JP2006316092A - Polyphenylene ether, method for producing the same and use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyphenylene ether that is useful as an electric and an electronic materials, especially as a solder resist material, is easily crosslinked and provides a cured material having excellent heat resistance, dielectric characteristics and chemical resistance and a curable resin composition that is useful as a solder resist for FPC and has flexibility or ductility. <P>SOLUTION: (i) The polyphenylene ether has a structure represented by general formula (1), a structure represented by general formula (2) or a structure represented by general formula (3) and contains one or more kinds of functional groups selected from the group consisting of a hydroxy group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group and a cyanate group. (ii) The curable resin composition comprises the curable polyphenylene ether (A), a curing agent (B) and, if necessary, a curable resin (C) and/or a flexibility imparting agent (D). (iii) The cured material is obtained by curing the curable resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel polyphenylene ether suitable for use in electrical and electronic materials such as printed circuit boards and insulating sealants. More specifically, the present invention relates to a polyphenylene ether having a crosslinkable curable functional group, a production method thereof, a curable resin composition containing the polyphenylene ether, a cured product thereof, and a solder resist application thereof.

  Polyphenylene ether is a resin obtained by oxidative polymerization of a phenol compound, and has high heat resistance and excellent dielectric properties. Therefore, it is a material suitable for printed circuit boards and resists for electrical and electronic equipment. In general, an electronic material such as a resist is usually used in a form in which a resin component is dissolved in a solvent such as varnish or ink. Therefore, it is desirable that the molecular weight of polyphenylene ether is low in the process such as coating. However, it has not always been easy to produce a low molecular weight polyphenylene ether suitable for an electronic material. In particular, when polyphenylene ether is produced from phenol or monosubstituted phenol, gel formation is likely to occur during oxidative polymerization, and it is difficult to produce low molecular weight polyphenylene ether. For this reason, 2,6-disubstituted phenols such as 2,6-dimethylphenol are usually used for the production of polyphenylene ether.

  As a low molecular weight polyphenylene ether, Japanese Patent Application Laid-Open No. 2003-12796 (Patent Document 1) proposes a polyphenylene ether derived from a 2,6-disubstituted phenol obtained by copolymerizing a specific biphenol compound and a 2,6-disubstituted phenol. Has been. However, since a special biphenol compound is used, there is a problem that the resulting polyphenylene ether is expensive.

  As polyphenylene ether from monosubstituted phenol, Japanese Patent Application Laid-Open No. 10-168179 (Patent Document 2) proposes polyphenylene ether obtained by polymerizing 2-phenylphenol. This polyphenylene ether is described as being superior in heat resistance and the like compared to a normal polyphenylene ether obtained by polymerizing 2,6-dimethylphenol. However, since 2-phenylphenol is a monosubstituted phenol, it is still gelled. It was difficult to produce a low molecular weight substance used for an electronic material such as a resist.

  On the other hand, the use of flexible printed wiring boards (FPC) such as chip-on-film (COF) and system-on-film (SOF) has been increasing in recent years. Therefore, the appearance of a material for an insulating protective film (solder resist) having excellent insulating properties and heat resistance is desired.

  However, when the above polyphenylene ether is used in such a field, although it has excellent insulating properties and heat resistance, it has high rigidity and has problems such as generation of cracks. It is flexible or soft, such as a solder resist for FPC. Therefore, it has been difficult to apply to applications that require high performance.

Japanese Patent Laid-Open No. 2003-12796 JP-A-10-168179

  Accordingly, the present invention provides a cured product having excellent heat resistance, dielectric properties and chemical resistance, which is easily crosslinked and cured, and is useful as an electric / electronic material such as a printed circuit board and an insulating sealant, particularly a solder resist material. The object is to economically provide a low molecular weight polyphenylene ether. Another object of the present invention is to provide a curable resin composition having flexibility or flexibility that can be used for a solder resist for FPC and the like.

  As a result of intensive studies in view of the above situation, the present inventor has found that when a specific phenol compound having a cycloalkyl group at the o (ortho) -position is oxidatively polymerized, even if it is a monosubstituted phenol, a special biphenol compound is not used. A polyphenylene ether having a relatively low molecular weight is obtained, and this and a polyphenylene ether in which a functional group such as an epoxy group is introduced into this hydroxyl group can be easily crosslinked and cured to produce a cured product having excellent heat resistance, dielectric properties and chemical resistance. The present invention has been found to be effective in solving the above-mentioned problems, and the present invention has been completed.

（式中、Ｒ¹およびＲ²はそれぞれ独立してハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ¹またはＲ²が複数存在する場合各々は同一でも異なってもよく、ｐは０または１〜３の整数であり、ｑは０または１〜５の整数であり、ｎは２〜１０００の整数である。）
で示される化学構造を有し、かつ水酸基、エポキシ基、アリル基、アクリロイル基、メタクリロイル基およびシアナート基からなる群から選ばれる１種以上の官能基を１以上有するポリフェニレンエーテル。
２．一般式（２）

（式中、Ｒ³は単結合、炭素数１〜３０の２価の炭化水素基、酸素原子、硫黄原子またはスルホニル基を表し、Ｒ⁴はハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ⁴が複数存在する場合各々は互いに同一でも異なってもよく、ｒおよびｓはそれぞれ独立して０または１〜４の整数である。）
で示される化学構造および／または一般式（３）

（式中、Ｒ⁵はハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ⁵が複数存在する場合各々は互いに同一でも異なってもよく、ｔは０または１〜４の整数であり、Ｒ⁶はｍ価の炭化水素基であり、ｍは３〜６の整数である。）
で示される化学構造をさらに有する前記１に記載のポリフェニレンエーテル。
３．一般式（４）

（式中、Ｒ¹、Ｒ²、ｐおよびｑは前記１の記載と同じ意味を表し、Ｘ¹は水素原子、メチル基、フッ素原子、塩素原子、臭素原子またはヨウ素原子を表す。）
で示されるモノフェノール化合物を単独で、または他のフェノール化合物と共に酸化重合して得られる前記１に記載のポリフェニレンエーテル。
４．一般式（４）

（式中、Ｒ¹、Ｒ²、ｐおよびｑは前記１の記載と同じ意味を表し、Ｘ¹は水素原子、メチル基、フッ素原子、塩素原子、臭素原子またはヨウ素原子を表す。）
で示されるモノフェノール化合物と一般式（５）

（式中、Ｒ³、Ｒ⁴、ｒおよびｓは前記２の記載と同じ意味を表す。）
および／または一般式（６）

（式中、Ｒ⁵、Ｒ⁶、ｔおよびｍは前記２の記載と同じ意味を表す。）
で示されるポリフェノール化合物とを酸化重合して得られる前記２に記載のポリフェニレンエーテル。
５．一般式（８）

（式中、Ｒ¹、Ｒ²、ｐ、ｑおよびｎは前記１の記載と同じ意味を表し、Ｒ⁷、Ｒ⁸、およびＲ⁹はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ¹⁰はヘテロ原子を含んでいてもよい２価の炭化水素基を表す。）
で示される化学構造を有する前記１〜４のいずれかの項に記載のポリフェニレンエーテル。
６．数平均分子量が５００〜20,000である前記１〜６のいずれかの項に記載のポリフェニレンエーテル。
７．エポキシ当量が３００〜2,000である前記１〜７のいずれかの項に記載のポリフェニレンエーテル。
８．一般式（４）

（式中、Ｒ¹およびＲ²はそれぞれ独立してハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ¹またはＲ²が複数存在する場合各々は同一でも異なってもよく、ｐは０または１〜３の整数であり、ｑは０または１〜５の整数であり、Ｘ¹は水素原子、メチル基、フッ素原子、塩素原子、臭素原子またはヨウ素原子を表す。）
で示されるモノフェノール化合物、および所望により一般式（５）

（式中、Ｒ³は単結合、炭素数１〜３０の２価の炭化水素基、酸素原子、硫黄原子またはスルホニル基を表し、Ｒ⁴はハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ⁴が複数存在する場合各々は互いに同一でも異なってもよく、ｒおよびｓはそれぞれ独立して０または１〜４の整数である。）
および／または一般式（６）

（式中、Ｒ⁵はハロゲン原子または炭素数１〜２０の炭化水素基を表し、Ｒ⁵が複数存在する場合各々は互いに同一でも異なってもよく、ｔは０または１〜４の整数であり、Ｒ⁶はｍ価の炭化水素基であり、ｍは３〜６の整数である。）
で示されるポリフェノール化合物を酸化（共）重合する工程を含むことを特徴とするポリフェニレンエーテルの製造方法。
９．（Ａ）前記１〜７のいずれかに記載のポリフェニレンエーテルおよび（Ｂ）硬化剤を含有することを特徴とするポリフェニレンエーテル組成物。
１０．さらに、（Ｃ）硬化性樹脂を含有する前記９に記載のポリフェニレンエーテル組成物。
１１．さらに、可撓性付与剤（Ｄ）を含有する前記９または１０に記載のポリフェニレンエーテル組成物。
１２．前記９〜１１のいずれかに記載のポリフェニレンエーテル組成物の硬化物。
１３．ソルダーレジスト用である前記１〜７のいずれかに記載のポリフェニレンエーテル。
１４．ソルダーレジスト用である前記９〜１１のいずれかに記載のポリフェニレンエーテル組成物。
１５．ソルダーレジスト用である前記１２に記載の硬化物。 That is, this invention relates to the following curable polyphenylene ether, its manufacturing method, the curable resin composition containing it, its hardened | cured material, and those solder resist uses.
1. General formula (1)

