［４］
前記式（８）で示される未変性ポリフェニレンエーテルと、前記式（１０）の不飽和化合物との反応が、前記有機アミン触媒の存在化で実施され、前記有機アミン触媒がジメチルアミノピリジンである、［３］に記載の製造方法
［５］
請求項１に記載の変性ポリフェニレンエーテルを含む、ことを特徴とする熱硬化組成物。
［６］
基材と、請求項５に記載の熱硬化組成物とを含む、ことを特徴とするプリプレグ。
［７］
前記基材がガラスクロスである、請求項６に記載のプリプレグ。
［８］
請求項６又は７に記載のプリプレグの硬化物と、金属箔とを含む、ことを特徴とする積層体。 That is, the present invention is as follows.
[1]
A modified polyphenylene ether represented by the following formula (1).
The polystyrene-equivalent number average molecular weight is 500 to 15,000.
Based on the total amount of the modified polyphenylene ether, the content of methacrylic acid is less than 200 ppm, the total content of methacrylic anhydride and vinyl chloride is less than 200 ppm, the content of the organic amine catalyst is less than 200 ppm, and the chloride ion. A modified polyphenylene ether characterized by a content of less than 1500 ppm.

... Equation (1)
(In the formula (1), Z is a partial structure of a valence represented by the following formula (2), a represents an integer of 2 to 6, and Y is independently represented by the following formula (4). It is a divalent linking group having a structure, n represents the number of repetitions of Y, each is an integer of 0 to 200 independently, and at least one n in a (-Yn-A) is an integer of 1 or more. A is a group represented by the following formula (5).

... Equation (2)
In the formula (2), X is an arbitrary linking group having a valence, and ^R4 is any of a linear alkyl group having 1 to 8 carbon atoms and a partial structure represented by the following formula (3). The carbon atom of the benzene ring to which —O— is bonded is at the 1-position, and is bonded to at least one of the carbon atoms at the 2-position or the 6-position, and k is an independently integer of 1 to 4.

... formula (3)
In formula (3), R ¹¹ is an alkyl group having 1 to 8 carbon atoms which may be substituted independently, and R ¹² is an alkylene group having 1 to 8 carbon atoms which may be substituted independently. There, b is 0 or 1, respectively, and R ¹³ is either a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, and a phenyl group which may be substituted.

... Equation (4)
In formula (4), R ²¹ is independently any one of a hydrocarbon group having 1 to 6 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, and a halogen atom. Is.

... Equation (5)
In the above formula (5), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an aryloxy. It is either a group, an amino group, or a hydroxyalkyl group, and R ³² is independently a hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group), and s is an integer of 0 to 5. )
[2]
A method for producing a modified polyphenylene ether, which comprises a reaction step between an unmodified polyphenylene ether represented by the following formula (8) and an unsaturated compound of the following formula (10).

... Equation (8)
(In the formula (8), Z is a partial structure of a valence represented by the following formula (2), a represents an integer of 2 to 6, and Y is independently represented by the following formula (4). It is a divalent linking group having a structure, n represents the number of repetitions of Y, each is an integer of 0 to 200 independently, and at least one n in a (-Yn-A) is an integer of 1 or more. Is.

... Equation (2)
In the formula (2), X is an arbitrary linking group having a valence, and ^R4 is any of a linear alkyl group having 1 to 8 carbon atoms and a partial structure represented by the following formula (3). The carbon atom of the benzene ring to which —O— is bonded is at the 1-position, and is bonded to at least one of the carbon atoms at the 2-position or the 6-position, and k is an independently integer of 1 to 4.

... formula (3)
In formula (3), R ¹¹ is an alkyl group having 1 to 8 carbon atoms which may be substituted independently, and R ¹² is an alkylene group having 1 to 8 carbon atoms which may be substituted independently. There, b is 0 or 1, respectively, and R ¹³ is either a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, and a phenyl group which may be substituted.

... Equation (4)
In formula (4), R ²¹ is independently any one of a hydrocarbon group having 1 to 6 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, and a halogen atom. Is.

... formula (10)
In the above formula (10), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an aryloxy. It is either a group, an amino group, or a hydroxyalkyl group, and R ³² is independently a hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group), and s is an integer of 0 to 5. )
[3]
The production according to [2], wherein the reaction between the unmodified polyphenylene ether represented by the formula (8) and the unsaturated compound of the formula (10) is carried out in the presence of an organic amine catalyst or a Lewis acid catalyst. Method.
[4]
The reaction between the unmodified polyphenylene ether represented by the formula (8) and the unsaturated compound of the formula (10) is carried out in the presence of the organic amine catalyst, and the organic amine catalyst is dimethylaminopyridine. The manufacturing method according to [3] [5]
A thermosetting composition comprising the modified polyphenylene ether according to claim 1.
[6]
A prepreg comprising a substrate and the thermosetting composition according to claim 5.
[7]
The prepreg according to claim 6, wherein the base material is glass cloth.
[8]
A laminate comprising the cured product of the prepreg according to claim 6 or 7 and a metal foil.

According to the present invention, it is possible to provide a modified polyphenylene ether having a high glass transition temperature after curing, and a thermosetting composition containing the modified polyphenylene ether.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to this embodiment, and the present invention is appropriately modified within the scope of the gist thereof. Can be carried out.
In this specification, A (numerical value) to B (numerical value) mean A or more and B or less.

・・・式（１）
（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（－Ｙｎ－Ａ）中少なくとも１つのｎは１以上の整数である。

・・・式（２）
式（２）中、Ｘはａ価の任意の連結基であり、Ｒ^４は炭素数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、－Ｏ－が結合するベンゼン環の炭素原子を１位とし、２位又は６位の少なくとも一方の炭素原子に結合しており、ｋは各々独立に１～４の整数である。

・・・式（３）
式（３）中、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、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のアルキル基及び置換されていてもよいフェニル基のいずれかである。

・・・式（４）
式（４）中、Ｒ^２１は各々独立に、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。

・・・式（５）
式（５）中、Ｒ^３１は各々独立に、水素原子、水酸基、炭素数１～３０の炭化水素基（例えば、鎖状炭化水素基、環状炭化水素基）、アリール基、アルコキシ基、アリロキシ基、アミノ基、及びヒドロキシアルキル基のいずれかであり、Ｒ^３２は各々独立に、炭素数１～３０の炭化水素基（例えばアルキレン基）であり、ｓは０～５の整数である。） <Modified polyphenylene ether>
The modified polyphenylene ether of the present embodiment is represented by the following formula (1), and the content of methacrylic acid is less than 200 ppm and the total content of methacrylic acid anhydride and vinyl chloride is based on the total amount of the modified polyphenylene ether. The content of the organic amine catalyst is less than 200 ppm, the content of chloride ion is less than 1500 ppm, and the polystyrene-equivalent number average molecular weight is 500 to 15,000.

... Equation (1)
(In the formula (1), Z is a partial structure of a valence represented by the following formula (2), a represents an integer of 2 to 6, and Y is independently represented by the following formula (4). It is a divalent linking group having a structure, n represents the number of repetitions of Y, each is an integer of 0 to 200 independently, and at least one n in a (-Yn-A) is an integer of 1 or more. Is.

... Equation (2)
In the formula (2), X is an arbitrary linking group having a valence, and ^R4 is any of a linear alkyl group having 1 to 8 carbon atoms and a partial structure represented by the following formula (3). The carbon atom of the benzene ring to which —O— is bonded is at the 1-position, and is bonded to at least one of the carbon atoms at the 2-position or the 6-position, and k is an independently integer of 1 to 4.

... formula (3)
In formula (3), R ¹¹ is an alkyl group having 1 to 8 carbon atoms which may be substituted independently, and R ¹² is an alkylene group having 1 to 8 carbon atoms which may be substituted independently. Yes, b is 0 or 1 independently, and R ¹³ is either a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, and a phenyl group which may be substituted.

... Equation (4)
In formula (4), R ²¹ is independently any one of a hydrocarbon group having 1 to 6 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, and a halogen atom. Is.

... Equation (5)
In formula (5), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an allyloxy group. , Amino group, and hydroxyalkyl group, each of R ³² is independently a hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group), and s is an integer of 0 to 5. )

In the present embodiment, the above Z (partial structure represented by the formula (2)) is also referred to as a central phenol moiety, and the reaction is carried out when the polyfunctional unmodified polyphenylene ether which is the raw material of the modified polyphenylene ether of the present embodiment is polymerized. It means the central skeleton as the starting point, and its structure can be identified by analyzing the modified polyphenylene ether by a method such as NMR, mass spectrometry, and pyrolysis GC-MS. As a specific method for identifying the structure of the central phenol site from the modified polyphenylene ether, electric field desorption mass spectrometry (FD-MS), which is known to be less likely to cause fragmentation, is carried out, and the interval between detected ions is detected. It is possible to estimate the iterative unit by. Further, there is a method of estimating the structure of the central phenol site by combining it with the peak analysis of fragment ions and the structural analysis by NMR by the electron ionization method (EI).

