JP7202920B2 - Polyphenylene ether-containing resin composition - Google Patents

Description

The present invention relates to a polyphenylene ether-containing resin composition and the like.

In recent years, with the remarkable progress in information network technology and the expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to meet these demands, materials for substrates such as printed wiring boards must have properties such as flame retardancy, heat resistance, and peel strength with copper foil, which have been conventionally required. Dielectric loss tangent is required. Therefore, further improvement of resin compositions used for substrate materials such as printed wiring boards has been studied.

Among substrate materials, polyphenylene ether (PPE) has a relatively low dielectric constant and a relatively low dielectric loss tangent, and is suitable as a printed wiring board material that meets the above requirements. For example, the polyphenylene ether-containing resin composition described in Patent Document 1 controls the average number of phenolic hydroxyl groups per polyphenylene ether molecule within a specific range, or specifies the content of multiple polyphenylene ethers with different molecular weights. This is intended to improve moldability, heat resistance, adhesion and electrical properties.

WO2012/081705

Regarding the polyphenylene ether-containing resin composition described in Patent Document 1, there is still room for investigation regarding electrical properties, for example, reduction of dielectric constant and dielectric loss tangent.

Accordingly, an object of the present invention is to provide a polyphenylene ether-containing resin composition having excellent electrical properties, and electronic circuit board materials, resin films, prepregs and laminates formed using the same.

｛式中、
Ｘは、ａ価の任意の連結基であり、ａは２．５以上の数であり、
Ｒ^５は、各々独立に任意の置換基であり、ｋは各々独立に１～４の整数であり、ｋ個あるＲ^５のうちの少なくとも１つは、下記式（２）：

（式中、Ｒ^１１は、各々独立にＣ_１－８のアルキル基であり、Ｒ^１２は、各々独立にＣ_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、Ｃ_１－８のアルキル基又はフェニル基のいずれかを示し、かつ前記アルキル基、アルキレン基及びフェニル基は、Ｃ_１－８の条件を満たす限度で置換基を有してよい）
で表される部分構造を含み、
Ｙは、各々独立に下記式（３）：

（式中、Ｒ^２１は、各々独立にＣ_１－６の飽和又は不飽和の炭化水素基であり、Ｒ^２２は、各々独立に水素原子又はＣ_１－６の飽和又は不飽和の炭化水素基であり、かつ前記飽和又は不飽和の炭化水素基はＣ_１－６の条件を満たす限度で置換基を有していてもよい）
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１～２００の整数であり、
Ｌは、任意の２価の連結基、又は単結合であり、かつ
Ａは、各々独立に、炭素－炭素二重結合及び／又はエポキシ結合を含有する置換基を示す｝
で表される構造を有し、かつ数平均分子量が５００～８，０００であるポリフェニレンエーテル成分Ａ；
（ｂ）架橋剤；及び
（ｃ）有機過酸化物；
を含む樹脂組成物。
［２］
前記架橋剤が、炭素－炭素不飽和二重結合を１分子中に平均２個以上有し、前記架橋剤の数平均分子量が４，０００以下であり、かつ前記ポリフェニレンエーテル成分Ａ：前記架橋剤の重量比が、２５：７５～９５：５である、項目１に記載の樹脂組成物。
［３］
前記架橋剤が、トリアリルシアヌレート、トリアリルイソシアヌレート、及びポリブタジエンから成る群より選択される少なくとも一種の化合物を含む、項目１又は２に記載の樹脂組成物。
［４］
前記有機過酸化物の１分間半減期温度が、１５５℃～１８５℃である、項目１～３のいずれか１項に記載の樹脂組成物。
［５］
前記有機過酸化物の含有量が、前記ポリフェニレンエーテル成分Ａと前記架橋剤の合計質量１００質量部を基準として、０．０５質量部～５質量部である、項目１～４のいずれか１項に記載の樹脂組成物。
［６］
前記樹脂組成物が、熱可塑性樹脂をさらに含み、前記熱可塑性樹脂が、ビニル芳香族化合物とオレフィン系アルケン化合物とのブロック共重合体及びその水素添加物、並びにビニル芳香族化合物の単独重合体から成る群より選択される少なくとも１種であり、かつ前記ブロック共重合体又はその水素添加物の前記ビニル芳香族化合物由来の単位の含有率が２０質量％以上である、項目１～５のいずれか１項に記載の樹脂組成物。
［７］
前記熱可塑性樹脂の重量平均分子量が、１０，０００～３００，０００である、項目６に記載の樹脂組成物。
［８］
前記熱可塑性樹脂の含有量が、前記ポリフェニレンエーテル成分Ａ及び前記架橋剤の合計質量１００質量部を基準として、２質量部～２０質量部である、項目６又は７に記載の樹脂組成物。
［９］
前記樹脂組成物が、難燃剤をさらに含み、かつ前記難燃剤が、前記樹脂組成物の硬化後に前記樹脂組成物中で他の含有成分と相溶しない、項目１～８のいずれか１項に記載の樹脂組成物。
［１０］
項目１～９のいずれか１項に記載の樹脂組成物を含む、電子回路基板材料。
［１１］
項目１～９のいずれか１項に記載の樹脂組成物を含む、樹脂フィルム。
［１２］
基材と、項目１～９のいずれか１項に記載の樹脂組成物との複合体である、プリプレグ。
［１３］
前記基材がガラスクロスである、項目１２に記載のプリプレグ。
［１４］
項目１１に記載の樹脂フィルム、又は項目１２若しくは１３に記載のプリプレグの硬化物と、金属箔との積層体。 The present inventors have made intensive studies to solve the above problems, and found that by specifying the structure and molecular weight of polyphenylene ether in a resin composition containing polyphenylene ether, a cross-linking agent, and an organic peroxide, the resin composition The inventors have found that the electrical properties of cured products can be improved, and have completed the present invention. That is, the present invention is as follows.
[1]
(a) the following formula (1):