(In the formula, R ¹ and R ² each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ¹ or R ² are present, each may be the same or different, and p is 0 or an integer of 1 to 3, q is an integer of 0 or 1 to 5, and n is an integer of 2 to 1000.)
And a polyphenylene ether having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group and a cyanate group.
2. General formula (2)

(In the formula, R ³ represents a single bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom, a sulfur atom or a sulfonyl group, and R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. And when a plurality of R ⁴ are present, each may be the same or different, and r and s are each independently 0 or an integer of 1 to 4.)
And / or general formula (3)

(Wherein R ⁵ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵ are present, each may be the same as or different from each other, and t is 0 or an integer of 1 to 4) R ⁶ is an m-valent hydrocarbon group, and m is an integer of 3 to ^6. )
2. The polyphenylene ether according to 1 above, further having a chemical structure represented by:
3. General formula (4)

(Wherein R ¹ , R ² , p and q represent the same meaning as described in 1 above, and X ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)
2. The polyphenylene ether according to 1 above, which is obtained by oxidative polymerization of the monophenol compound represented by the formula alone or together with another phenol compound.
4). General formula (4)

(Wherein R ¹ , R ² , p and q represent the same meaning as described in 1 above, and X ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)
And a monophenol compound represented by the general formula (5)

(In the formula, R ³ , R ⁴ , r and s represent the same meaning as described in 2 above.)
And / or general formula (6)

(In the formula, R ⁵ , R ⁶ , t and m have the same meaning as described in 2 above.)
3. The polyphenylene ether according to 2 above, obtained by oxidative polymerization of a polyphenol compound represented by the formula:
5. General formula (8)

(Wherein R ¹ , R ² , p, q and n represent the same meaning as described in 1 above, and R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom or a carbon number of 1; Represents a hydrocarbon group of ˜20, and R ¹⁰ represents a divalent hydrocarbon group which may contain a hetero atom.)
The polyphenylene ether according to any one of 1 to 4 above, which has a chemical structure represented by:
6). The polyphenylene ether according to any one of 1 to 6 above, wherein the number average molecular weight is 500 to 20,000.
7). The polyphenylene ether according to any one of 1 to 7 above, wherein the epoxy equivalent is 300 to 2,000.
8). General formula (4)

(In the formula, R ¹ and R ² each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ¹ or R ² are present, each may be the same or different, and p is (0 or an integer of 1 to 3, q is an integer of 0 or 1 to 5, and X ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
And, if desired, general formula (5)

(In the formula, R ³ represents a single bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom, a sulfur atom or a sulfonyl group, and R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. And when a plurality of R ⁴ are present, each may be the same or different, and r and s are each independently 0 or an integer of 1 to 4.)
And / or general formula (6)

(Wherein R ⁵ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵ are present, each may be the same as or different from each other, and t is 0 or an integer of 1 to 4) R ⁶ is an m-valent hydrocarbon group, and m is an integer of 3 to ^6. )
A process for producing a polyphenylene ether, comprising a step of oxidizing (co) polymerizing a polyphenol compound represented by formula (1).
9. (A) A polyphenylene ether composition comprising the polyphenylene ether according to any one of 1 to 7 and (B) a curing agent.
10. Furthermore, the polyphenylene ether composition of said 9 containing (C) curable resin.
11. Furthermore, the polyphenylene ether composition of said 9 or 10 containing a flexibility imparting agent (D).
12 Hardened | cured material of the polyphenylene ether composition in any one of said 9-11.
13. The polyphenylene ether according to any one of 1 to 7 above, which is used for a solder resist.
14 The polyphenylene ether composition according to any one of 9 to 11, which is used for a solder resist.
15. 13. The cured product as described in 12 above, which is for solder resist.

According to the present invention, a low molecular weight polyphenylene ether suitable for an electronic material can be easily obtained by oxidative polymerization of a specific phenol compound having a cycloalkyl group at the o-position.
The cured polyphenylene ether obtained by crosslinking and curing the polyphenylene ether of the present invention has high heat resistance and excellent dielectric properties or chemical resistance.
The polyphenylene ether of the present invention easily crosslinks and cures, and the resulting cured product has excellent insulating properties and heat resistance, and is suitable for electrical and electronic materials such as printed boards and insulating sealants, especially for solder resist materials. Is suitable.
The cured product of the composition containing the polyphenylene ether and the flexibility-imparting agent of the present invention suppresses the generation of cracks during bending, and is particularly suitable for printed circuit boards and insulating seals in fields requiring flexibility or flexibility. Suitable for electrical and electronic materials such as chemicals, especially for flexible solder resist materials.

で示される化学構造ユニットを有する。 [Curable polyphenylene ether]
The curable polyphenylene ether of the present invention has the general formula (1)

It has a chemical structural unit shown by.

In formula (1), R ¹ and R ² each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ¹ or R ² are present, each may be the same or different. . Examples of the halogen atom related to R ¹ and R ² include a chlorine atom, a bromine atom, and a fluorine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms according to R ¹ and R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t- Chain or cyclic alkyl groups such as butyl group, n-pentyl group, n-hexyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; arylalkyl groups such as benzyl group and phenethyl group Is mentioned. Of these, a halogen atom or a phenyl group is preferable, and a phenyl group is most preferable.

In the formula (1), p is 0 or an integer of 1 to 3, preferably 0 or 1, and most preferably 0. Q is 0 or an integer of 1 to 5, preferably 0 or 1, and most preferably 0. In the formula (1), when p or q is not 0, R ¹ and R ² are each independently selected from a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms. N in Formula (1) is an integer of 2 to 1000, preferably 2 to 100, more preferably 2 to 50, particularly preferably 2 to 30, and most preferably 3 to 20. When n is less than 2, the heat resistance when cured is insufficient. Further, when a composition such as a resist is used, the viscosity of the composition is lowered, which may hinder the coating. Moreover, when n exceeds 1000, the solubility with respect to a solvent may fall, or the mixing | blending to compositions, such as a resist, may become difficult.
The value of n can be obtained as follows. That is, the phenolic hydroxyl group mainly remaining at the terminal of the polyphenylene ether is sufficiently reacted with a silylating agent such as trimethylchlorosilane or an acylating agent such as acetic anhydride to be converted into a silyl group or an acyl group. The proton nuclear magnetic resonance spectrum (hereinafter sometimes referred to as ¹ H-NMR spectrum) of the polyphenylene ether having a silyl group or an acyl group is measured, and the formula (1) with respect to 1 equivalent of the silyl group or acyl group is measured. The equivalent of the chemical structure is determined and this is taken as the value of n. In addition, when absorption derived from a silyl group or an acyl group in the ¹ H-NMR spectrum overlaps with absorption derived from the chemical structure of the formula (1), measurement is performed by appropriately converting a phenolic hydroxyl group to another functional group. be able to.

で示される化学構造および／または一般式（３）

で示される化学構造をさらに有していてもよい。 The polyphenylene ether of the present invention has the general formula (2)

And / or general formula (3)

It may further have a chemical structure represented by

In formula (2), R ³ is a single bond, a divalent hydrocarbon group, an oxygen atom, a sulfur atom or a sulfonyl group having 1 to 30 carbon atoms. Specific examples of the divalent hydrocarbon group having 1 to 30 carbon atoms include methylene group, ethylene group, ethylidene group, isopropylidene group, benzylidene group, cyclopentylidene group, cyclohexylidene group, fluorene-9,9- A diyl group etc. are mentioned. Of these, a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms is preferable, and a single bond, a methylene group, or an isopropylidene group is particularly preferable.

In formula (2), R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁴ are present, each may be the same as or different from each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, t-butyl group, and phenyl group. R and s are each independently 0 or an integer of 1 to 4, preferably 0 or 2.

In formula (3), R ⁵ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵ are present, each may be the same as or different from each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, t-butyl group, and phenyl group. Moreover, t is 0 or an integer of 1-4, and 0 or 2 is preferable.

In the formula (3), R ⁶ is an m (3-6) valent arbitrary hydrocarbon group, and specific examples thereof include a methylidine group and an ethylidine group. Moreover, in Formula (3), m is an integer of 3-6, and 3 is preferable.

  The polyphenylene ether of the present invention contains one or more functional groups selected from the group consisting of a hydroxyl group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group, and a cyanate group in one molecule of the polyphenylene ether. When two or more functional groups are present in one molecule, each may be the same or different.

（式中、Ｒ⁷、Ｒ⁸およびＲ⁹は、それぞれ独立して水素原子、ハロゲン原子または炭素数１〜２０の炭化水素基を表わす。）
で示されるものが好ましい。 Here, the epoxy group is represented by the general formula (7).

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms)
Is preferred.

In the formula (7), examples of the halogen atom related to R ⁷ , R ⁸ and R ⁹ include a chlorine atom, a bromine atom and a fluorine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms according to R ⁷ , R ⁸ and R ⁹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. , T-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group and other chain or cyclic alkyl groups, phenyl group, tolyl group, naphthyl group and other aryl groups, benzyl group, phenethyl group and other aryl groups An alkyl group etc. are mentioned. Among these, a hydrogen atom, a methyl group, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.