・・・式（２）
式（２）中のａは、式（１）中のａと同じ整数である。式（２）で表される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。中でも、溶媒への溶解性に一層優れ、硬化後のガラス転移温度が一層高い変性ポリフェニレンエーテルとなる観点から、ａ個の各部分構造は同じ構造であることが好ましい。
式（２）中のａ個の－Ｏ－末端は、式（１）のＹに直接結合してよい。 As described above, the modified polyphenylene ether has a structure in which a partial structure (phenol substituted with ^R4 or the like) is bonded to the a-valent central portion X of the a-valent partial structure (that is, the a-valent partial structure). , Z) represented by the formula (2) is bound to (-Yn-A) in the formula (1).

... Equation (2)
The a in the equation (2) is the same integer as the a in the equation (1). In the central phenol site represented by the formula (2), each of the a partial structures may have the same structure or may be different. Above all, from the viewpoint of becoming a modified polyphenylene ether having further excellent solubility in a solvent and having a higher glass transition temperature after curing, it is preferable that each partial structure of a has the same structure.
The a-O-terminals in the formula (2) may be directly bonded to the Y in the formula (1).

In the formula (2), X is an arbitrary linking group having a valence, and is not particularly limited, but is selected from, for example, hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; nitrogen, phosphorus, silicon and oxygen. , Hydrocarbon groups containing one or more atoms; atoms such as nitrogen, phosphorus, silicon; or groups combining these; and the like. X may be a linking group excluding a single bond. X may be a linking group that links the a-valued substructures to each other.
As the above X, R ⁴ is bonded via an a-valent alkyl skeleton bonded to the benzene ring to which R ⁴ is bonded, a single bond, an ester bond, or the like via a single bond or an ester bond. Examples thereof include an a-valent aryl skeleton bonded to a benzene ring, an a-valent heterocyclic skeleton bonded to a benzene ring to which ^R4 is bonded via a single bond or an ester bond, and the like.
Here, the alkyl skeleton is not particularly limited, but for example, the branched end of a chain hydrocarbon (for example, a chain saturated hydrocarbon) branched into at least a number of carbon atoms of 2 to 6 becomes a benzene ring having a partial structure. Examples thereof include a skeleton that is directly bonded (a benzene ring may be bonded to a branch end, and there may be a branch end to which the benzene ring is not bonded). 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 ^R4 via a single bond or an alkyl chain. Examples thereof include a skeleton bonded to a benzene ring. Further, the heterocyclic skeleton is not particularly limited, and examples thereof include a skeleton in which the triazine ring is bonded to the benzene ring to which ^R4 is bonded via a single bond or an alkyl chain.

・・・式（３）
上記式（３）中、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、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のアルキル基及び置換されていてもよいフェニル基のいずれかである。式（３）中の左側の末端（－（Ｒ^１２）側末端）が、ベンゼン環の炭素原子と直接結合してよい。
上記置換基としては、ハロゲン原子等が挙げられる。 In the formula (2), R ⁴ is independently any of a linear alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group and an n-propyl group, and a partial structure represented by the following formula (3). The carbon atom of the benzene ring to which —O— is bonded is at the 1-position, and it is bonded to at least one carbon atom at the 2-position or the 6-position, and k is an independently integer of 1 to 4.

... formula (3)
In the above formula (3), R ¹¹ is an alkyl group having 1 to 8 carbon atoms which may be substituted independently, and R ¹² is an alkylene group having 1 to 8 carbon atoms which may be substituted independently. B is independently 0 or 1, and R ¹³ is either a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, or a phenyl group which may be substituted. The left end (-(R ¹² ) side end) in formula (3) may be directly bonded to the carbon atom of the benzene ring.
Examples of the substituent include halogen atoms and the like.

The above formula (3) is preferably a group containing secondary and / or tertiary carbon, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, 2,2-. Examples thereof include a dimethylpropyl group and a structure having a phenyl group at the terminal thereof, and a tert-butyl group is more preferable.

The benzene ring of the above formula (2) is a carbon other than the 2-position and the 6-position when the carbon atom to which the (Yn—A) of the above formula (1) is bonded via an oxygen atom is set to the 1-position. The central portion X may be bonded to the atom, and it is preferable that the central portion X is bonded to the 4-position.

・・・式（４）
上記式（４）中、Ｒ^２１は各々独立に、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、Ｒ^２１はメチル基であることが好ましい。式（４）の左側の末端が、式（１）中のＺ（例えば式（２）中の－Ｏ－）に直接結合してよく、右側の末端がＡに直接結合してよい。 Y is a divalent linking group having the structure of the following formula (4) independently.

... Equation (4)
In the above formula (4), R ²¹ is independently any of a hydrocarbon group having 1 to 6 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, and a halogen atom. It is preferable that R ²¹ is a methyl group. The left end of formula (4) may be directly attached to Z in formula (1) (eg —O— in formula (2)) and the right end may be directly attached to A.

・・・式（５）
上記式（５）中、Ｒ^３１は各々独立に、水素原子、水酸基、炭素数１～３０の炭化水素基（例えば、鎖状炭化水素基、環状炭化水素基）、アリール基、アルコキシ基、アリロキシ基、アミノ基、及びヒドロキシアルキル基のいずれかである。
Ｒ^３２は各々独立に、炭素数１～３０の炭化水素基（例えば、アルキレン基）である。
ｓは、０～５の整数である。
式（５）中の左側の末端が、式（１）中のＹ（例えば、式（４）の右側の末端）に直接結合してよい。 In the above formula (1), A is a hydrogen atom or a group represented by the following formula (5), and is preferably a group represented by the following formula (5).

... Equation (5)
In the above formula (5), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an aryloxy. It is either a group, an amino group, and a hydroxyalkyl group.
Each of R ³² is independently a hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group).
s is an integer from 0 to 5.
The left end in formula (5) may be directly attached to Y in formula (1) (eg, the right end in formula (4)).

From the viewpoint of obtaining a modified polyphenylene ether having a higher glass transition temperature after curing and further excellent solubility in a solvent, the substituent represented by the above formula (5) is preferably a methacryloyl group.

Specific examples of the hydrocarbon group of R ³¹ include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl and 2-methylbutyl. , 3-Methylbutyl, Amil, Cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, Cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methyl Pentil, 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, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1- To dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethyl Xyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-di Methylhexyl, 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-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methyl Pentyl, 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. 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, benzyl, 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, 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-methyl With heptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl. be.

Specific examples of the hydrocarbon group of R ³² include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene and 1-ethyl. -1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butyllene, 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, 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-Cyclohexene Silen, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2,3-dimethyl-1,3-cyclopentylene, 2,4-dimethyl To -1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1methyl-1,7-heptylene, 1-ethyl1,6- Xylene, 1-propyl-1,5-pentylene, 2-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptyrene, 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, 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) Ethyl, 1,1 -(2-Methylenepropyl) 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-cyclohexylene, 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- Examples thereof include phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene and the like. Preferred are 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-heptyrene, 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, dodecylmethylene, more 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, 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-Methylene Lu-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, dodecylmethylene, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, penta. Methylene, 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 dodecylmethylene.

The modified polyphenylene ether of the present embodiment may contain polyphenylene ether in which one or more A is a hydrogen atom in the structure of the above formula (1), but from the viewpoint of obtaining a high glass transition temperature in the thermosetting composition, It is more preferable that the structure of the above formula (1) does not contain polyphenylene ether in which one or more A is a hydrogen atom.

The modified polyphenylene ether of the present embodiment is based on the modified polyphenylene ether represented by the above formula (1), methacrylic acid of less than 200 mass ppm, methacrylic acid anhydride and vinyl methacrylate of less than 200 mass ppm, less than 200 mass ppm. The organic amine catalyst and the chloride ion of less than 1500 mass ppm are preferable, and the methacrylic acid of less than 100 mass ppm and the methacrylic acid of less than 100 mass ppm are based on the modified polyphenylene ether represented by the above formula (1). More preferably, it is an anhydride and vinyl methacrylate, an organic amine catalyst of less than 100 mass ppm, and a chloride ion of less than 1000 mass ppm.

・・・式（６）
（式（６）中、Ｒ^２１は、上記式（４）と同様の基が挙げられ、上記式（４）と同じであることが好ましい。）

・・・式（７）
（式（７）中、Ｘ、Ｒ^４、ｋ、ａは、上記式（２）と同様のものが挙げられ、上記式（２）と同じであることが好ましい。Ｘに結合するａ個の部分構造は、それぞれ同じであってもよいし異なっていてもよいが、同じであることが好ましい。） The modified polyphenylene ether is obtained by copolymerizing, for example, a monovalent phenol compound represented by the following formula (6) and a polyvalent (a-valent) phenol compound (central phenol) represented by the following formula (7). , Unmodified polyphenylene ether is obtained, followed by a modification reaction. Details of the manufacturing method will be described later.

... Equation (6)
(In the formula (6), R ²¹ has the same group as the above formula (4), and is preferably the same as the above formula (4).)

... formula (7)
(In the formula (7), X, ^R4 , k, a are the same as those in the above formula (2), and are preferably the same as the above formula (2). The partial structures may be the same or different, but are preferably the same.)

Examples of the monovalent phenol compound represented by the above formula (6) include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, and 2-ethyl-6-n-. Propylphenol, 2-methyl-6-chlorphenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol , 2,6-di-n-propylphenol, 2-ethyl-6-chlorphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6- Examples include ditrilphenol and the like. Of these, 2,6-dimethylphenol, 2,6-diethylphenol, and 2,6-diphenylphenol are particularly preferable because they are inexpensive and easily available.