{In the formula,
X is any a-valent linking group, a is a number of 2.5 or more,
Each R ⁵ is independently an optional substituent, each k is independently an integer of 1 to 4, and at least one of k R ⁵ is represented by the following formula (2):

(wherein each R ¹¹ is independently a C _1-8 alkyl group, each R ¹² is independently a C _1-8 alkylene group, each b is independently 0 or 1, and R ¹³ represents either a hydrogen atom, a C _1-8 alkyl group or a phenyl group, and the alkyl group, alkylene group and phenyl group have substituents to the extent that the conditions for C _1-8 are satisfied; good)
contains a substructure represented by
Y is each independently represented by the following formula (3):

(wherein R ²¹ is each independently a C _1-6 saturated or unsaturated hydrocarbon group, R ²² is each independently a hydrogen atom or a C _1-6 saturated or unsaturated hydrocarbon group and the saturated or unsaturated hydrocarbon group may have a substituent to the extent that the conditions for C _1-6 are satisfied)
is a divalent linking group having a structure represented by n represents the number of repetitions of Y, each independently an integer of 1 to 200,
L is any divalent linking group or single bond, and A each independently represents a substituent containing a carbon-carbon double bond and/or an epoxy bond}
A polyphenylene ether component A having a structure represented by and a number average molecular weight of 500 to 8,000;
(b) a cross-linking agent; and (c) an organic peroxide;
A resin composition comprising:
[2]
The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds per molecule, the number-average molecular weight of the cross-linking agent is 4,000 or less, and the polyphenylene ether component A: the cross-linking agent The resin composition according to item 1, wherein the weight ratio of is 25:75 to 95:5.
[3]
3. The resin composition according to item 1 or 2, wherein the cross-linking agent contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.
[4]
4. The resin composition according to any one of items 1 to 3, wherein the organic peroxide has a 1-minute half-life temperature of 155°C to 185°C.
[5]
Any one of items 1 to 4, wherein the content of the organic peroxide is 0.05 parts by mass to 5 parts by mass based on the total mass of 100 parts by mass of the polyphenylene ether component A and the cross-linking agent. The resin composition according to .
[6]
The resin composition further contains a thermoplastic resin, and the thermoplastic resin is a block copolymer of a vinyl aromatic compound and an olefinic alkene compound, a hydrogenated product thereof, and a homopolymer of a vinyl aromatic compound. Any one of items 1 to 5, which is at least one selected from the group consisting of, and the content of units derived from the vinyl aromatic compound in the block copolymer or the hydrogenation thereof is 20% by mass or more. 1. The resin composition according to item 1.
[7]
7. The resin composition according to item 6, wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000.
[8]
The resin composition according to item 6 or 7, wherein the content of the thermoplastic resin is 2 parts by mass to 20 parts by mass based on the total mass of 100 parts by mass of the polyphenylene ether component A and the cross-linking agent.
[9]
Any one of items 1 to 8, wherein the resin composition further comprises a flame retardant, and the flame retardant is incompatible with other components in the resin composition after curing of the resin composition. The described resin composition.
[10]
An electronic circuit board material comprising the resin composition according to any one of items 1 to 9.
[11]
A resin film comprising the resin composition according to any one of Items 1 to 9.
[12]
A prepreg that is a composite of a substrate and the resin composition according to any one of items 1 to 9.
[13]
A prepreg according to item 12, wherein the base material is glass cloth.
[14]
A laminate of the resin film according to item 11 or the cured product of the prepreg according to item 12 or 13 and a metal foil.