（式中、Ｒ¹、Ｒ²、ｐ、ｑおよびｎは前記式（１）の場合と同じ意味を表わし、Ｒ⁷、Ｒ⁸、Ｒ⁹は、前記式（７）の場合と同じ意味を表わし、Ｒ¹⁰はヘテロ原子を含んでいてもよい２価の炭化水素基を表す。）
で示される化学構造を有するものが好ましい。 When the polyphenylene ether of the present invention has the epoxy group, the general formula (8)

(Wherein R ¹ , R ² , p, q and n represent the same meaning as in formula (1), and R ⁷ , R ⁸ and R ⁹ have the same meaning as in formula (7). R ¹⁰ represents a divalent hydrocarbon group which may contain a hetero atom.)
Those having a chemical structure represented by

In the formula (8), R ¹ , R ² , p, q, n and R ⁷ , R ⁸ , R ⁹ and preferred ones thereof are the same as those in the formulas (1) and (7). In formula (8), R ¹⁰ is a divalent hydrocarbon group which may contain a hetero atom. Specific examples thereof include aliphatic groups which may be branched, such as alkylene groups such as methylene group, ethylene group, propylene group, tetramethylene group and hexamethylene group, alkylidene groups such as ethylidene group, propylidene group and isopropylidene group. Examples thereof include an aliphatic or aromatic cyclic divalent hydrocarbon group such as a chain divalent hydrocarbon group, a cyclohexylene group, and a phenylene group.

で示される２価のメチレンフェニレン基および一般式（１０）

で示される２価のフェニレンエーテル基が挙げられる。 In the formula (8), as another example of R ¹⁰ , the general formula (9)

And a divalent methylenephenylene group represented by the general formula (10)

The bivalent phenylene ether group shown by these is mentioned.

In the formula (10), R ¹¹ represents a fluorine atom, a chlorine atom, a bromine atom, or a hydrocarbon group having 1 to 10 carbon atoms. A plurality of R ¹¹ exist when “u + w” in formula (10) is 2 or more. When a plurality of R ¹¹ are present, each may be the same or different. u and w are each independently 0 or an integer of 1 to 4. Preferable specific examples of the hydrocarbon group having 1 to 10 carbon atoms include a methyl group and an ethyl group.

In the formula (10), R ¹² represents a single bond, an aliphatic chain divalent hydrocarbon group which may be branched such as an alkylene group such as a methylene group, an alkylidene group such as an ethylidene group or an isopropylidene group, or cyclopentyl. Bivalent hydrocarbon groups such as an aliphatic cyclic divalent hydrocarbon group such as a lidene group and cyclohexylidene group, an aromatic cyclic divalent hydrocarbon group such as a fluorene-9,9-diyl group, a sulfonyl group, a sulfur atom, and an oxygen atom. Represents a linking group.

Of the specific examples of R ¹⁰ in formula (8), the phenylene ether group and methylene group represented by formula (10) are preferred, and the methylene group is particularly preferred.

（式中、Ｒ¹、Ｒ²、ｐおよびｑは前記式（１）の場合と同じ意味を表し、Ｘ¹は水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子を表す。）
で示されるモノフェノール化合物を単独で、または他のフェノール化合物好ましくは一般式（５）

（式中の記号は前記式（２）の場合と同じ意味を表す。）
および／または一般式（６）

（式中の記号は前記式（３）の場合と同じ意味を表す。）
で示されるポリフェノール化合物と共に酸化重合することにより製造するか、または得られるポリフェニレンエーテルに、水酸基、エポキシ基、アリル基、アクリロイル基、メタクリロイル基およびシアナート基からなる群から選ばれる１種以上の官能基を１以上導入する反応に付すことにより製造することができる。 [Production method of polyphenylene ether]
The polyphenylene ether of the present invention has the general formula (4)

(In the formula, R ¹ , R ² , p and q represent the same meaning as in formula (1), and X ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)
A monophenol compound represented by the formula (5) alone or other phenol compound, preferably

(The symbols in the formula have the same meaning as in formula (2).)
And / or general formula (6)

(The symbols in the formula have the same meaning as in the formula (3).)
One or more functional groups selected from the group consisting of a hydroxyl group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group and a cyanate group are produced by oxidative polymerization together with the polyphenol compound represented by It can manufacture by attaching | subjecting to reaction which introduces 1 or more.

In formula (4), the meanings and preferred examples of R ¹ , R ² , p and q are the same as in the case of formula (1), and X ¹ is preferably hydrogen. In formula (5), the meanings and preferred examples of R ³ , R ⁴ , r and s are the same as those in formula (2). Further, in formula (6), the meanings and preferred examples of R ⁵ , R ⁶ , m and t are the same as those in formula (3).

  Specific examples of the monophenol compound represented by the formula (4) include 2-cyclohexylphenol, 5-methyl-2-cyclohexylphenol, 6-methyl-2-cyclohexylphenol, 5-chloro-2-cyclohexylphenol, 6- Examples include chloro-2-cyclohexylphenol, and among these, 2-cyclohexylphenyl, 5-methyl-2-cyclohexylphenol, and 6-methyl-2-cyclohexylphenol are preferable, and 2-cyclohexylphenol is most preferable.

  Specific examples of the polyphenol compound represented by the formula (5) include 2,2′-biphenol, 4,4′-biphenol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane. 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxy) Phenyl) fluorene, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) phenylmethane, 1,1-bis (4-hydride) Xyl-3,5-dimethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, etc. Is mentioned.

  Specific examples of the polyphenol compound represented by the formula (6) include tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane and the like.

  There is no particular limitation on the method of oxidative (co) polymerizing the monophenol compound represented by the formula (4) and, if desired, another phenol compound, preferably the polyphenol compound represented by the formula (5) and / + or the formula (6). However, it can be performed, for example, by the following method.

  That is, it is usually polymerized by the action of an oxidizing agent such as air or oxygen in the presence of a transition metal complex catalyst. Although it will not specifically limit if it is a complex catalyst containing a transition metal as a transition metal complex catalyst, The 4th-11th group transition metal complex catalyst which uses an organic ligand compound as a ligand is preferable.

  Among these transition metal complexes, transition metal complexes of the first transition element series are preferable. Specific examples thereof include vanadium, manganese, iron, cobalt, nickel, and copper complexes, and a particularly preferable transition metal complex is a copper complex. As the metal atom of the transition metal complex, one having a valence usually existing in nature can be appropriately selected and used. In the case of copper, for example, monovalent or divalent copper can be used. These transition metal complexes can be obtained by bringing a transition metal compound and a bidentate ligand compound into contact with each other by a known method.

  Such transition metal compounds are preferably transition metal salts. Specific examples thereof include transition metal halides, sulfates, acetates, benzoates, etc. Among them, transition metal halides (chlorine, bromine, iodide, etc.) are preferred, and monovalent copper chlorides. Bromide is particularly preferred.

  Organic ligand compounds include ligand compounds in which the coordination atom is a nitrogen atom, phosphorus atom, oxygen atom or sulfur atom, or a cyclopentadienyl-type anion skeleton bonded to a transition metal atom by η5 coordination bond. A ligand compound having a group having the above group is preferable, and a compound in which the coordination atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom is more preferable, and the coordination atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom. Certain bidentate ligand compounds are particularly preferred.

  Specific examples of these bidentate ligand compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 2,3-dimethyl- 2,3-butanediol, 1,2-cyclohexanediol, 1,2-ethanedithiol, 1,3-propanedithiol, catechol, hydroxyacetic acid, 2-hydroxypropionic acid, 2-hydroxybutyric acid, ethyl hydroxyacetate, hydroxyacetone 2-ketopropionic acid, 2-ketobutyric acid, ethyl 2-ketopropionate, acetylacetone, 3-methyl-2,4-pentanedione, acetylacetaldehyde, 2,4-hexanedione, 2,4-heptanedione, 5 -Methyl-2,4-hexanedione, 5,5-dimethyl-2,4-hexa Dione, benzoylacetone, benzoylacetophenone, salicylaldehyde, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoroacetylacetone, 3-methoxy-2,4-pentanedione, 3- Cyano-2,4-pentanedione, 3-nitro-2,4-pentanedione, 3-chloro-2,4-pentanedione, acetoacetic acid, methyl acetoacetate, ethyl acetoacetate, acetoacetamide, malonic acid, malon Dimethyl acid, diethyl malonate, salicylic acid, methyl salicylate, salicylic acid amide, glycine, alanine, valine, leucine, phenylalanine, monoethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2 -Propanol, 3-amino-2-but Nord, 3-amino-2,3-dimethyl-2-butanol, 2-amino-1-cyclohexanol, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N -Phenylethanolamine, N-methylpropanolamine, N-phenylpropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-salicylidenemethylamine, N-salicylideneethylamine, N- Salicylidenepropylamine, N-salicylidenebutylamine, N-salicylideneaniline, 4- (N-methylimino) -2-pentanone, 4- (N-ethylimino) -2-pentanone, 4- (N-propyl) Imino) -2-pentanone, 4- (N-phenylimino) 2-pentanone, 2- (N-methylimino) propionic acid, 3- (N-methylimino) propionic acid, ethyl 3- (N-methylimino) propionate, 2- (N-methylimino) butyric acid, 2- (N- Methylimino) propanol, 2,3-butanedione, 3,4-hexanedione, 2,5-dimethyl-3,4-hexanedione, 2,2-dimethyl-3,4-hexanedione, 2,2,5,5 -Tetramethyl-3,4-hexanedione, 1,2-cyclohexanedione, 2- (N-methylimino) -3-butanone, 2- (N-ethylimino) -3-butanone, 2- (N-propylimino) -3-butanone, 2- (N-butylimino) -3-butanone, 2- (N-phenylimino) -3-butanone, 3- (N-methylimino) -3-hexanone, -(N-methylimino) -cyclohexanone, methyl 2- (N-methylimino) -propionate, ethyl 2- (N-methylimino) -butyrate, ethylenediamine, 1,3-propanediamine, 1,2-phenylenediamine, 2, 2'-bipyridyl, 2,3-butanedioxime, 2,4-bis (N-methylimino) -pentane, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, Nn-propylethylenediamine, N-iso-propyl Ethylenediamine, Nt-butylethylenediamine, N-phenylethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N, N′-trimethylethylenediamine, N, N, N ′, N′-tetra Methylethylenediamine, N, N, N ', N' Tetraethylethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 2,3-butanediamine, 1,2-cyclohexanediamine, 1,2-cyclohexenediamine, 1,2-phenylenediamine, 2,2′- Diamine compounds such as bipyridyl; dioxime compounds such as 2,3-butanedioxime and 2,4-pentanedioxime; 2,3-bis (N-methylimino) -butane and 2,3-bis (N-phenylimino) And diimino compounds such as -butane, 1,3-bis (N-methylimino) -butane, and 2,4-bis (N-methylimino) -pentane. Among these, a diamine compound is preferable, and ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, and 1,3-propanediamine are more preferable.