The above-mentioned phenol compound may be used alone or in combination of two or more.

The a-valent phenol compound represented by the above formula (7) includes the corresponding monovalent phenol compound, aldehydes (for example, formaldehyde, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone). , Cyclohexanone, etc.), or by reaction with dihalogenated aliphatic hydrocarbons, reaction between corresponding monovalent phenol compounds, etc., can be industrially advantageous.

Among the phenol compounds represented by the above formula (7), examples of phenol compounds having two phenol units in the molecule are listed below.
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4'-methylenebis (2,6-dimethylphenol) , Bis (4-hydroxy-3-methylphenyl) sulfide, Bis (4-hydroxy-3,5-dimethylphenyl) sulfone, α, α'-bis (4-hydroxy-3,5-dimethylphenyl) -1, 4-Diisopropylbenzene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (2-methyl-4) -Hydroxy-5-t-butylphenyl) butane and the like can be mentioned, but the present invention is not limited thereto.

Further, among the phenol compounds represented by the above formula (7), examples of phenol compounds having three or more phenol units in the molecule are listed below.
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 (2,3,6-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- (4- (4-) Hydroxyphenyl) cyclohexylidene] bis (2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl) methylene] -bis (2,3,6-trimethylphenol), 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-dimethyl) Phenyl) 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-methylpheni) Le) 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-[(2,3,3) 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-methyl) Phenyl) methyl] phenol], 4,4'-cyclohexylidenebis [2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl) methyl] phenol], 4,4'-cyclohexylidenebis [2-Cyclohexyl-6-[(4-hydroxy-2-methyl-5-cyclohexylphenyl) methyl] phenol] Phenol Le], 4,4'-cyclohexylidenebis [2-cyclohexyl-6-[(2,3,4-trihydroxyphenyl) methyl] phenol], 4,4', 4'', 4'''- (1,2-Ethandiylidene) Tetrax (2,6-dimethylphenol), 4,4', 4'', 4'''-(1,4-phenylenedimethyliden) Tetrax (2,6-dimethylphenol), 1,1,3-Tris- (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane and the like can be mentioned, but the present invention is not limited thereto.

Particularly preferable a-valent phenol compounds (central phenol) are 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and 1,1-bis (2-methyl-4-hydroxy-5-t-). Butylphenyl) butane, 4,4'-[(4-hydroxyphenyl) methylene] bis (2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl) methylene] bis (2,6-dimethyl) Phenol), 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-terchary butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-t-butylphenyl) butane.

The number of phenolic hydroxyl groups in the a-valent phenol compound (central phenol) is not particularly limited as long as it is 2 or more, but it is preferable because it may be difficult to control the thermosetting rate if the number of polyphenylene ether terminals is large. The number is 2 to 6, more preferably 2 to 4.

When the a-valent phenol compound (central phenol) represented by the formula (7) is contained, the amount of the divalent phenolic compound of the formula (7) with respect to all the monovalent phenols represented by the formula (6) is Although not particularly limited, it is preferably 2 to 30 mol% with respect to all monohydric phenols.

In the modified polyphenylene ether of the present embodiment, the polyfunctional polyphenylene ether which is a raw material of the modified polyphenylene ether having the structure of the above formula (1) rebalances the monofunctional polyphenylene ether with the polyhydric phenol in the presence of an oxidizing agent. It can also be produced by a distribution reaction. The redistribution reaction is known in the art and is described, for example, in US Pat. No. 3,494,236 of Cooper et al. And US Pat. No. 5,880,221 of Liska et al.

However, when a polyfunctional polyphenylene ether is produced by a redistribution reaction, a peroxide is often used as a reaction initiator and an oxidizing agent, and this peroxide is highly reactive and has various forms of by-products. To generate. A typical example of the by-product is a peroxide adduct to the polyphenylene ether produced. Further, not only the polyfunctional polyphenylene ether which is the target product, but also the monofunctional polyphenylene ether which is the raw material and the by-product in which the peroxide is added to the polyhydric phenol are produced, so that the above formula (1) which is the target product is produced. The purity of the modified polyphenylene ether having the above structure is reduced, and the average number of functional groups per central phenol site is also reduced.

The number average molecular weight (Mn) of the modified polyphenylene ether in the present embodiment is preferably 500 to 15,000, more preferably 1,000 to 10,000, still more preferably 1,500 to 8,000. Is. When the number average molecular weight (Mn) is within the above range, the fluidity when dissolved in the solvent for producing the varnish in the process of applying to the substrate material is further improved, and the processability at the time of applying the substrate material is ensured. be able to.
The number average molecular weight can be measured by the method described in Examples described later.

The average number of functional groups of the modified polyphenylene ether in the present embodiment is preferably 1.8 to 6.0, more preferably 2.0 to 4.0, still more preferably 2.5 to 4.0. be. When the average number of functional groups is within the above range, the thermosetting rate of the polyphenylene ether terminal can be controlled and poor thermosetting can be suppressed.
The average number of functional groups can be measured by the method described in Examples described later.

・・・式（８）
（（８）中、Ｚ、Ｙ、ｎ、ａは式（１）と同様のものが挙げられ、同じであることが好ましい。） <Manufacturing method of modified polyphenylene ether>
The method for producing the modified polyphenylene ether of the present embodiment is, for example, a polyfunctional polyphenylene ether having a hydroxyl group at the molecular end represented by the following formula (8) by a polymerization method (in the present specification, the unmodified polyphenylene ether, It can be produced by synthesizing an unmodified polyphenylene ether) and introducing the A substituent in the formula (1) into its terminal hydroxyl group, that is, by modifying it.

... Equation (8)
(In (8), Z, Y, n, and a are the same as those in the formula (1), and are preferably the same.)

(Polymerization process)
Here, in the method for producing an unmodified polyfunctional polyphenylene ether, it is preferable to use an aromatic solvent which is a good solvent for the unmodified polyfunctional polyphenylene ether as the polymerization solvent in the polymerization step.
Here, the good solvent of the unmodified polyfunctional polyphenylene ether is a solvent capable of dissolving the polyfunctional polyphenylene ether, and examples of such a solvent include benzene, toluene, and xylene (o-, m-, p. (Including each isomer of-), aromatic hydrocarbons such as ethylbenzene and styrene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; nitro compounds such as nitrobenzene; and the like.

As the polymerization catalyst used in this embodiment, a known catalyst system that can be generally used for producing polyphenylene ether can be used. As a generally known catalyst system, one consisting of a transition metal ion having an oxidation-reduction ability and an amine compound capable of forming a complex with the transition metal ion is known, and for example, it is composed of a copper compound and an amine compound. A catalytic system, a catalytic system composed of a manganese compound and an amine compound, a catalytic system composed of a cobalt compound and an amine compound, and the like. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a slight alkali or a further amine compound may be added thereto.

The polymerization catalyst preferably used in this embodiment is a catalyst composed of a copper compound, a halogen compound and an amine compound as a constituent component of the catalyst, and more preferably a diamine compound represented by the following formula (9) as an amine compound. Is a catalyst containing.

・・・式（９）
式（９）中、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７は、それぞれ独立に、水素原子、炭素数１から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い。Ｒ^１８は、炭素数２から５の直鎖状又はメチル分岐を持つアルキレン基である。

... formula (9)
In formula (9), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, and not all of them are hydrogen atoms at the same time. .. ^R18 is an alkylene group having a linear or methyl branch having 2 to 5 carbon atoms.

Examples of the copper compounds of the catalyst component described here are listed. As a suitable copper compound, a cuprous compound, a cupric compound or a mixture thereof can be used. Examples of the cupric compound include cupric chloride, cupric bromide, cupric sulfate, cupric nitrate and the like. Further, as the cuprous compound, for example, cuprous chloride, cuprous bromide, cuprous sulfate, cupric nitrate and the like can be exemplified. Among these, particularly preferable metal compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Further, these copper salts may be synthesized at the time of use from halogens or acids corresponding to oxides (for example, cuprous oxide), carbonates, hydroxides and the like. The method often used is a method prepared by mixing the cuprous oxide exemplified above with hydrogen halide (or a solution of hydrogen halide).

Examples of the halogen compound 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. Further, these can be used as a solution using an aqueous solution or an appropriate solvent. These halogen compounds may be used alone as components, or may be used in combination of two or more. Preferred halogen compounds are an aqueous solution of hydrogen chloride and an aqueous solution of hydrogen bromide.
The amount of these compounds used is not particularly limited, but is preferably 2 times or more and 20 times or less as the halogen atom with respect to the molar amount of the copper atom, and the use of the copper atom is preferable with respect to 100 mol of the phenol compound added to the polymerization reaction. The amount ranges 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, N-i-propylethylenediamine, N, N'-i-propylethylenediamine, Nn -Butylethylenediamine, N, N'-n-butylethylenediamine, Ni-i-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- Examples thereof include diamino-2-methylpropane, N, N, N', N'-tetramethyl-1,4-diaminobutane, N, N, N', N'-tetramethyl-1,5-diaminopentane and the like. .. The preferred diamine compound for this embodiment is one in which the alkylene group connecting the two nitrogen atoms has 2 or 3 carbon atoms. The amount of these diamine compounds used is not particularly limited, but is preferably in the range of 0.01 mol to 10 mol with respect to 100 mol of the phenol compound added to the polymerization reaction.