According to the present invention, the polyphenylene ether-containing resin composition has excellent electrical properties and can be used to provide electronic circuit board materials, resin films, prepregs and laminates.

1 is the result of ¹ H-NMR measurement of modified polyphenylene ether 1 (modified PPE1) obtained in Example 1. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, the form (only henceforth "this embodiment") for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the present embodiment described below, and various modifications can be made within the scope of the gist of the present invention.

Resin composition The resin composition according to the present embodiment contains polyphenylene ether (PPE), a cross-linking agent, and an organic peroxide, and optionally a flame retardant, other additives, a thermoplastic resin, a silica filler, Solvents and the like can be further included. The constituent elements of the resin composition according to this embodiment will be described below.

Polyphenylene ether (PPE)
Generally, polyphenylene ether (PPE) has a repeating structure composed of substituted or unsubstituted phenylene ether units. As used herein, the term "polyphenylene ether" shall include dimers, trimers, oligomers and polymers. Although the PPE may contain copolymerization constituent units other than phenylene ether units, the amount of such copolymerization constituent units is typically 0% or more or greater than 0% based on the number of total unit structures. and 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

Typical PPE include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6 -phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), etc., as well as 2,6-dimethylphenol and other phenols (e.g., 2,3,6- trimethylphenol, 2-methyl-6-butylphenol, etc.), and PPE copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols.

で表される構造を有し、かつ数平均分子量が５００～８，０００であるポリフェニレンエーテル成分Ａを含む。 Polyphenylene ether component A (PPE-A)
The resin composition according to the present embodiment has the following formula (1) as a polyphenylene ether component:

and a polyphenylene ether component A having a number average molecular weight of 500 to 8,000.

In formula (1), X is an a-valent linking group, a is a number of 2.5 or more, preferably an integer of 3 or more, more preferably an integer of 3-6. Specific examples of X include, for example, a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon or oxygen; or an element such as nitrogen, phosphorus, silicon or containing these and the like.

で表される部分構造を含む。 R ⁵ is an optional substituent, k is an integer of 1 to 4, and when k is 2 or more, two R ⁵ may be linked to form a ring, At least one of the k R ⁵ is represented by the following formula (2):

Including the partial structure represented by.

In formula (2), each R ¹¹ is independently a C _1-8 alkyl group, each R ¹² is independently a C _1-8 alkylene group, b is independently 0 or 1, and R ¹³ represents either a hydrogen atom, a C _1-8 alkyl group or a phenyl group, and these alkyl groups, alkylene groups and phenyl groups have substituents to the extent that the conditions for C _1-8 are satisfied; good too.

The partial structure represented by formula (2) preferably has secondary and/or tertiary carbon atoms, such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, It can have a 2,2-dimethylpropyl group, or a structure having a phenyl group at the end thereof. The partial structure represented by formula (2) is preferably directly bonded to the benzene ring to which R5 in formula ( ¹ ) is bonded. Further, the partial structure represented by formula (2) is bonded to the 2-position and/or 6-position (ortho position to -O-) of the benzene ring to which R ⁵ in formula (1) is bonded. preferably.