  Generally the usage-amount of these bidentate ligand compounds is 0.01-50 equivalent with respect to a transition metal compound, and 0.1-10 equivalent is further more preferable.

  The amount of the transition metal complex catalyst used is generally preferably from 0.01 to 50 mol%, more preferably from 0.02 to 10 mol% as the amount corresponding to the transition metal atom based on the phenol compound to be polymerized. In this invention, a catalyst can be used individually by 1 type or in mixture of 2 or more types. It is also effective to use a desiccant such as magnesium sulfate in combination.

  As the oxidizing agent used for the oxidative polymerization of the phenol compound, known ones can be used, but oxygen and peroxide are preferable. Oxygen can be a mixture with an inert gas or air can be used. Specific examples of the peroxide include hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid and the like.

  There is no restriction | limiting in particular in the usage-amount of these oxidizing agents. In the case of oxygen, a large excess is used relative to the phenolic compound to be polymerized. When using a peroxide, although an equivalent-3 equivalent is normally used with respect to the said phenol compound, an equivalent-2 equivalent is preferable.

  A solvent can be used in the polymerization of the phenol compound. Specific examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol; benzene, naphthalene, toluene, xylene, ethylbenzene, cumene , Aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, chloronaphthalene, nitrobenzene, methoxybenzene, dimethoxybenzene, and benzonitrile; nitro compounds such as nitromethane and nitroethane; ether compounds such as diethyl ether, dipropyl ether, and ethylene glycol dimethyl ether And halogenated hydrocarbons such as chloroform and dichloromethane; and chain and cyclic aliphatic hydrocarbons such as hexane, heptane and cyclohexane. Among these, a water-insoluble solvent is preferable, and aromatic hydrocarbons are more preferable. These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the density | concentration of the said phenolic compound at the time of superposition | polymerization, Usually, superposition | polymerization is performed in the range which the density | concentration of the phenolic compound in a reaction system becomes 5-70 mass%, More preferably, it is 10-50 mass%. Moreover, superposition | polymerization temperature is 0-200 degreeC normally, 10-100 degreeC is preferable and 20-80 degreeC is more preferable.

  In the polymerization of the phenol compound, a phenol compound other than the phenol compound, for example, 2,6-diphenylphenol can be copolymerized as a copolymerization component. The polyphenylene ether thus obtained is also included in the polyphenylene ether of the present invention.

  The polyphenylene ether of the present invention contains a paraphenylene ether component having the chemical structure represented by the formula (1) as a main component, but a minor component produced in the production process of the curable polyphenylene ether, such as orthophenylene. The polyphenylene ether of the present invention includes an ether component and a biphenylene ether component in which an oxidation reaction occurs at the hydrogen atom portion of the phenyl group as a substituent.

  Further, phenylphenol compounds outside the range represented by formula (4), such as 3-phenylphenol compounds such as 3-phenylphenol, 6-methyl-3-phenylphenol, 6-chloro-3-phenylphenol, etc. Those containing polyphenylene ether obtained by oxidation (co) polymerization are also included in the polyphenylene ether of the present invention.

  The polyphenylene ether of the present invention has at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group, and a cyanate group, and has these crosslinkable functional groups. The curable polyphenylene ether is selected from the group consisting of a hydroxyl group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group, and a cyanate group by a method known per se to a polyphenylene ether obtained by oxidation (co) polymerization of the phenol compound. Can be produced by introducing one or more polymerization-curable functional groups.

[Method of introducing polymerization-curable functional group]
Polyphenylene ether having one or more functional groups selected from the group consisting of epoxy groups (typically represented by formula (7)), allyl groups, acryloyl groups, and methacryloyl groups in one molecule of polyphenylene ether Can be produced as follows. That is, an epoxy group, an allyl group, or an allyl group is obtained by a known method of etherifying or esterifying a phenolic hydroxyl group present at the terminal of a polyphenylene ether having no functional group obtained by oxidative polymerization of the phenol compound. A polyphenylene ether having a functional group can be produced by introducing one or more polymerization-curable functional groups selected from the group consisting of a group, an acryloyl group and a methacryloyl group. Next, a method for introducing these polymerization-curable functional groups including introduction of a hydroxyl group and a cyanate group will be described.

(1) Introduction of hydroxyl group Since the polyphenylene ether obtained by oxidation (co) polymerization of the phenol compound has a phenolic hydroxyl group, a polyphenylene ether having a hydroxyl group can be obtained without any further reaction. In addition, an alcoholic hydroxyl group can be introduced by reacting an epoxy compound such as ethylene oxide with the phenolic hydroxyl group.

で示されるエポキシ化合物を反応させることにより行われる。 (2) Introduction of epoxy group Introduction of an epoxy group is, for example, an epoxy compound, typically a phenolic hydroxyl group present at the terminal of a polyphenylene ether obtained by oxidative (co) polymerization of the phenol compound, typically Formula (11)

It reacts with the epoxy compound shown by these.

In formula (11), R ⁷ , R ⁸ and R ⁹ represent the same meaning as in formula (7), R ¹⁰ represents the same meaning as in formula (8), and X ² represents a chlorine atom. Halogen atoms such as bromine atom and fluorine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; sulfonyloxy groups such as methanesulfonyloxy group, p-toluenesulfonyloxy group and trifluoromethanesulfonyloxy Represents.

  Specific examples of the epoxy compound represented by the formula (11) include chloromethyloxirane, bromomethyloxirane, methanesulfonyloxymethyloxirane, p-toluenesulfonyloxymethyloxirane, and chloromethyloxirane is preferable.

  The reaction between the polyphenylene ether obtained by oxidative (co) polymerization of the phenol compound and the epoxy compound represented by the formula (11) is preferably performed at 0 to 200 ° C. in the absence of a solvent or in a solvent, preferably in the presence of a base. Can be done at temperature. The base used here is lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, lithium methoxide, lithium ethoxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide. Etc.

(3) Introduction of allyl group The introduction of allyl group is, for example, preferably allyl chloride, allyl bromide, methane for the phenolic hydroxyl group at the end of polyphenylene ether obtained by oxidative (co) polymerization of the phenol compound. It is carried out by reacting an allyl compound such as allyl sulfonate and allyl p-toluenesulfonate. This reaction can be carried out at a temperature of 0 to 200 ° C. in the absence of a solvent or in a solvent, preferably in the presence of a base. As a base used here, the same thing as the case where the said epoxy compound is made to react is mentioned.

(4) Introduction of acryloyl group and methacryloyl group The introduction of acryloyl group and methacryloyl group is, for example, preferably acryloyl chloride with respect to the phenolic hydroxyl group at the end of polyphenylene ether obtained by oxidation (co) polymerization of the phenol compound. , Acryloyl bromide, methacryloyl chloride, methacryloyl bromide and other acrylic acid halides or methacrylic acid halides, and acid anhydrides such as acrylic acid anhydrides and methacrylic acid anhydrides. This reaction can be carried out at a temperature of 0 to 200 ° C. without solvent or in a solvent.

(5) Introduction of cyanate group For introduction of cyanate group, for example, cyanogen chloride such as cyan chloride is preferably added to the phenolic hydroxyl group at the terminal of polyphenylene ether obtained by oxidative (co) polymerization of the phenol compound. This is done by reacting. This reaction can be performed at a temperature of −30 to 50 ° C. without solvent or in a solvent.

  The polyphenylene ether of the present invention has a number average molecular weight of usually 500 to 20,000, preferably 1,000 to 12,000, more preferably 1,000 to 8,000, most preferably measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC). Is between 1,000 and 5,000. When the number average molecular weight is less than the above range, the coatability in the case of a composition such as a resist may be lowered. On the other hand, when the number average molecular weight exceeds the above range, the coating property when the composition is a resist or the like may be lowered, or the solubility in a solvent may be lowered.

  When the polyphenylene ether of the present invention has an epoxy group, the epoxy equivalent is preferably from 300 to 2,000, particularly preferably from 500 to 1,000, where the balance between heat resistance and curability is particularly good.

[Curable resin composition]
A first aspect of the polyphenylene ether composition of the present invention is a curable resin composition containing (A) the polyphenylene ether of the present invention and (B) a curing agent.
When the polyphenylene ether of the present invention has a hydroxyl group, the (B) curing agent comprises (B-1) an epoxy group, an ester group, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid halide group, and an isocyanate group. A compound having two or more functional groups selected from the group. Specific examples thereof include polyepoxy compounds such as ethylene glycol diglycidyl ether, polycarboxyl compounds such as pyromellitic acid, trimellitic acid, and benzophenone tetracarboxylic acid, or acid anhydrides thereof, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate. And polyisocyanate compounds such as In addition, (B) hardening | curing agent may be used individually, or 2 or more types may be mixed and used for it.