In the present embodiment, primary amines and secondary monoamines can be included as constituents of the polymerization catalyst. The secondary monoamine is not limited to, but is not limited to, for example, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, and the like. Di-t-butylamines, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamines, methylpropylamines, methylbutylamines, cyclohexylamines, N-phenylmethanolamines, N-phenylethanolamines. , 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 can be mentioned.

A tertiary monoamine compound may also be contained as a constituent component of the polymerization catalyst in the present embodiment. The tertiary monoamine compound is an aliphatic tertiary amine including an alicyclic tertiary amine. For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine and the like can be mentioned. 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 with respect to 100 mol of the phenol compound added to the polymerization reaction.

In the present embodiment, there is no limitation on the addition of a surfactant which has been conventionally known to have an effect of improving the polymerization activity. Examples of such a surfactant include trioctylmethylammonium chloride known by trade names of Aliquat 336 and Capriquat. The amount used is preferably in the 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 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 an inert gas such as air and nitrogen are optional. Can be used as a mixture of the above. Normal pressure is sufficient as the internal pressure during the polymerization reaction, but it can be used under reduced pressure or pressurized as needed.

The polymerization temperature is not particularly limited, but if it is too low, the reaction will not proceed easily, and if it is too high, the reaction selectivity may decrease and high molecular weight components may be generated. Therefore, the temperature is 0 to 60 ° C., preferably 10 to 50. It is in the range of ° C.

In the method for producing an unmodified polyfunctional polyphenylene ether, it is preferable to polymerize in a solution state (also referred to as “solution polymerization” in the present specification) at the time of polyphenylene ether polymerization. Even when a central phenol having a bulky structure is used by the solution polymerization, the polyphenylene ether component that does not contain the structure of the above formula (8) and the polyphenylene ether component that does not contain the structure of the above formula (8) during the production of the unmodified polyfunctional polyphenylene ether can be used. It is possible to reduce the proportion of by-products produced by the oxide and to produce the modified polyphenylene ether containing the structure of the above formula (1) as the target product with high purity.

(Copper extraction and by-product removal process)
In the present embodiment, there is no particular limitation on the post-treatment method after the completion of the polymerization reaction. Usually, an acid such as hydrochloric acid or acetic acid, ethylenediaminetetraacetic acid (EDTA) and a salt thereof, nitrilotriacetic acid and a salt thereof are added to the reaction solution to inactivate the catalyst. Further, a method for removing a by-product of a divalent phenol compound generated by the polymerization of polyphenylene ether can also be carried out by using a conventionally known method. If the metal ion as a catalyst is substantially inactivated as described above, the mixture is decolorized simply by heating it. It is also possible to add a required amount of a known reducing agent. Known reducing agents include hydroquinone, sodium nitionate and the like.

(Liquid-liquid separation process)
In the method for producing an unmodified polyfunctional polyphenylene ether, water is added to extract a compound in which a copper catalyst has been deactivated, liquid-liquid separation is performed between the organic phase and the aqueous phase, and then the aqueous phase is removed. The copper catalyst may be removed from the foundation. The liquid-liquid separation step is not particularly limited, and examples thereof include static separation and separation by a centrifuge. In order to promote the liquid-liquid separation, a known surfactant or the like may be used.

(Concentration / drying process)
Subsequently, in the method for producing the modified polyphenylene ether of the present embodiment, the organic phase containing the unmodified polyfunctional polyphenylene ether after liquid-liquid separation may be concentrated and dried by volatilizing the solvent.
This step may be omitted when the modification reaction (reaction of introducing the substituent A in the formula (1) into the terminal of the unmodified polyfunctional polyphenylene ether) is subsequently carried out.

The method for volatilizing the solvent contained in the organic phase is not particularly limited, but the method of transferring the organic phase to a high-temperature concentration tank and distilling off the solvent to concentrate the solvent, or the method of distilling toluene using an apparatus such as a rotary evaporator. Examples thereof include a method of removing and concentrating.

The temperature of the drying treatment in the drying step is preferably at least 60 ° C. or higher, more preferably 80 ° C. or higher, further preferably 120 ° C. or higher, and most preferably 140 ° C. or higher. When the polyfunctional polyphenylene ether is dried at a temperature of 60 ° C. or higher, the content of high boiling point volatile components in the polyphenylene ether powder can be efficiently reduced.

In order to obtain unmodified polyfunctional polyphenylene ether with high efficiency, a method of increasing the drying temperature, a method of increasing the degree of vacuum in a drying atmosphere, a method of stirring during drying, etc. are effective, but in particular, drying. A method of raising the temperature is preferable from the viewpoint of manufacturing efficiency. In the drying step, it is preferable to use a dryer having a mixing function. Examples of the mixing function include a stirring type and a rolling type dryer. As a result, the amount of processing can be increased and the productivity can be maintained high.

(Degeneration reaction process)
There is no limitation on the method of introducing the substituent of A (the functional group of the above formula (5)) into the terminal of the unmodified polyphenylene ether, for example, the hydroxyl group at the terminal of the unmodified polyphenylene ether and the carbon-carbon double. It is obtained by a reaction of forming an ester bond with a carboxylic acid having a bond (hereinafter, simply referred to as "carboxylic acid").
As a method for forming an ester bond, various known methods can be used. For example, a. Reaction of carboxylic acid halide with hydroxyl group at the end of polymer, b. Formation of ester bonds by reaction with carboxylic acid anhydride, c. Direct reaction with carboxylic acid, d. Examples thereof include a method based on a transesterification reaction with an ester. The above a to d carboxylic acid halides, carboxylic acid anhydrides, carboxylic acids, and esters are referred to as modifiers.
The reaction of a with a carboxylic acid halide is one of the most common methods. Chlorides and bromides are generally used as the carboxylic acid halides, but other halogens may be used. The reaction may be either a direct reaction with a hydroxyl group or a reaction with an alkali metal salt of the hydroxyl group. Since an acid such as hydrogen halide is generated in the direct reaction between the carboxylic acid halide and the hydroxyl group, a weak base such as an amine may coexist for the purpose of trapping the acid. In the reaction with the carboxylic acid anhydride of b or the direct reaction with the carboxylic acid of c, a compound such as carbodiimides or dimethylaminopyridine may coexist in order to activate the reaction site and promote the reaction. ..
In the case of the transesterification reaction of d, it is desirable to remove the produced alcohols as necessary. Further, known metal catalysts may coexist in order to promote the reaction. After the reaction, it may be washed with water, an acidic or alkaline aqueous solution in order to remove by-products such as amine salts, or the polymer solution is dropped into a poor solvent such as alcohols and reprecipitated. , You may collect the object. Further, after washing the polymer solution, the solvent may be distilled off under reduced pressure to recover the polymer.

・・・式（１０）
上記式（１０）中、Ｒ^３１は各々独立に、水素原子、水酸基、炭素数１～３０の炭化水素基（例えば、鎖状炭化水素基、環状炭化水素基）、アリール基、アルコキシ基、アリロキシ基、アミノ基、及びヒドロキシアルキル基のいずれかである。
Ｒ^３２は各々独立に、炭素数１～３０の炭化水素基（例えば、アルキレン基）である。
Ｒ^３１としては、上述と同様の化合物が挙げられ、同様の化合物が好ましい。また、Ｒ^３２としては、上述と同様の化合物が挙げられ、同様の化合物が好ましい。
ｓは、０～５の整数である。 As a method of introducing the substituent of A (the functional group of the above formula (5)) into the terminal of the unmodified polyphenylene ether, vinyl carboxylate represented by the formula (10) may be used. An organic amine catalyst or a Lewis acid catalyst may coexist in order to activate the reaction site and promote the reaction. As the organic amine catalyst, diaminopyridine (particularly preferably dimethylaminopyridine) having a high ability to activate a carbonyl group is preferable. The Lewis acid catalyst is not particularly limited, but aluminum chloride, trifluoroborane, scandium (III) triflate and the like are preferable.

... formula (10)
In the above formula (10), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an aryloxy. It is either a group, an amino group, and a hydroxyalkyl group.
Each of R ³² is independently a hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group).
Examples of R ³¹ include the same compounds as described above, and similar compounds are preferable. Further, examples of R ³² include the same compounds as described above, and similar compounds are preferable.
s is an integer from 0 to 5.

As the denaturing agent as described above, methacrylic acid anhydride, methacrylic acid chloride, and vinyl chloride are preferable because they are commercially available and easily available. In the case of methacrylic acid anhydride, methacrylic acid is generated as a leaving group, and in the case of methacryloyl chloride, chloride ion is generated as a leaving group. Chloride ions are included. On the other hand, when vinyl methacrylate is used, the leaving group is acetaldehyde gas, and vinyl methacrylate is preferable because the leaving group can be easily removed from the reaction solution. Examples of the method for removing acetaldehyde gas include methods such as nitrogen bubbling to a reaction solution and vacuum drying.

Examples of the impurities contained in the modified polyphenylene ether represented by the following formula (1) include methacrylic acid anhydride and vinyl methacrylate derived from a modifying agent. Examples thereof include methacrylic acid, methyl methacrylate and chloride ions generated as deactivating and leaving groups of modifiers, and organic amines used as catalysts.