の部分は、以下のいずれかの構造：

であることが好ましく、それらの具体例としては、以下の化合物から、末端のフェノール性水酸基の水素を全て取り除いたものが挙げられる：
４，６－ジｔｅｒｔ－ブチルベンゼン１，２，３－トリオール、２，６－ビス（３－ｔｅｒｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、２，４，６－トリス（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシベンジル）メシチレン、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］、１，３，５－トリス［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス［［４－（１，１－ジメチルエチル）－３－ヒドロキシ－２，６－ジメチルフェニル］メチル］－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン。 Of the structures represented by formula (1), the following:

The part of is one of the following structures:

Specific examples thereof include the following compounds in which all the hydrogen atoms of terminal phenolic hydroxyl groups are removed:
4,6-di-tert-butylbenzene 1,2,3-triol, 2,6-bis(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol, 1,1,3- Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,4,6-tris(3′,5′-di-tert-butyl-4′-hydroxybenzyl)mesitylene, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl] methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy- 2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

で表される構造を有する２価の連結基（置換基を有するフェノール単位）であり、そして式（１）におけるｎは、Ｙの繰り返し数を表し、各々独立に、０～２００の整数である。 Each Y in formula (1) is independently represented by the following formula (3):

is a divalent linking group (a phenol unit having a substituent) having a structure represented by, and n in formula (1) represents the number of repetitions of Y, each independently being an integer of 0 to 200 .

In formula (3), R ²¹ is independently a C _1-6 saturated or unsaturated hydrocarbon group, preferably methyl, ethyl, n-propyl, vinyl, allyl, ethynyl, propargyl group, etc., more preferably a methyl group or an ethyl group, and still more preferably a methyl group. R ²² is independently a hydrogen atom or a C _1-6 saturated or unsaturated hydrocarbon group, preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, etc., more preferably a hydrogen atom, It is a methyl group, more preferably a hydrogen atom. Here, the saturated or unsaturated hydrocarbon group may have substituents to the extent that C _1-6 conditions are satisfied.

表される。 A in formula (1) is a substituent containing a carbon-carbon double bond and/or an epoxy bond, and specific examples of A are the following formulas (4) to (8):

expressed.

In formulas (4) to (8), each R ³¹ is independently hydrogen, hydroxyl, or a C _1-30 hydrocarbon group, aryl group, alkoxy group, aryloxy group, amino group or hydroxyalkyl group. Each R ³² is independently a C _1-30 hydrocarbon group. Each R ³³ is independently hydrogen, hydroxyl, or a C _1-30 hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, hydroxyalkyl group, vinyl group or isopropenyl group ^; At least one of them is a vinyl group or an isopropenyl group. s and t are integers from 0 to 5;

Specific examples of hydrocarbon groups for 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, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4 -dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2 ,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl , 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methyl heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 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.

Hydrocarbon groups for R ³¹ are preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl , 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl , 3-methylcyclohexyl, 4-methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably methyl and ethyl , n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl , n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethyl xyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, etc., more preferably methyl, ethyl, n-propyl, 2 -propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2- methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl , decyl, isodecyl, undecyl, de Decyl, benzyl and the like.

Specific examples of hydrocarbon groups for R ³² include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl -1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1 ,2-cyclopentylene, 1,3-cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene , hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1 ,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4 -butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene , 2,3-dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl -1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 1,1 -dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl -1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1 ,5-pentylene, 3,4-dimethyl-1,5-pentylene, 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl-3,3-dimethyl-1,4-butylene, 1 , 2,3-trimethyl-1,4-butylene and the like.

Specific examples of hydrocarbon groups for R ³² include 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, 3-methyl -1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2, 3-dimethyl-1,3-cyclopentylene, 2,4-dimethyl-1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1-methyl-1,7-heptylene, 1-ethyl-1,6-hexylene, 1-propyl-1,5-pentylene, 2-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl- 1,6-hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1, 6-hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6- Hexylene, 2,5-dimethyl-1,6-hexylene, 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 and the like.