  When the polyphenylene ether of the present invention has an epoxy group, (B) curing agent is a compound used as a curing agent or curing accelerator for (B-2) epoxy resin. These can be used without limitation of known curing agents or curing accelerators, preferably (b-1) nitrogen-containing compounds, (b-2) polyvalent carboxylic acids or polyvalent carboxylic acids. Selected from anhydride, (b-3) polyhydric phenol compound, (b-4) organophosphorus compound, (b-5) organometallic compound, and (b-6) sulfonium salt compound and / or iodonium salt compound It is.

(B-1) Nitrogen-containing compound The nitrogen-containing compound used in the present invention is a compound having at least one carbon-nitrogen bond, preferably amines, nitrogen-containing heterocyclic compounds, ammonium salts, and polyamides. Chosen from the kind. Examples of amines include aliphatic and aromatic primary, secondary and tertiary amines. The aromatic amine here refers to an amine having a structure in which an amino group is directly bonded to an aromatic ring composed only of carbon such as a benzene ring.

  Specific examples of the primary or secondary amine among the aliphatic amines include ethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, triethylenetetramine, dimethylaminopropylamine, mensendiamine, N-aminoethylethanolamine, polyethylene Glycol bis (2-aminoethyl) ether, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, m-xylylenediamine, 3,9-bis (3-aminopropyl) spiro-2,4 , 8,10-tetraoxaundecane and the like.

  Specific examples of tertiary amines among aliphatic amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, N, N-dimethyloctylamine, N, N-dimethylbenzylamine, 2 , 4,6-tris (dimethylaminophenol), N, N, N ′, N′-tetramethylethylenediamine and the like.

  Specific examples of the aromatic amine include metaphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, and 2,2-bis [4. -(4-aminophenoxy) phenyl] propane, diaminodiphenyl sulfone, m-aminophenol and the like.

  Other specific examples of amines include polyamines such as tetramethylguanidine, dicyandiamide, urea, urea derivatives, polybasic hydrazides; organic acid salts and / or epoxy adducts thereof; amine complexes of boron trifluoride, etc. Is mentioned.

  Specific examples of nitrogen-containing heterocyclic compounds include pyridines such as pyridine, picoline, and lutidine; imidazole, 2-ethyl-4-methylimidazole, N-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazo Imidazoles such as lithium trimellitate and 2-methylimidazolium isocyanurate; Morpholines such as N-methylmorpholine and N-ethylmorpholine; 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo And [5,4,0] undec-7-ene.

  Other examples of nitrogen-containing heterocyclic compounds include triazine compounds. Specific examples thereof include melamine, N-ethylenemelamine, N, N ′, N ″ -triphenylmelamine, and hexa (N-methyl). Melamines such as melamine; guanamines such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, acetoguanamine, benzoguanamine; cyanuric acid, Isocyanuric acid, trimethyl cyanurate, trismethyl isocyanurate, triethyl cyanurate, trisethyl isocyanurate, tri (n-propyl) cyanurate, tris (n-propyl) isocyanurate, diethyl cyanurate, N, N'-diethyl isocyanurate , Methyl cyanurate, methyl Cyanuric acids such as cyanurate and the like.

  Specific examples of ammonium salts include tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, phenyltributylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride And quaternary ammonium salts such as bromide, benzyltrimethylammonium bromide, octyltrimethylammonium bromide, decyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and phenyltributylammonium bromide.

  Specific examples of polyamides include polyaminoamides having primary and secondary amino groups obtained by subjecting dimer acid to a polyamine such as diethylenetriamine or triethylenetetraamine by condensation reaction.

(B-2) Polyvalent carboxylic acid or polyvalent carboxylic acid anhydride The polyvalent carboxylic acid or polyvalent carboxylic acid anhydride is a compound having two or more carboxyl groups in one molecule, or an anhydride thereof. Examples include aromatic polycarboxylic acids such as phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) and the like Examples include anhydride, maleic anhydride, succinic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, polyadipic anhydride, chlorendic anhydride, tetrabromophthalic anhydride, and the like.

(B-3) Polyhydric phenol compound The polyhydric phenol compound used in the present invention is a compound having two or more phenolic hydroxyl groups in one molecule. Specific examples thereof include polyvinylphenol and brominated polyvinylphenol. Bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, phenol novolac resin, cresol novolac resin, dicyclopentadiene type phenol resin which is a condensation reaction product of dicyclopentadiene and phenol, and the like.

(B-4) Organophosphorus Compound The organophosphorus compound used in the present invention is a compound having at least one carbon-phosphorus bond, and examples thereof include phosphine and phosphonium salts. Specific examples thereof include organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride. Is mentioned.

(B-5) Organometallic compound The organometallic compound used in the present invention is a metal compound having a function of curing an epoxy resin, and examples thereof include organic acid metal salts, 1,3-diketone metal complex salts, metal alkoxides, and the like. It is done. Specific examples thereof include dibutyltin dilaurate, dibutyltin maleate, organic acid metal salts such as zinc 2-ethylhexanoate, 1,3-diketone metal complex salts such as nickel acetylacetonate and zinc acetylacetonate, titanium tetrabutoxide, Examples thereof include metal alkoxides such as zirconium tetrabutoxide and aluminum butoxide.

(B-6) Sulfonium salt compound and / or iodonium salt compound The sulfonium salt compound used in the present invention is a compound having one or more sulfonium cations in one molecule, and the iodonium salt compound is 1 in one molecule. It is a compound having the above iodonium cation. Specific examples thereof include diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, and the like.

  When the polyphenylene ether of the present invention has an allyl group, an acryloyl group or a methacryloyl group, (B) the curing agent is (B-3) a radical polymerization initiator. These are compounds that generate radicals upon irradiation with heat or light, and known radical initiators can be used without particular limitation. Specific examples thereof include benzoyl peroxide, dicumyl peroxide, 2, 5 -Organic peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne, azobisisobutyronitrile An azo compound such as

  When the polyphenylene ether of the present invention has a cyanate group, the (B) curing agent is a compound that accelerates the triazine ring formation reaction by trimerization of the (B-4) cyanate group. Specific examples thereof include acids such as mineral acids and Lewis acids; bases such as sodium alcoholates and tertiary amines; salts such as sodium carbonate, manganese, iron, cobalt, nickel, copper, zinc, tin and the like 2- Examples thereof include organometallic salt compounds such as ethyl hexanoate and naphthenate, and organometallic complexes such as acetylacetone complex.

  The amount of these (B) curing agents used is arbitrary as long as the object can be achieved, but is usually 0.001 to 200 parts by mass and 0.01 to 25 parts by mass with respect to 100 parts by mass of the polyphenylene ether of the present invention. Is preferable, and 0.1 to 15 parts by mass is particularly preferable.

  The 2nd aspect of the curable resin composition of this invention is a curable resin composition containing (A) polyphenylene ether of this invention, (B) hardening | curing agent, and (C) curable resin.

  The (C) curable resin used in the present invention is any resin that can be thermally cured or photocured, and is preferably an epoxy resin. As an epoxy resin used here, what is necessary is just to contain two or more epoxy groups in one molecule, and it is used by combining 1 type or 2 types or more. Typical examples include bisphenol A glycidyl ether epoxy resins obtained by reaction of phenols or alcohols with chloromethyloxirane, brominated bisphenol A glycidyl ether epoxy resins, glycidyl ether type epoxy resins such as cresol novolac epoxy resins, Glycidyl ester type epoxy resin obtained by reaction of carboxylic acids with chloromethyloxirane, Glycidylamine type epoxy resin obtained by reaction of amines or cyanuric acid with chloromethyloxirane, Internal epoxy resin obtained by oxidation of double bond [For details, see, for example, “Epoxy Resin Handbook” edited by Masaki Shinbo (published by Nikkan Kogyo Shimbun, 1987)].

  (C) The usage-amount of curable resin is 1-500 mass parts normally with respect to 100 mass parts of (A) polyphenylene ether, 2-200 mass parts is preferable, and 5-100 mass parts is especially preferable.

  A third aspect of the curable resin composition of the present invention is a curable resin composition containing (A) polyphenylene ether, (B) a curing agent, and (D) a flexibility-imparting agent. ) It may contain a curable resin. In the curable resin composition of the present invention, (D) the flexibility, flexibility, or impact resistance of the curable resin composition is improved by the presence of the flexibility imparting agent. Use as a solder resist becomes easy.

  The (D) component flexibility imparting agent used in the present invention is a compound that imparts flexibility to the resin. For example, (d-1) a conjugated diene polymer or copolymer for an epoxy resin. , (D-2) polyurethane compound, (d-3) polyalkylene glycol compound, (d-4) polycarbonate compound, (d-5) polyester compound, (d-6) polyacrylate or polymethacrylate compound It is. Any of non-reactive compounds and reactive compounds can be used as these, but reactive compounds are preferably used. Furthermore, although either resinous or elastomeric can be used, it is preferable to use an elastomeric compound.

(D-1) Conjugated diene polymer or copolymer In the present invention, the conjugated diene polymer or copolymer (d-1) used as the flexibility imparting agent of component (D) is butadiene, isoprene and chloroprene. These are compounds obtained by copolymerizing conjugated diene compounds such as singly or with other polymerizable compounds, and compounds obtained by subjecting them to further chemical reaction. These can be used in combination.