It is preferable that the amount of impurities contained in the modified polyphenylene ether represented by the above formula (1) is small.
The present inventor lowers the mass ratio of methacrylic acid, methacrylic anhydride, vinyl methacrylate, organic amine catalyst, and chloride ion among the impurities contained in the modified polyphenylene ether represented by the above formula (1). Therefore, it was found that the glass transition temperature becomes particularly high after the composition containing the modified polyphenylene ether represented by the above formula (1) is cured.
The organic amine catalyst is a compound having a tertiary amine, for example, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5. -Diazabicyclo [4.3.0] nonen-5, 1,4-diazabicyclo [2.2.2] octane, 1-azabicyclo [2.2.2] octane can be mentioned. The organic amine catalyst may be an organic amine catalyst added to the reaction for introducing the substituent A into the unmodified polyphenylene ether described above.
The chloride ion refers to ^Cl- .
The mass ratio of methacrylic acid in the modified polyphenylene ether is, for example, an introduction method in which the reactivity of the modifying agent is high and a high introduction rate of the substituent A can be easily achieved. Reaction of methacrylic acid halides with hydroxyl groups at the end of the polymer, b. It is used in the formation of ester bonds by reaction with methacrylic acid anhydride, and avoids the use of methacrylic acid halides and methacrylic acid anhydrides that are easily deactivated by reaction with trace amounts of water in the system to generate methacrylic acid. It can be reduced by using vinyl methacrylate, which has low reactivity with water. Further, in the case of methacrylic anhydride, an equivalent amount of methacrylic acid is by-produced as a leaving group. It is difficult to completely remove methacrylic acid as a by-product even if the modified polyphenylene ether is washed with an alcohol-based solvent that is a poor solvent, so it is important to change the type of modifier and prevent it from being generated in the system. be.
The total mass ratio of methacrylic anhydride and vinyl methacrylate in the modified polyphenylene ether is excessive, for example, by selecting a more active chemical species as the organic amine catalyst used in the reaction between the modifier and the unmodified polyphenylene ether. It can be lowered by not adding any modifiers.
The mass ratio of the organic amine catalyst in the modified polyphenylene ether can be lowered, for example, by reducing the addition rate of the organic amine catalyst or using a highly active Lewis acid catalyst.
The mass ratio of chloride ions in the modified polyphenylene ether is, for example, a. Amine hydrochloride used in the reaction between a methacrylic acid halide and the hydroxyl group at the end of the polymer, which is easily deactivated by a reaction with a trace amount of water in the system, and is produced by a side reaction with hydrochloric acid or the above-mentioned organic amine catalyst coexisting. It can be reduced by avoiding the use of methacrylic acid halides that generate the above, and by using vinyl methacrylate, which has low reactivity with water.
By lowering methacrylic acid, methacrylic acid anhydride, vinyl methacrylate, organic amine catalyst, and chloride ion in the thermosetting composition described later, it is possible to suppress curing defects due to acids and low molecular weight components, and thermosetting is possible. The Tg of the composition can be improved.
The methacrylic acid, methacrylic anhydride, vinyl methacrylate, organic amine catalyst and chloride ion in the modified polyphenylene ether can be measured by the methods described in Examples described later.

The method for producing the modified polyphenylene ether of the present embodiment is not limited to the above-mentioned method for producing the modified polyphenylene ether of the present embodiment, and is described above in the polymerization step, the copper extraction and by-product removing step, and the liquid-liquid separation step. , The order and number of concentration / drying steps may be adjusted as appropriate.

<Thermosetting composition>
The modified polyphenylene ether of the present embodiment can be used as a thermosetting composition. The thermosetting composition is not particularly limited as long as it contains a modified polyphenylene ether, but preferably further contains a cross-linking agent and an organic peroxide, and if desired, a thermoplastic resin, a flame retardant, and other additives. , Silica filler, solvent and the like can be further contained. The components of the thermosetting composition of this embodiment will be described below.

(Modified polyphenylene ether)
As described above, the modified polyphenylene ether of the present embodiment may be used as a single resin component in a thermosetting composition, may be used in combination with a polyphenylene ether having another structure, or various known additions may be used. It can also be used in combination with agents.
When used in combination with other components, the content of the modified polyphenylene ether in the thermosetting composition is preferably 0.5 to 95% by mass, more preferably 20 to 93% by mass, and even more preferably 40 to 40%. It is 90% by mass.

(Crosslinking agent)
In the thermosetting composition of the present embodiment, any cross-linking agent having an ability to cause or promote a cross-linking reaction can be used.
The cross-linking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the cross-linking agent is 4,000 or less, an increase in the viscosity of the thermosetting composition can be suppressed, and good resin fluidity at the time of heat molding can be obtained.
The number average molecular weight may be a value measured by a general molecular weight measuring method, and specific examples thereof include a value measured by using GPC.

From the viewpoint of the cross-linking reaction, the cross-linking agent preferably has two or more carbon-carbon unsaturated double bonds in one molecule on average. The cross-linking agent may be composed of one kind of compound or two or more kinds of compounds.
The term "carbon-carbon unsaturated double bond" as used herein means a double bond located at the end branched from the main chain when the cross-linking agent is a polymer or an oligomer. Examples of carbon-carbon unsaturated double bonds include 1,2-vinyl bonds in polybutadiene.

When the number average molecular weight of the cross-linking agent is less than 600, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 2 to 4. Number of cross-linking agents When the average molecular weight is 600 or more and less than 1,500, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 4 to 26. Number of cross-linking agents When the average molecular weight is 1,500 or more and less than 4,000, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent may be 26 to 60. preferable. When the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is equal to or more than the above-mentioned specific value, so that the thermosetting composition of the present embodiment has the reactivity of the cross-linking agent. Further, the crosslink density of the cured product of the thermosetting composition is further improved, and as a result, more excellent heat resistance can be imparted. On the other hand, when the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is equal to or less than the above-mentioned specific value, thereby imparting even better resin fluidity during heat molding. can.

Examples of the cross-linking agent include a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a trialkenyl cyanurate compound such as triallyl cyanurate (TAC), and a polyfunctional methacrylate having two or more methacrylic groups in the molecule. Compounds, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene, vinyl benzyl compounds such as divinylbenzene having vinyl benzyl groups in the molecule. , 4,4'-Bismaleimide Diphenylmethane and the like have polyfunctional maleimide compounds having two or more maleimide groups in the molecule. These cross-linking agents may be used alone or in combination of two or more. The cross-linking agent preferably contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. By including the cross-linking agent at least one of the compounds described above, the thermosetting composition is more excellent in compatibility and coatability between the cross-linking agent and the modified polyphenylene ether, and is mounted on an electronic circuit board. Then, the substrate characteristics tend to be further improved.

The mass ratio of the modified polyphenylene ether to the cross-linking agent (modified polyphenylene ether: cross-linking agent) determines the compatibility between the cross-linking agent and the modified polyphenylene ether, the coatability of the thermosetting composition, and the characteristics of the mounted electronic circuit board. From the viewpoint of further excellence, it is preferably 25:75 to 95: 5, and more preferably 32:68 to 85:15.

(Organic peroxide)
In this embodiment, any organic peroxide having the ability to accelerate the polymerization reaction of the thermosetting composition containing the modified polyphenylene ether and the cross-linking agent can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t-butylper). Oxy) Hexane-3, di-t-butyl peroxide, t-butylcumyl peroxide, di (2-t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) ) Octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide and other peroxides. A radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the thermosetting composition. Above all, from the viewpoint of being able to provide a cured product having excellent heat resistance and mechanical properties obtained, and having a lower dielectric constant and dielectric loss tangent, 2,5-dimethyl-2,5-di (t-butylperoxy). ) Hexin-3, di (2-t-butylperoxyisopropyl) benzene, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane are preferred.

The 1-minute half-life temperature of the organic peroxide is preferably 155 to 185 ° C, more preferably 160 to 180 ° C, still more preferably 165 to 175 ° C. The 1-minute half-life temperature of the organic peroxide is in the range of 155 to 185 ° C., so that the compatibility between the organic peroxide and the modified PPE, the coatability of the heat-curable composition, and the mounted electronic circuit It tends to be more excellent in the characteristics of the substrate.
In the present specification, the 1-minute half-life temperature is a temperature at which the time during which the organic peroxide is decomposed and the amount of active oxygen thereof is halved is 1 minute. The 1-minute half-life temperature is such that the organic peroxide is dissolved in a radical-inactive solvent such as benzene to a concentration of 0.05 to 0.1 mol / L, and the organic peroxide solution is prepared with nitrogen. It is a value confirmed by the method of thermal decomposition by atmosphericization.

Examples of organic peroxides having a 1-minute half-life temperature in the range of 155 to 185 ° C. include t-hexylperoxyisopropyl monocarbonate (155.0 ° C.) and t-butylperoxy-3,5,5-. Trimethylhexanoate (166.0 ° C), t-butylperoxylaurate (159.4 ° C), t-butylperoxyisopropylmonocarbonate (158.8 ° C), t-butylperoxy2-ethylhexylmonocarbonate (158.8 ° C) 161.4 ° C), t-hexylperoxybenzoate (160.3 ° C), 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (158.2 ° C), t-butylperoxyacetate (158.2 ° C) 159.9 ° C), 2,2-di- (t-butylperoxy) butane (159.9 ° C), t-butylperoxybenzoate (166.8 ° C), n-butyl 4,4-di- (159.9 ° C) 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.), t-butylcumyl peroxide (173.3 ° C.) and the like. ..