Furthermore, specific examples of hydrocarbon groups for R ³² include 1-(2-methylpropyl)-1,4-butylene, 1-(2-methylpropyl)-2-methyl-1,4-butylene, 1, 1-(2-methylpropyl)ethylene, 1,1-(2-methylpropyl)ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3- Propylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl- 1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl -1,4-cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4 -methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-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-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene and the like.

The hydrocarbon group for R ³² is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl- 1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1, 3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylene, 1-methyl-1,6- Hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5- pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1, 4-cyclohexylene, octamethylene, 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5- methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5- ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like, 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 Chill-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 and the like, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2 -propylene, 1,1-dimethylethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, Octamethylene, 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7 -heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6 -hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene, and the like.

Specific examples of substituents containing a carbon-carbon double bond for A in formula (1) include vinyl group, allyl group, isopropenyl group, 1-butenyl group, 1-pentenyl group, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-isopropenylbenzyl group, m- vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenylpropenyl group, p-vinylphenylbutenyl group, m-vinyl phenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group, o-vinylphenylbutenyl group, methacryl group, acrylic group, 2 -ethylacryl group, 2-hydroxymethylacryl group and the like.

により表される。また、Ｌが任意の２価の連結基である場合、かかるＬの具体例は、例えば、下記式：

｛式中、ａ、Ｒ^５、ｋ、Ｘ、Ｙ及びｎは、式（１）の説明において定義したとおりである｝
で表される構造を有する。 L in formula (1) is any divalent linking group or single bond (direct bond). When L is a single bond, the structure represented by formula (1) has the following formula:

is represented by Further, when L is any divalent linking group, specific examples of such L include the following formula:

{Wherein, a, R ⁵ , k, X, Y and n are as defined in the description of formula (1)}
It has a structure represented by

｛式中、ｎは、Ｙの繰り返し数を表し、０～２００の整数である｝
で表される分岐構造などが挙げられる。 The structure represented by formula (1) can take various branched structures depending on the value of the valence a of X. For example, if a = 3 in equation (1), the following equation:

{Wherein, n represents the number of repetitions of Y and is an integer from 0 to 200}
A branched structure represented by is mentioned.

Specific examples of the structure represented by formula (1) include the structures shown below.

In the above formula, Z is any linking group corresponding to X in formula (1). R ¹ is a substituent represented by formula (2), and b is an integer of 1-4. The position of ^R1 is not limited, and ^R1 may take any position. In addition, when b is 2 or more, each of a plurality of R ¹ may have the same structure or a different structure. Examples of R ¹ include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2,2-dimethylpropyl group, and structures having a phenyl group at the end of these groups. . A is a substituent containing carbon-carbon double bonds and/or epoxy bonds. R ² is hydrogen or a hydrocarbon group having a chain or cyclic structure with 1 to 8 carbon atoms. When there is more than one R ² , each substituent may be the same or different. Specific examples of R ² include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group and n-octyl. group, phenyl group, benzyl group, 2-ethylhexyl group, etc., and from the viewpoint of reactivity during synthesis, etc., hydrogen, methyl, ethyl, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group , n-hexyl, cyclohexyl, n-heptyl and n-octyl groups are preferred. However, if the reactivity during synthesis can also be controlled by appropriately setting the position of R ² or the reaction conditions during synthesis, the structure of R ² is not limited and the conditions of C _1-8 are satisfied. Any structure is acceptable within the scope. Z is a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon and oxygen; or an element such as nitrogen, phosphorus, silicon or a group containing these.

上記式において、Ｒ^４～Ｒ^１０は、同じでも異なっていてもよく、水素又はＣ_１－８の炭化水素基を示す。また、Ｒ^３１～Ｒ^３３は、同じでも異なっていてもよく、水素又はＣ_１－６の炭化水素基を示す。ｊ、ｋ、ｌ、及びｍは、同じでも異なっていてもよく、０～４の整数である。Ｒ^４～Ｒ^１０の具体例としては、水素、メチル基、エチル基、ｎ－プロピル基、イソプロピルｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、２－ペンチル基、３－ペンチル基、シクロペンチル基、ｎ－ヘキシル基、２－ヘキシル基、３－ヘキシル基、シクロヘキシル基、ｎ－ヘプチル基、２－ヘプチル基、３－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基等が挙げられる。Ｒ^３１～Ｒ^３３の具体例としては、水素、メチル基、エチル基、ｎ－プロピル基、イソプロピルｎ－ブチル基、イソブチル基、ｎ－ペンチル基、２－ペンチル基、３－ペンチル基、シクロペンチル基、ｎ－ヘキシル基、２－ヘキシル基、３－ヘキシル基、シクロヘキシル基が挙げられる。 Specific examples of the hydrocarbon group for Z include structures represented by the following formulas.