  Specific examples of the conjugated diene polymer or copolymer (d-1) include 1,2-polybutadiene, 1,4-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,4-polybutadiene, and carboxyl group-terminated. 1,2-polybutadiene, carboxyl-terminated 1,4-polybutadiene, reaction product of hydroxyl-terminated 1,2-polybutadiene and bisphenol A diglycidyl ether, glycidylated product of hydroxyl-terminated 1,4-polybutadiene, 1,2-polybutadiene or Liquid or solid polybutadienes such as epoxidized 1,4-polybutadiene and hydrogenated products thereof; hydroxyl-terminated 1,4-polyisoprene, maleic anhydride-modified 1,4-polyisoprene, and hydrogenated products thereof Liquid or solid polyisoprene such as products; Liquid or solid butadiene-acrylonitrile copolymers such as xylyl-terminated butadiene-acrylonitrile copolymers, amino-terminated butadiene-acrylonitrile copolymers, and hydrogenated products thereof; liquid or solid butadiene-styrene copolymers Examples thereof include polymers, liquid or solid isoprene-styrene copolymers and hydrogenated products or epoxidized products thereof; and polychloroprenes.

(D-2) Polyurethane Compound In the present invention, the polyurethane compound (d-2) used as the flexibility imparting agent of the component (D) is a compound having two or more urethane bonds in one molecule, and is a polyisocyanate. It can be obtained by reacting a narate and a polyol by a method known per se. These may be liquid or solid.

  Polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m, or p)- Xylylene diisocyanate, methylene bis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, etc. Of diisocinate. These polyisocyanates can be used alone or in combination of two or more.

  Specific examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol. 1,6-hexanediol, 1,4-cyclohexanedimethanol, and polyalkylene glycols such as polyethylene oxide, polypropylene oxide, and polytetramethylene glycol.

(D-3) Polyalkylene glycol compound In the present invention, the polyalkylene glycol compound (d-3) used as the flexibility imparting agent of the component (D) has a structure in which two or more molecules of alkylene glycol are dehydrated and condensed. It is obtained by ring-opening polymerization of alkylene oxide. Specific examples of the polyalkylene glycol (d-3) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like.

(D-4) Polycarbonate Compound In the present invention, the polycarbonate compound (d-4) used as the flexibility imparting agent of the component (D) is a compound having two or more carbonate bonds in one molecule. Examples include polytrimethylene carbonate, polytetramethylene carbonate, polypentamethylene carbonate, polypropylene carbonate, poly-2,2-dimethyl-1,3-propylene carbonate, poly-1,4-cyclohexylene carbonate, polyhexamethylene carbonate , Poly (cyclohexane-1,4-dimethylene) carbonate and the like.

(D-5) Polyester compound In the present invention, the polyester compound (d-5) used as the flexibility imparting agent of the component (D) is a compound having two or more ester bonds in one molecule. It can be obtained by reacting a carboxylic acid or its derivative with a polyol. Specific examples of the polyester compound (d-5) include polyethylene terephthalate, polybutylene phthalate, polyethylene naphthalate, polyepsilon caprolactone, polycaprolactone diol and the like.

(D-6) Polyacrylate or polymethacrylate compound In the present invention, the polyacrylate or polymethacrylate compound (d-6) used as the flexibility imparting agent of the component (D) is an acrylic acid and / or methacrylic acid ester. It may be a homopolymer or a copolymer, and other components may be copolymerized.

  Specific examples of acrylic acid and / or methacrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) Acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( Alkyl (meth) acrylates such as meth) acrylate; cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Cycloaliphatic (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylcarbitol (meth) acrylate, nonylphenyl (meth) acrylate, nonylphenylcarbi Aromatic (meth) acrylates such as tall (meth) acrylate and nonylphenoxy (meth) acrylate; 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-tert-butylaminoethyl (meth) ) (Meth) acrylate having an amino group such as acrylate; methacryloxyethyl phosphate, bis-methacryloxyethyl phosphate, methacryloxyethyl phenyl acid phosphate (phenyl-P) ) And the like; glycidyl (meth) acrylate; allyl (meth) acrylate; phenoxyethyl acrylate and the like.

  Specific examples of components other than acrylic acid esters and methacrylic acid esters include unsaturated compounds having a carboxyl group or acid anhydride group such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, itaconic anhydride, styrene, vinyl And vinyl aromatic compounds such as toluene.

[Method for producing curable resin composition]
The polyphenylene ether composition of the present invention can be produced by mixing the above-mentioned components by a usual method. The mixing method is not particularly limited, and a part of the components may be mixed and then the remaining components may be mixed, or all the components may be mixed at once. In addition, an organic solvent may be added to the composition as necessary for viscosity adjustment or the like. By adjusting the viscosity, the coating performance by roller coating, spin coating, screen coating, curtain coating, etc. is improved, and printing by screen printing or the like is facilitated. From such a viewpoint, the amount of the organic solvent used is preferably such that the viscosity of the composition is 100 to 500,000 mPa · s (measured at 25 ° C. with a Brookfield Viscometer), and more preferably 500 to 500,000 mPa · s. preferable.

  Specific examples of the organic solvent include ketone solvents such as ethyl methyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetoacetate, γ-butyrolactone, and butyl acetate; alcohol solvents such as butanol and benzyl alcohol. Solvent for cellosolve such as carbitol acetate and methyl cellosolve acetate, carbitol and their esters and ether derivatives; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl Amide solvents such as -2-pyrrolidone; Dimethyl sulfoxide; Phenol solvents such as phenol and cresol; Nitro compound solvents; Toluene, xylene, hexamethylbenzene, cumene aromatic solvents; Tetralin, Decalin, Dipe Solvents such as aromatic or alicyclic such as consisting of hydrocarbons, such as ten, and the like. These can be used alone or in combination of two or more.

Moreover, additives, such as a thermal-polymerization inhibitor, a thickener, an antifoamer, a leveling agent, an adhesiveness imparting agent, can be added to the polyphenylene ether composition of this invention as needed.
Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine and the like.
Examples of the thickener include asbestos, olben, benton, montmorillonite and the like.
The antifoaming agent is used for eliminating bubbles generated at the time of printing, coating or curing, and specific examples thereof include acrylic and silicone surfactants.
The leveling agent is used to lose unevenness on the surface of the film that occurs during printing and coating, and specific examples thereof include acrylic and silicone surfactants.
Examples of the adhesion imparting agent include imidazole, thiazole, triazole, and silane coupling agents.

In addition, as other additives, for example, an ultraviolet ray preventive agent, a plasticizer, a flow control agent, and the like can be added for the purpose of storage stability within the range where the effects and effects of the present invention are exhibited.
Examples of the flow regulator include inorganic or organic fillers, waxes, surfactants, and the like.
Specific examples of the inorganic filler include talc, barium sulfate, barium titanate, silica, alumina, clay, magnesium carbonate, calcium carbonate, aluminum hydroxide, and a silicate compound.
Specific examples of the organic filler include silicone resin, silicone rubber, and fluorine resin.
Specific examples of the wax include polyamide wax and oxidized polyethylene wax.
Specific examples of the surfactant include silicone oil, higher fatty acid ester, amide and the like.
These fluidity modifiers can be used alone or in combination of two or more.

  The polyphenylene ether composition of the present invention can be made into a cured product by coating it on a substrate or the like with a suitable thickness and thermosetting. Although the thickness of a coating film is arbitrary, it is 0.1 micrometer-200 micrometers normally. The curing temperature can be any temperature in consideration of the type of curing agent, but is usually room temperature to 300 ° C.

  The polyphenylene ether and the polyphenylene ether composition of the present invention can be used for various applications such as paints and casting materials. In particular, the insulating protective film of the printed wiring board, the insulating resin layer or the sealing agent between the layers of the multilayer printed wiring board Suitable for use as

［測定条件］
ＧＰＣ装置：昭和電工（株）製、ＳＨＯＤＥＸ ＳＹＳＴＥＭ１１、
カラム ：昭和電工（株）製、ＳＨＯＤＥＸ ＫＦ−８０２およびＫＦ−８０２.５を
この順に接続したもの、
溶媒 ：テトラヒドロフラン、
流量 ：1.0ｍＬ／ｍｉｎ、
測定温度 ：４０℃。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In Examples and Comparative Examples, the glass transition temperature and thermal decomposition temperature of the cured products were measured by the following methods.
1) Measurement of glass transition temperature The glass transition temperature was measured with a differential scanning calorimeter (DSC, trade name: Thermo Plus TG8230) manufactured by Rigaku Denki Co., Ltd. in the air at a heating rate of 20 ° C./min.
2) Measurement of thermal decomposition temperature It was measured in the air at a heating rate of 20 ° C./min with a thermogravimetric meter (TGA, trade name: Thermo Plus TG8120) manufactured by Rigaku Corporation.
3) Measurement of gel permeation chromatography (GPC) [preparation of calibration curve]
First, at least 10 types of commercially available standard polystyrenes with known average molecular weights were used to determine the respective retention times. A calibration curve was prepared by approximating the relationship between average molecular weight and retention time with a cubic curve.
[Measurement]
Dissolve 10 mg of sample in 2 mL of tetrahydrofuran, and inject 0.5 mL into the column through a line filter using a loop injector. The obtained elution curve data is automatically calculated in a data processor such as Shimadzu CR-3A based on the calibration curve created above to obtain Mn and Mw. Here, the peak was divided at intervals of 10 seconds, the molecular weight of each dividing point was Mi, and the peak height was Hi, and the calculation was performed according to the following formula.