The content of the organic peroxide is based on a total of 100 parts by mass of the modified polyphenylene ether and the cross-linking agent, and the compatibility between the organic peroxide and the modified PPE and the coatability of the heat-curable composition are further excellent. Therefore, it is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, and the heat-curing composition is an electronic circuit substrate. From the viewpoint of excellent substrate characteristics, it is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less.

(Thermoplastic resin)
In this embodiment, any thermoplastic resin can be used. The thermoplastic resin is a hydrogenated product obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound and a hydrogenated product thereof (a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound). It is preferably at least one selected from the group consisting of block copolymers) and homopolymers of vinyl aromatic compounds.
The weight average molecular weight of the thermoplastic resin is preferably more than 50,000 from the viewpoint of further excellent compatibility with the modified polyphenylene ether, resin fluidity, coatability of the thermosetting composition, heat resistance at the time of curing, and the like. It is 780,000 or less, more preferably 60,000 to 750,000, still more preferably 70,000 to 700,000.
The thermosetting composition contains a modified polyphenylene ether, a cross-linking agent and an organic peroxide and a thermoplastic resin having the type and weight average molecular weight described above, and is compatible with the modified PPE and other contained components. In addition, the coatability on a substrate or the like tends to be good, and the substrate characteristics when incorporated into an electronic circuit board may also be excellent.
The weight average molecular weight is determined by the method described in Examples described later.

The content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is preferably 20% by mass or more, more preferably 22% by mass or more, and 24% by mass or more with respect to the lower limit. , 26% by mass or more, 28% by mass or more, 30% by mass or more, 32% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 69% by mass or less, 68% by mass or less, and 67% by mass or less. When the content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is 20 to 70% by mass, the compatibility with the modified polyphenylene ether is further improved and / or with the metal leaf. Adhesion strength tends to be further improved.

The vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene.
The olefin-based alkene compound may be any alkene having a linear or branched structure in the molecule, and examples thereof include ethylene, propylene, butylene, isobutylene, butadiene, and isoprene.
As the thermoplastic resin, from the viewpoint of further excellent compatibility with the modified polyphenylene ether, a styrene-butadiene block copolymer, a styrene-ethylene-butadiene block copolymer, a styrene-ethylene-butylene block copolymer, and a styrene-butadiene -Butylene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, styrene-isobutylene block copolymer, hydrogenated product of styrene-butadiene block copolymer, styrene-ethylene-butadiene Selected from the group consisting of block copolymer hydrogenated products, styrene-butadiene-butylene block copolymer hydrogenated products, styrene-isoprene block copolymer hydrogenated products, and styrene homopolymers (polystyrene). It is preferably at least one kind, and more preferably one or more kinds selected from the group consisting of a styrene-butadiene block copolymer, a hydrogenated additive of a styrene-butadiene block copolymer, and polystyrene.

The hydrogenation rate of the hydrogenated product is not particularly limited, and a carbon-carbon unsaturated double bond derived from an olefin-based alkene compound may partially remain.

The content of the thermoplastic resin is 2 to 20 parts by mass, preferably 3 to 19 parts by mass, and 4 to 18 parts by mass based on a total of 100 parts by mass of the modified polyphenylene ether and the cross-linking agent. More preferably, it is more preferably 5 to 17 parts by mass. When this content is within the above numerical range, the thermosetting composition of the present embodiment is more excellent in compatibility and coatability between the thermoplastic resin and the modified polyphenylene ether, and is mounted on an electronic circuit board. It tends to be more excellent in substrate characteristics.

The thermosetting composition of the present embodiment may also contain a thermoplastic resin other than the thermoplastic resin having the type and weight average molecular weight described above.

(Flame retardants)
The thermosetting composition of the present embodiment may contain any flame retardant. The flame retardant is not particularly limited as long as it is incompatible with other components in the thermosetting composition after curing from the viewpoint of improving heat resistance. Preferably, the flame retardant is incompatible with the modified polyphenylene ether and / or the cross-linking agent in the thermosetting composition after curing.
Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide and zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide and the like. Aromatic bromine compounds of the above; phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate and the like can be mentioned. These flame retardants may be used alone or in combination of two or more. Among these, the flame retardant is preferably decabromodiphenylethane from the viewpoint of further excellent compatibility between the flame retardant and the modified PPE, coatability of the thermosetting composition, and characteristics of the mounted electronic circuit board. ..

The content of the flame retardant is not particularly limited, but is preferably 5 with respect to a total of 100 parts by mass of the modified polyphenylene ether and the cross-linking agent from the viewpoint of maintaining the flame retardancy of V-0 level of UL standard 94. By mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more. Further, from the viewpoint that the dielectric constant and the dielectric loss tangent of the obtained cured product can be kept low, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less. ..

(Silica filler)
The thermosetting composition of the present embodiment may contain a silica filler. Examples of the silica filler include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, hollow silica and the like.
The content of the silica filler may be 10 to 100 parts by mass with respect to 100 parts by mass in total of the modified polyphenylene ether and the cross-linking agent. Further, the silica filler may be surface-treated with a silane coupling agent or the like on its surface.

In addition to the flame retardant and the silica filler, the heat-curing composition of the present embodiment may further contain a heat stabilizer, an antioxidant, a UV absorber, a surfactant, an additive such as a lubricant, a solvent and the like.
When the thermosetting composition of the present embodiment contains a solvent, the thermosetting composition can be in the form of a varnish in which the solid component in the thermosetting composition is dissolved or dispersed in the solvent, and the heat of the present embodiment can be obtained. A resin film can be formed from the cured composition.

(solvent)
As the solvent, aromatic compounds such as toluene and xylene, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, chloroform and the like are preferable from the viewpoint of solubility. These solvents may be used alone or in combination of two or more.

<Prepreg>
The prepreg of the present embodiment is a composite containing a base material and the thermosetting composition, preferably a base material, and the thermosetting composition of the present embodiment impregnated or coated on the base material. The prepreg can be obtained, for example, by impregnating a varnish of the thermosetting composition with a base material such as glass cloth, and then drying and removing the solvent component with a hot air dryer or the like.

As the base material, various glass cloths such as roving cloths, cloths, chopped mats and surfaced mats; asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; all aromatic polyamide fibers, all aromatic polyesters. Woven or non-woven fabrics obtained from liquid crystal fibers such as fibers and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth and felt; carbon fiber cloth, kraft paper, cotton paper, cloth obtained from paper-glass mixed fiber yarn, etc. Natural cellulose-based base material; polytetrafluoroethylene porous film and the like can be mentioned. These base materials may be used alone or in combination of two or more.

The proportion of the thermosetting composition solid content (components other than the solvent of the thermosetting composition) of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. .. When the above ratio is 30% by mass or more, the insulation reliability tends to be further improved when the prepreg is used for an electronic substrate or the like. When the above ratio is 80% by mass or less, it tends to be more excellent in mechanical properties such as bending elastic modulus in applications such as electronic substrates.

<Laminated body>
The laminate of the present embodiment is a metal-clad laminate obtained by laminating and curing a thermosetting composition of the present embodiment or a prepreg of the present embodiment and a metal foil. The metal-clad laminate preferably has a form in which a cured product of a prepreg (hereinafter, also referred to as a “cured product complex”) and a metal foil are laminated and adhered to each other, and is preferably used as a material for an electronic substrate. Be done.
Examples of the metal foil include aluminum foil and copper foil, and among these, copper foil is preferable because of its low electrical resistance.
The cured product complex to be combined with the metal foil may be one sheet or a plurality of sheets, and depending on the intended use, the metal foil is laminated on one side or both sides of the composite and processed into a laminated plate.

As a method for producing a metal-clad laminate, for example, a composite composed of a thermosetting composition and a base material (for example, the above-mentioned prepreg) is formed, and after laminating this with a metal foil, the thermosetting composition is produced. A method of obtaining a laminated board in which a cured product laminated body and a metal foil are laminated can be mentioned.
One of the particularly preferable uses of the metal-clad laminate is a printed wiring board. It is preferable that at least a part of the metal foil is removed from the metal-clad laminated board of the printed wiring board.

<Printed wiring board>
In the printed wiring board of the present embodiment, at least a part of the metal foil is removed from the metal-clad laminate of the present embodiment. The printed wiring board of the present embodiment can be typically formed by a method of pressure heating molding using the prepreg of the present embodiment described above. Examples of the base material include the same as described above for the prepreg.
The printed wiring board of the present embodiment has excellent heat resistance and electrical characteristics (low dielectric constant and low dielectric loss tangent) by containing the thermosetting composition of the present embodiment, and further has electrical characteristics due to environmental changes. It is possible to suppress fluctuations in the air, and it also has excellent insulation reliability and mechanical properties.

Hereinafter, the present embodiment will be described in more detail based on the 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.