[Measurement condition]
GPC device: Showa Denko Co., Ltd., SHODEX SYSTEM11,
Column: Showa Denko Co., Ltd., SHODEX KF-802 and KF-802.5
Connected in this order,
Solvent: tetrahydrofuran,
Flow rate: 1.0 mL / min,
Measurement temperature: 40 ° C.

Example 1
1) Polymerization of 2-cyclohexylphenol 190 g of 2-cyclohexylphenol, 250 mL of toluene and 1.16 g of tetramethylethylenediamine were added to a 1-liter separable flask equipped with a Dimroth and an air introduction tube, and dissolved while stirring. Next, 0.99 g of cuprous bromide (CuBr) was added with stirring. Then, it heated at 60 degreeC, blowing air in the reaction mixture from the air introduction pipe | tube. Next, 30 g of anhydrous magnesium sulfate was added and polymerization was carried out for 16 hours. After completion of the polymerization, 200 mL of a 5 mass% aqueous solution of ethylenediaminetetraacetic acid disodium salt was added to the reaction mixture and stirred. This mixture was transferred to a separatory funnel, the aqueous layer was removed, and the oil layer was washed with 200 mL of a 5 mass% aqueous solution of ethylenediaminetetraacetic acid disodium salt. This washing was repeated until the aqueous layer was not colored, and the oil layer was washed with saturated brine, and then the oil layer was dried over anhydrous magnesium sulfate. Thereafter, anhydrous magnesium sulfate was filtered from the oil layer, and the filtrate was added dropwise to 2 liters of stirred methanol. The produced precipitate was filtered with suction, washed with methanol, air-dried, and dried under reduced pressure at 60 ° C. for 6 hours. The IR spectrum of the obtained polyphenylene ether confirmed the decrease in the absorption peak of the phenolic hydroxyl group. The number average molecular weight and weight average molecular weight measured by gel permeation chromatography of the obtained polyphenylene ether were 1,250 and 4,100, respectively.

2) Introduction of epoxy group into polyphenylene ether A solution prepared by dissolving 40 g of the polyphenylene ether obtained above in 360 g of chloromethyloxirane was heated to 100 ° C. while stirring with a magnetic stirrer. Next, at this temperature, a solution prepared by dissolving 3.1 g of sodium methoxide in 30 g of ethanol was added dropwise over 1 hour, and the mixture was stirred for 6 hours. Subsequently, after cooling a reaction material to room temperature, the depositing solid was filtered and the excess chloromethyl oxirane was distilled off under reduced pressure. The obtained mixture was dropped into 1 liter of stirred methanol, and the precipitated solid was suction filtered and washed with methanol, and then dried under reduced pressure at 60 ° C. for 6 hours. The number average molecular weight and weight average molecular weight measured by GPC of the resulting curable polyphenylene ether having an epoxy group were 1,320 and 4,300, respectively. The appearance of a peak derived from an epoxy group was confirmed by IR spectrum, and the epoxy equivalent measured by the hydrochloric acid-pyridine method was 736.

3) Preparation of cured product of polyphenylene ether having an epoxy group 1.0 g of curable polyphenylene ether having an epoxy group obtained above as curable polyphenylene ether (A) was dissolved in 2.0 g of toluene. To this solution, 0.48 g of a 10% by mass m-xylylenediamine / toluene solution was added as an epoxy resin curing agent (B) to obtain a uniform solution. The obtained solution was cast on a polyimide film, air-dried at room temperature for 30 minutes, and then cured at 160 ° C. for 30 minutes. The glass transition temperature measured by DSC of the obtained cured product was 178 ° C. Moreover, the mass reduction | decrease rate of 500 degreeC measured by TGA was 46 mass%.

Example 2
1) Copolymerization of 2-cyclohexylphenol and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane 200 g of 2-cyclohexylphenol was added to a 1 liter separable flask equipped with a Dimroth and an air introduction tube, 17 g of 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 250 ml of toluene and 1.16 g of tetramethylethylenediamine were added and dissolved while stirring. Next, 0.99 g of cuprous bromide (CuBr) was added with stirring. Then, it heated at 60 degreeC, blowing air in the reaction mixture from the air introduction pipe | tube. Next, 30 g of anhydrous magnesium sulfate was added and polymerization was carried out for 12 hours. After completion of the polymerization, 200 mL of a 5 mass% aqueous solution of ethylenediaminetetraacetic acid disodium salt was added to the reaction mixture and stirred. This mixture was transferred to a separatory funnel, the aqueous layer was removed, and the oil layer was washed with 200 mL of a 5 mass% aqueous solution of ethylenediaminetetraacetic acid disodium salt. This washing was repeated until the aqueous layer was not colored, and the oil layer was washed with saturated brine, and then the oil layer was dried over anhydrous magnesium sulfate. Thereafter, anhydrous magnesium sulfate was filtered from the oil layer, and the filtrate was added dropwise to 2 liters of stirred methanol. The produced precipitate was filtered with suction, washed with methanol, air-dried, and dried under reduced pressure at 60 ° C. for 6 hours. The number average molecular weight and weight average molecular weight measured by gel permeation chromatography of the obtained polyphenylene ether were 1,130 and 3,510, respectively.

2) Preparation of cured product of polyphenylene ether (A) As a curable polyphenylene ether, 1.0 g of the curable polyphenylene ether obtained above was dissolved in 2.0 g of toluene. To this solution, 4.0 g of a 10% by mass benzophenone tetracarboxylic anhydride / methyl ethyl ketone solution as (B) curing agent was added to obtain a uniform solution. The obtained solution was cast on a polyimide film, air-dried at room temperature for 30 minutes, and then cured at 160 ° C. for 30 minutes.

3) Introduction of epoxy group into polyphenylene ether A solution obtained by dissolving 40 g of the polyphenylene ether obtained above in 360 g of chloromethyloxirane was heated to 100 ° C. while stirring with a magnetic stirrer. Next, at this temperature, a solution of 3.5 g of sodium methoxide dissolved in 30 g of ethanol was added dropwise over 1 hour, and the mixture was stirred for 6 hours. Subsequently, after cooling a reaction material to room temperature, the depositing solid was filtered and the excess chloromethyl oxirane was distilled off under reduced pressure. The obtained mixture was added dropwise to 1 liter of stirred methanol, and the precipitated solid was suction filtered, washed with methanol, and dried under reduced pressure at 55 ° C. for 6 hours. The number average molecular weight and the weight average molecular weight measured by GPC of the obtained curable polyphenylene ether having an epoxy group were 1,320 and 3,720, respectively. The epoxy equivalent measured by the hydrochloric acid-pyridine method was 693.

4) Preparation of Cured Polyphenylene Ether Having Epoxy Group (A) 1.0 g of curable polyphenylene ether having an epoxy group obtained above as curable polyphenylene ether was dissolved in 2.0 g of toluene. To this solution, 0.48 g of 10% by mass m-xylylenediamine / toluene solution was added as a (B) epoxy resin curing agent to obtain a uniform solution. The obtained solution was cast on a polyimide film, air-dried at room temperature for 30 minutes, and then cured at 160 ° C. for 30 minutes. The glass transition temperature of the obtained cured product measured by a differential scanning calorimeter was 180 ° C. (temperature increase rate: 20 ° C./min).

Example 3
1) Copolymerization of 2-cyclohexylphenol and 2,2-bis (4-hydroxyphenyl) propane In Example 2, instead of 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 was used. , 2-bis (4-hydroxyphenyl) propane was used except that it was used. The number average molecular weight and weight average molecular weight measured by GPC of the obtained polyphenylene ether were 1,420 and 3,980, respectively.

2) Introduction of epoxy group into polyphenylene ether In the same manner as in Example 2, epoxy was introduced into the polyphenylene ether obtained in 1) above. The number average molecular weight and the weight average molecular weight measured by GPC of the obtained curable polyphenylene ether were 1,640 and 4,210, respectively. Moreover, the epoxy equivalent measured by the hydrochloric acid-pyridine method was 831.

Example 4
1) Polymerization of 3-methyl-6-cyclohexylphenol The same procedure as in Example 1 was conducted except that 3-methyl-6-cyclohexylphenol was used instead of 2-cyclohexylphenol. The number average molecular weight and weight average molecular weight measured by GPC of the obtained polyphenylene ether were 1,040 and 3,540, respectively.

2) Introduction of epoxy group into polyphenylene ether In the same manner as in Example 1, epoxy was introduced into the polyphenylene ether obtained in 1) above. The number average molecular weight and weight average molecular weight measured by GPC of the obtained curable polyphenylene ether were 1,100 and 3,730, respectively. The epoxy equivalent measured by the hydrochloric acid-pyridine method was 692.

Comparative Example 1
1) Synthesis of polyphenylene ether 1.1 g of CuCl, 66.3 g of di-n-butylamine, and 500 g of methyl ethyl ketone were charged in a 2 liter separable flask equipped with an air introduction tube, and the temperature was raised to 40 ° C. While stirring this mixture, 20.9 g of 3,3,5,5′-tetramethyl-1,1′-biphenyl-4,4′-diol dissolved in 600 g of methyl ethyl ketone and 75.6 g of 2,6-dimethylphenol were dissolved. The mixed solution was added dropwise over 120 minutes while performing air bubbling at 2 liters / minute, and further stirred for 30 minutes after the completion of the dropwise addition while bubbling air at 2 liters / minute. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. The aqueous phase was separated, and the oil layer was washed with 0.1N aqueous HCl three times and further with ion exchange water. Methyl ethyl ketone was distilled off from this solution and concentrated, and then added dropwise to methanol. The resulting precipitate was suction filtered and then dried under reduced pressure to obtain polyphenylene ether. This had a number average molecular weight of 1,870 and a weight average molecular weight of 2,420.