(1) Number average molecular weight (Mn)
Using gel permeation chromatography System21 manufactured by Showa Denko KK as a measuring device, a calibration curve was prepared from standard polystyrene and ethylbenzene, and the calibration curve was used to obtain the number average molecular weight (Mn) of the obtained modified polyphenylene ether. ) Was measured.
As standard polystyrene, the molecular weights are 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, Those of 1,300 and 550 were used.
As the column, two K-805L manufactured by Showa Denko KK were connected in series. Chloroform was used as the solvent, the flow rate of the solvent was 1.0 mL / min, and the temperature of the column was 40 ° C. As a sample for measurement, a 1 g / L chloroform solution of modified polyphenylene ether was prepared and used. The UV wavelength of the detection unit was 254 nm for standard polystyrene and 283 nm for polyphenylene ether.
The number average molecular weight (Mn) (g / mol) was calculated from the ratio of the peak area based on the curve showing the molecular weight distribution obtained by GPC based on the above measurement data.

(2) Glass transition temperature (Tg) of the cured product of the thermosetting composition
The dynamic viscoelasticity of the laminated plates produced in Examples and Comparative Examples was measured, and the temperature at which tan δ was maximized was determined as the glass transition temperature (Tg) (° C.). A dynamic viscoelastic device (RHEOVIBRON model DDV-01FP, manufactured by ORIENTEC) was used as the measuring device. The laminated plate is cut into strips having a length of about 35 mm, a width of about 12 mm, and a thickness of about 0.5 mm so that the warp of the glass cloth has a long side, and used as a test piece. The measurement was performed at.

(3) Relative permittivity of the cured product of the heat-cured composition The relative permittivity of the laminated plates produced in Examples and Comparative Examples at 10 GHz was measured by the cavity resonance method. As a measuring device, a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator CP series) manufactured by Kanto Electronics Applied Development Co., Ltd. were used. The laminated board was cut into strips having a width of about 2 mm, a length of 50 mm, and a thickness of about 0.5 mm so that the warp of the glass cloth had a long side. Next, the cells were placed in an oven at 105 ° C. ± 2 ° C. and dried for 2 hours, and then allowed to stand in an environment at 23 ° C. and a relative humidity of 50 ± 5% for 24 ± 5 hours. Then, the relative permittivity was measured by using the above measuring device in an environment of 23 ° C. and a relative humidity of 50 ± 5%.

(4) Quantification of impurities in modified polyphenylene ether Analysis by GC / MS. Using GC-6890 MSD-5973 manufactured by Azilent, column: HP-5MS (L: 30m ID: 0.25mm Film thickness: 0.25μm), carrier gas: helium, the temperature of the sample inlet is 325 ° C. The column temperature was maintained at 325 ° C., detected by an MSD detector, and by-products were quantified by electron ionization mass spectrometry of the separated gas.

(5) Quantification of chloride ion in modified polyphenylene ether The chloride ion content (mass ppm) in the modified polyphenylene ether was determined by ion chromatography of the modified polyphenylene ether to be measured.

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

(Manufacturing Example 1)
Pre-arranged 0.12 g in a 1.5 liter jacketed reactor with a spudger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux cooler on the vent gas line at the top of the reactor. A mixture of cuprous oxide and 1.29 g of hydrogen bromide and 0.28 g of N, N'-di-t-butylethylenediamine, 10.22 g of dimethyl-n-butylamine, 2.23 g of di. -N-butylamine, 885.6 g of toluene, 69.39 g of 2,6-dimethylphenol, 30.61 g of 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (Made by ADEKA: AO-30), 0.05 g of trioctylmethylammonium chloride was added. Then, with vigorous stirring, air was started to be introduced into the reactor at a rate of 1.05 L / min from the spudger, and at the same time, the polymerization temperature was adjusted by passing a heat medium through the jacket so as to maintain 20 ° C. 200 minutes after the introduction of air was started, the ventilation of the air was stopped, nitrogen gas was replaced in the reactor, and then 1.49 g of ethylenediamine tetraacetic acid tetrasodium salt tetrahydrate was added to this polymerization mixture (Dojin Chemical Research). It was added as an aqueous solution of (manufactured reagent) and 200 g of water.
Further, a mixed solution of 1.0 g of hydroquinone and 40 g of water was added, and the mixture was kept warm at 20 ° C. for 1 hour to reduce the by-produced diphenoquinone, then heated to 70 ° C. and copper at 70 ° C. for 1 hour. Extraction was performed. Then, it was separated into an unmodified polyphenylene ether solution (organic phase) and an aqueous phase to which the catalyst metal was transferred by static separation. The organic layer was concentrated by an evaporator to obtain an unmodified polyphenylene ether in a solid state.

(Manufacturing Example 2)
Pre-arranged 0.062 g in a 1.5 liter jacketed reactor with a spudger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux cooler on the vent gas line at the top of the reactor. A mixture of cuprous oxide and 0.69 g of 47% hydrogen bromide, 0.20 g of N, N'-di-t-butylethylenediamine, 2.81 g of dimethyl-n-butylamine, 1.31 g of di. -N-butylamine, 865.0 g of toluene, 72.3 g of 2,6-dimethylphenol, 34.53 g of 2,3,6-trimethylphenol, 23.16 g of 2,2-bis (3,5-dimethyl) -4-Hydroxyphenyl) propane, 0.05 g of trioctylmethylammonium chloride was added. Then, with vigorous stirring, air was started to be introduced into the reactor at a rate of 1.37 L / min from the spudger, and at the same time, the polymerization temperature was adjusted by passing a heat medium through the jacket so as to maintain 20 ° C. 200 minutes after the start of introducing air, the aeration of air was stopped, nitrogen gas was replaced in the reactor, and then 0.70 g of ethylenediamine tetraacetic acid tetrasodium salt tetrahydrate was added to this polymerization mixture (Dojin Chemical Research). (Manufactured reagent) was added as an aqueous solution of 200 g of water. Further, a mixed solution of 1.2 g of hydroquinone and 40 g of water was added, and the mixture was kept warm at 20 ° C. for 1 hour to reduce the by-produced diphenoquinone, then heated to 70 ° C. and copper at 70 ° C. for 1 hour. Extraction was performed. Then, it was separated into an unmodified polyphenylene ether solution (organic phase) and an aqueous phase to which the catalyst metal was transferred by static separation. The organic layer was concentrated by an evaporator to obtain an unmodified polyphenylene ether in a solid state.

(Example 1)
30 g of the unmodified polyphenylene ether obtained in Production Example 1 in a 500 mL jacketed reactor equipped with a line for introducing nitrogen gas in the upper part of the reactor, a stirring turbine blade and baffle, and a reflux condenser in the vent gas line in the upper part of the reactor. Was put in. After replacing the inside of the reactor with nitrogen, 70 g of toluene and 104 g of dimethyl sulfoxide were added to prepare an unmodified polyphenylene ether solution. While stirring, 13.57 g of triethylamine was added using a syringe, and 2.34 g of dimethylaminopyridine was further added. Then, 8.58 g of vinyl methacrylate was collected in a syringe, added dropwise to the system, and stirring was continued at 110 ° C. for 18 hours. After returning to room temperature, 2.00 g of methanol was added to terminate the reaction. Then, the reaction solution was concentrated to a solid content concentration of 22% by mass, and then the reaction solution was added dropwise to 665.06 g of methanol to obtain a precipitate of modified polyphenylene ether. The wet-modified polyphenylene ether recovered by vacuum filtration was dissolved again in 180 g of toluene, 207.01 g of a sodium hydroxide aqueous solution having a pH of 10 was added, and liquid separation was carried out. The organic layer was concentrated to 110 g, and the organic layer was added dropwise to 567.67 g of methanol to obtain a wet-modified polyphenylene ether. The wet-modified polyphenylene ether was washed with 200 mL of methanol and vacuum dried at 110 ° C. for 2 hours to obtain a modified polyphenylene ether.
Next, to 79 parts by mass of the modified polyphenylene ether, 20 parts by mass of TAIC (manufactured by Nihon Kasei Co., Ltd.) and 1 part by mass of an organic peroxide (perbutyl P, manufactured by Nihon Kasei Co., Ltd.) were added to toluene, and the mixture was stirred and dissolved. A varnish was obtained (solid content concentration 58% by mass). After impregnating this varnish with L glass cloth (manufactured by Asahi Schebel Co., Ltd., style: 2116), excess varnish is scraped off by passing it through a predetermined slit, dried in a drying oven at 105 ° C. for a predetermined time, and toluene is used. Was removed to obtain a prepreg. When this prepreg was cut into a predetermined size and the mass of the prepreg was compared with the mass of a glass cloth of the same size, the solid content of the thermosetting composition in the prepreg was calculated to be 52% by mass. ..
A predetermined number of these prepregs are stacked, and copper foil (manufactured by Furukawa Electric Co., Ltd., thickness 35 μm, GTS-MP foil) is laminated on both sides of the stacked prepregs, and a vacuum press is performed to cover the copper. A laminated board was obtained. In this vacuum pressing step, first, the pressure is set to 40 kg / cm ² while heating from room temperature at a heating rate of 2 ° C./min, and then after the temperature reaches 200 ° C., the temperature is maintained at 200 ° C. The conditions of pressure 40 kg / cm ² and time 60 minutes were adopted.
Next, a laminated plate (thickness of about 0.5 mm) was obtained by removing the copper foil from the copper-clad laminate by etching.
The results of each analysis are shown in Table 1.