2) Introduction of epoxy group into polyphenylene ether An epoxy group was introduced into the polyphenylene ether obtained in 1) in the same manner as in Example 1, and the number average molecular weight was 2,260 by GPC, the weight average molecular weight was 3,280, and the hydrochloric acid-pyridine method was used. An epoxy group-containing curable polyphenylene ether having an epoxy equivalent of 1,100 was obtained.

3) Cured material preparation of polyphenylene ether having an epoxy group The same procedure as in Example 1 was carried out except that 0.31 g of a 10% by mass m-xylylenediamine / toluene solution was used. The mass reduction rate at 500 ° C. measured by TGA of the obtained cured product was 62% by mass.

Example 5
(A) As polyphenylene ether, 1.5 g of the epoxy group-containing polyphenylene ether obtained in Example 1 and (C) 0.5 g of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1206) as thermosetting resin Was dissolved in toluene. To this solution, 1.8 g of a 10% by mass m-xylylenediamine / toluene solution was added as a curing agent (B) to obtain a uniform solution. The obtained solution was cast on a polyimide film, air-dried at room temperature for 30 minutes, and then cured at 160 ° C. for 30 minutes. The glass transition temperature of the obtained cured product measured by a differential scanning calorimeter was 183 ° C. (temperature increase rate: 20 ° C./min).

Example 6
(A) Epoxy group-containing curable polyphenylene ether obtained in Example 2 as curable polyphenylene ether (1.4 g) and (D) Epoxy group-containing 1,2-polybutadiene (manufactured by Nippon Soda Co., Ltd.) EPB-13) 0.6 g was dissolved in toluene. To this solution, 1.1 g of a 10% by mass m-xylylenediamine / toluene solution was added as a (B) epoxy resin curing agent to obtain a uniform solution. The obtained solution was cast on a polyimide film, air-dried at room temperature for 30 minutes, and then cured at 160 ° C. for 30 minutes. When the laminate comprising the obtained cured product and polyimide film was bent at 180 ° C. with the cured product on the outside, no occurrence of cracks was observed.

Example 7
(D) A butadiene-acrylonitrile copolymer elastomer having a terminal amino group as a flexibility imparting agent (manufactured by Ube Industries, Hycar ATBN 1300 × 16) 0.6 g, and (B) 10% by mass as an epoxy resin curing agent The same procedure as in Example 6 was performed except that 0.62 g of m-xylylenediamine / toluene solution was used. When the laminate comprising the obtained cured product and polyimide film was bent at 180 ° C. with the cured product on the outside, no occurrence of cracks was observed.

Example 8
A 500 mL separable flask was charged with 160 g of dichloromethane, 50 g of the polyphenylene ether synthesized in Example 1 and 40 g of allyl bromide to obtain a uniform solution. Next, 120 mL of 1N sodium hydroxide solution was charged, and 5.6 g of benzyltri-n-butylammonium bromide was further added as a phase transfer catalyst, followed by stirring at room temperature for 5 hours. After the reaction mixture was filtered, the aqueous phase was separated, and the oil layer was washed with 0.1N aqueous HCl three times and further with ion-exchanged water. Methylene chloride was distilled off from this solution and concentrated, and then added dropwise to methanol. The obtained precipitate was subjected to suction filtration and then dried under reduced pressure to obtain a curable polyphenylene ether having an allyl group. The disappearance of the absorption peak of the phenolic hydroxyl group was confirmed by the IR spectrum of the obtained polyphenylene ether, and the appearance of a peak attributed to the allyl group was confirmed by the NMR spectrum.

Example 9
A 100 mL separable flask was charged with 40 g of pyridine and 10 g of the polyphenylene ether synthesized in Example 1 to obtain a uniform solution. Next, 40 g of acryloyl chloride was added dropwise over 60 minutes under ice cooling with stirring, and the mixture was allowed to warm to room temperature and left overnight. Thereafter, the reaction mixture was poured into 100 g of ice-cooled water little by little. The obtained precipitate was suction filtered, washed with methanol, and dried under reduced pressure to obtain polyphenylene ether having an acryloyl group. The disappearance of the absorption peak of the phenolic hydroxyl group was confirmed by the IR spectrum of the obtained polyphenylene ether, and the appearance of a peak attributed to the acryloyl group was confirmed by the NMR spectrum.

Example 10
A polyphenylene ether having a methacryloyl group was obtained in the same manner as in Example 9 except that methacryloyl chloride was used instead of acryloyl chloride. The disappearance of the absorption peak of the phenolic hydroxyl group was confirmed by the IR spectrum of the obtained curable polyphenylene ether, and the appearance of a peak attributed to the methacryloyl group was confirmed by the NMR spectrum.

Example 11
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was cooled to −10 ° C., and 20 mL of a methylene chloride solution of chlorocyan (0.013 mol) was charged. Thereafter, a solution prepared by dissolving 5 g of polyphenylene ether prepared in Example 1 and 1.31 g (0.013 mol) of triethylamine in 250 g of methyl ethyl ketone was dropped from the dropping funnel so that the temperature of the reaction solution was 10 ° C. or less. The reaction was performed for a minute. Then, it was washed with 0.1N aqueous hydrochloric acid solution three times and with ion exchange water, and the solid matter was filtered. After distilling off methylene chloride and methyl ethyl ketone from the filtrate, polyphenylene ether having a cyanate group was obtained by drying under reduced pressure. By adding 0.1 part by mass of tin octylate to 100 parts by mass of polyphenylene ether obtained by confirming the disappearance of the absorption peak of the phenolic hydroxyl group and the appearance of the absorption peak derived from the cyanate group by IR spectrum of the obtained polyphenylene ether. And cured at 220 ° C. for 5 hours.

Claims (15)

General formula (1)

(In the formula, R ¹ and R ² each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ¹ or R ² are present, each may be the same or different, and p is 0 or an integer of 1 to 3, q is an integer of 0 or 1 to 5, and n is an integer of 2 to 1000.)
And a polyphenylene ether having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an allyl group, an acryloyl group, a methacryloyl group and a cyanate group. General formula (2)

(In the formula, R ³ represents a single bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom, a sulfur atom or a sulfonyl group, and R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. And when a plurality of R ⁴ are present, each may be the same or different, and r and s are each independently 0 or an integer of 1 to 4.)
And / or general formula (3)

(Wherein R ⁵ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵ are present, each may be the same as or different from each other, and t is 0 or an integer of 1 to 4) R ⁶ is an m-valent hydrocarbon group, and m is an integer of 3 to ^6. )
The polyphenylene ether according to claim 1, further having a chemical structure represented by: General formula (4)

(Wherein R ¹ , R ² , p and q represent the same meaning as described in claim 1, and X ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)
The polyphenylene ether according to claim 1, which is obtained by oxidative polymerization of the monophenol compound represented by the formula alone or together with another phenol compound. General formula (4)

(Wherein R ¹ , R ² , p and q represent the same meaning as described in claim 1, and X ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)
And a monophenol compound represented by the general formula (5)

(Wherein R ³ , R ⁴ , r and s represent the same meaning as described in claim 2).
And / or general formula (6)

(Wherein R ⁵ , R ⁶ , t and m have the same meaning as described in claim 2).
The polyphenylene ether according to claim 2, which is obtained by oxidative polymerization of a polyphenol compound represented by the formula: General formula (8)

Wherein R ¹ , R ² , p, q and n represent the same meaning as described in claim 1, and R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom or carbon number. 1 to 20 hydrocarbon groups are represented, and R ¹⁰ represents a divalent hydrocarbon group which may contain a hetero atom.
The polyphenylene ether according to any one of claims 1 to 4, which has a chemical structure represented by:   The polyphenylene ether according to any one of claims 1 to 6, which has a number average molecular weight of 500 to 20,000.   The polyphenylene ether according to any one of claims 1 to 7, which has an epoxy equivalent of 300 to 2,000. General formula (4)

(In the formula, R ¹ and R ² each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ¹ or R ² are present, each may be the same or different, and p is (0 or an integer of 1 to 3, q is an integer of 0 or 1 to 5, and X ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
And, if desired, general formula (5)

(In the formula, R ³ represents a single bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom, a sulfur atom or a sulfonyl group, and R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. And when a plurality of R ⁴ are present, each may be the same or different, and r and s are each independently 0 or an integer of 1 to 4.)
And / or general formula (6)

(Wherein R ⁵ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵ are present, each may be the same as or different from each other, and t is 0 or an integer of 1 to 4) R ⁶ is an m-valent hydrocarbon group, and m is an integer of 3 to ^6. )
A process for producing a polyphenylene ether, comprising a step of oxidizing (co) polymerizing a polyphenol compound represented by formula (1).   (A) A polyphenylene ether composition comprising the polyphenylene ether according to any one of claims 1 to 7 and (B) a curing agent.   Furthermore, the polyphenylene ether composition of Claim 9 containing (C) curable resin.   Furthermore, the polyphenylene ether composition of Claim 9 or 10 containing a flexibility imparting agent (D).   Hardened | cured material of the polyphenylene ether composition in any one of Claims 9-11.   The polyphenylene ether according to claim 1, which is used for a solder resist.   The polyphenylene ether composition according to claim 9, which is used for a solder resist.   The cured product according to claim 12, which is used for a solder resist.