(Example 2)
The operation was carried out in the same manner as in Example 1 except that the solvent for the modification reaction was changed to 136 g of toluene and 34 g of dimethyl sulfoxide to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Example 3)
The operation was carried out in the same manner as in Example 1 except that the solvent for the modification reaction was changed to 34 g of toluene and 136 g of dimethyl sulfoxide to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Example 4)
30 g of the unmodified polyphenylene ether obtained in Production Example 2 in a 500 mL jacketed reactor equipped with a line for introducing nitrogen gas in the upper part of the reactor, a stirring turbine blade and baffle, and a reflux condenser in the vent gas line in the upper part of the reactor. Was put in. After replacing the inside of the reactor with nitrogen, 70 g of toluene and 104 g of dimethyl sulfoxide were added to prepare an unmodified polyphenylene ether solution. While stirring, 10.62 g of triethylamine was added using a syringe, and 1.83 g of dimethylaminopyridine was further added. Then, 6.72 g of vinyl methacrylate was collected in a syringe, added dropwise to the system, and stirring was continued at 110 ° C. for 18 hours.
Others were operated in the same manner as in Example 1 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Example 5)
The denaturation reaction was carried out using 4.74 g of scandium triflate without using dimethylaminopyridine and triethylamine. Moreover, the modification reaction was carried out using only 192 g of toluene as a solvent. Others were operated in the same manner as in Example 1 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Example 6)
The denaturation reaction was carried out using 4.74 g of scandium triflate without using dimethylaminopyridine and triethylamine. The modification reaction was carried out using 76.8 g of toluene and 115.2 g of dimethyl sulfoxide as a solvent. Others were operated in the same manner as in Example 1 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Example 7)
The denaturation reaction was carried out using 4.74 g of scandium triflate without using dimethylaminopyridine and triethylamine. Moreover, the modification reaction was carried out using only 192 g of toluene as a solvent. Others were operated in the same manner as in Example 4 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Comparative Example 1)
A stirrer was placed in a 300 ml three-necked flask, a Dimroth condenser with a three-way cock attached to the main tube was installed, and a rubber stopper with a thermometer was attached to one side tube. 73.5 g of toluene and 26.0 g of the unmodified polyphenylene ether obtained in Production Example 1 were mixed and heated to about 85 ° C. 0.33 g of dimethylaminopyridine was added. When all the solids seemed to be dissolved, 4.2 g of methacrylic anhydride was gradually added. The resulting solution was maintained at 85 ° C. for 3 hours with continuous mixing.
Others were operated in the same manner as in Example 1 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Comparative Example 2)
A stirrer was placed in a 300 ml three-necked flask, a Dimroth condenser with a three-way cock attached to the main tube was installed, and a rubber stopper with a thermometer was attached to one side tube. 73.5 g of toluene and 26.0 g of the unmodified polyphenylene ether obtained in Production Example 2 were mixed and heated to about 85 ° C. 0.33 g of dimethylaminopyridine was added. When all the solids seemed to be dissolved, 4.2 g of methacrylic anhydride was gradually added. The resulting solution was maintained at 85 ° C. for 3 hours with continuous mixing.
Others were operated in the same manner as in Example 1 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

(Comparative Example 3)
A stirrer was placed in a 300 ml three-necked flask, a Dimroth condenser with a three-way cock attached to the main tube was installed, and a rubber stopper with a thermometer was attached to one side tube. 20 g of the unmodified polyphenylene ether composition obtained in Production Example 1 was charged from the other side tube, and a rubber stopper was attached. After the inside of the flask was replaced with nitrogen, it was dissolved in 140 g of toluene using a syringe while stirring the inside with a magnetic stirrer, and then 6.32 g of triethylamine was added. Then, 3.27 g of methacryloyl chloride was collected in a syringe and dropped into the system from a rubber stopper. After the stirring was continued at room temperature for 3 hours after the completion of the dropping, the flask was heated in an oil bath and the reaction was continued in a reflux state. Heating was stopped when 2 hours had passed from the start of reflux, and after returning to room temperature, 1.00 g of methanol was added to stop the reaction. Next, the reaction solution was concentrated to a solid content concentration of 20% by weight, and then washed with water using ion-exchanged water having the same weight as the concentrated solution. Then, the water tank was removed, and the organic layer was added dropwise to methanol (5 times the weight of the organic layer) with stirring. The precipitate was then filtered and the filtrate was vacuum dried at 110 ° C. for 1 hour to give a modified polyphenylene ether composition.
Others were operated in the same manner as in Example 1 to obtain a modified polyphenylene ether and a laminated board.
The results of each analysis are shown in Table 1.

As shown in Table 1, by comparing with Comparative Examples 1 to 3, it was possible to obtain a thermosetting composition of the modified polyphenylene ether having an increased glass transition temperature by using the modified polyphenylene ethers of Examples 1 to 7. ..

Since the modified polyphenylene ether and the thermosetting composition of the present invention have a high glass transition temperature, they have industrial utility value as electronic material applications.

Claims (8)

A modified polyphenylene ether represented by the following formula (1).
The polystyrene-equivalent number average molecular weight is 500 to 15,000.
Based on the total amount of the modified polyphenylene ether, the content of methacrylic acid is less than 200 ppm, the total content of methacrylic anhydride and vinyl chloride is less than 200 ppm, the content of the organic amine catalyst is less than 200 ppm, and the chloride ion. A modified polyphenylene ether characterized by a content of less than 1500 ppm.

... Equation (1)
(In the formula (1), Z is a partial structure of a valence represented by the following formula (2), a represents an integer of 2 to 6, and Y is independently represented by the following formula (4). It is a divalent linking group having a structure, n represents the number of repetitions of Y, each is an integer of 0 to 200 independently, and at least one n in a (-Yn-A) is an integer of 1 or more. A is a group represented by the following formula (5).

... Equation (2)
In the formula (2), X is an arbitrary linking group having a valence, and ^R4 is any of a linear alkyl group having 1 to 8 carbon atoms and a partial structure represented by the following formula (3). The carbon atom of the benzene ring to which —O— is bonded is at the 1-position, and is bonded to at least one of the carbon atoms at the 2-position or the 6-position, and k is an independently integer of 1 to 4.

... formula (3)
In formula (3), R ¹¹ is an alkyl group having 1 to 8 carbon atoms which may be substituted independently, and R ¹² is an alkylene group having 1 to 8 carbon atoms which may be substituted independently. There, b is 0 or 1, respectively, and R ¹³ is either a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, and a phenyl group which may be substituted.

... Equation (4)
In formula (4), each of R ²¹ is independently any of a hydrocarbon group having 1 to 6 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, and a halogen atom. Is.

... Equation (5)
In the above formula (5), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an aryloxy. It is either a group, an amino group, or a hydroxyalkyl group, and R ³² is an independently hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group), and s is an integer of 0 to 5. ) A method for producing a modified polyphenylene ether, which comprises a reaction step between an unmodified polyphenylene ether represented by the following formula (8) and an unsaturated compound of the following formula (10).

... Equation (8)
(In the formula (8), Z is a partial structure of a valence represented by the following formula (2), a represents an integer of 2 to 6, and Y is independently represented by the following formula (4). It is a divalent linking group having a structure, n represents the number of repetitions of Y, each is an integer of 0 to 200 independently, and at least one n in a (-Yn-A) is an integer of 1 or more. Is.

... Equation (2)
In the formula (2), X is an arbitrary linking group having a valence, and ^R4 is any of a linear alkyl group having 1 to 8 carbon atoms and a partial structure represented by the following formula (3). The carbon atom of the benzene ring to which —O— is bonded is at the 1-position, and is bonded to at least one of the carbon atoms at the 2-position or the 6-position, and k is an independently integer of 1 to 4.

... formula (3)
In formula (3), R ¹¹ is an alkyl group having 1 to 8 carbon atoms which may be substituted independently, and R ¹² is an alkylene group having 1 to 8 carbon atoms which may be substituted independently. Yes, b is 0 or 1 independently, and R ¹³ is either a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, and a phenyl group which may be substituted.

... Equation (4)
In formula (4), R ²¹ is independently any one of a hydrocarbon group having 1 to 6 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, and a halogen atom. Is.

... formula (10)
In the above formula (10), each of R ³¹ independently has a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms (for example, a chain hydrocarbon group or a cyclic hydrocarbon group), an aryl group, an alkoxy group, or an aryloxy. It is either a group, an amino group, or a hydroxyalkyl group, and R ³² is independently a hydrocarbon group having 1 to 30 carbon atoms (for example, an alkylene group), and s is an integer of 0 to 5. ) The production according to claim 2, wherein the reaction between the unmodified polyphenylene ether represented by the formula (8) and the unsaturated compound of the formula (10) is carried out in the presence of an organic amine catalyst or a Lewis acid catalyst. Method. The reaction between the unmodified polyphenylene ether represented by the formula (8) and the unsaturated compound of the formula (10) is carried out in the presence of the organic amine catalyst, and the organic amine catalyst is dimethylaminopyridine. The manufacturing method according to claim 3. A thermosetting composition comprising the modified polyphenylene ether according to claim 1. A prepreg comprising a substrate and the thermosetting composition according to claim 5. The prepreg according to claim 6, wherein the base material is glass cloth. A laminate comprising the cured product of the prepreg according to claim 6 or 7 and a metal foil.