In the above formula, R ⁴ to R ¹⁰ may be the same or different and represent hydrogen or a C _1-8 hydrocarbon group. In addition, R ³¹ to R ³³ may be the same or different and represent hydrogen or a C _1-6 hydrocarbon group. j, k, l, and m, which may be the same or different, are integers from 0-4. Specific examples of R ⁴ to R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3- pentyl group, cyclopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-ethylhexyl group and the like mentioned. Specific examples of R ³¹ to R ³³ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group and cyclopentyl group. , n-hexyl group, 2-hexyl group, 3-hexyl group and cyclohexyl group.

上記式において、Ｒ^４～Ｒ^１０は、同じでも異なっていてもよく、水素又はＣ_１－８の炭化水素基を示す。ｊ、ｋ、ｌ、及びｍは、同じでも異なっていてもよく、０～４の整数である。Ｒ^４～Ｒ^１０の具体例としては、水素、メチル基、エチル基、ｎ－プロピル基、イソプロピルｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、２－ペンチル基、３－ペンチル基、シクロペンチル基、ｎ－ヘキシル基、２－ヘキシル基、３－ヘキシル基、シクロヘキシル基、ｎ－ヘプチル基、２－ヘプチル基、３－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基等が挙げられる。 Specific examples of hydrocarbon groups containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon and oxygen as Z are represented by the following formulas.

In the above formula, R ⁴ to R ¹⁰ may be the same or different and represent hydrogen or a C _1-8 hydrocarbon group. j, k, l, and m, which may be the same or different, are integers from 0-4. Specific examples of R ⁴ to R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3- pentyl group, cyclopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-ethylhexyl group and the like mentioned.

Specific examples of groups containing nitrogen, phosphorus, oxygen, etc. as Z are as follows.

Among the above specific examples, if the structure of A is specified for the first one, it will have a structure such as the following formula. The same applies to the case of 4 to 6 branches, and R ³¹ , R ³² , s and t in the following formula are as defined in the specific examples of A.

The number average molecular weight (Mn) of the polyphenylene ether component A is 500 to 8,000 in polystyrene equivalent molecular weight using GPC, and from the viewpoint of fluidity, compatibility with other components, etc., preferably 700 to 6. ,000, more preferably 900 to 4,500. Also, from the same point of view, the molecular weight distribution of the polyphenylene ether component A is preferably in the range of 1.1 to 5, 1.4 to 4, or 1.5 to 3 as Mw (weight average molecular weight) / Mn. is.

Modified polyphenylene ether having the structure of formula (1) in the present embodiment, for example, by preparing a polyphenylene ether by a redistribution reaction method using a phenylene ether polymer having a higher molecular weight, by introducing a group A to the end can be manufactured. In the case of production of polyphenylene ether by redistribution reaction, it is possible to produce according to the conditions defined in known reaction conditions. In this case, the resulting polymer has a lower molecular weight than the raw material phenylene ether polymer, so the ratio of the raw material polyphenylene ether and the polyfunctional phenol compound may be adjusted according to the target molecular weight.

Further, the substituent A in the formula (1), for example, the functional group represented by the formulas (4) to (7), the method of introducing the resulting polyphenylene ether polymer terminal is not limited, the functional group Various known methods may be employed depending on the type. For example, introduction of functional groups having structures of formula (4), (6) or (7) can generally follow the formation of ether bonds by Williamson synthesis methods. Introduction of a functional group having a structure of formula (5) is a reaction of forming an ester bond between a hydroxyl group at the end of a polyphenylene ether polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and a known ester Bonding methods are available.

Polyphenylene ether component A (PPE-A) has high curing reactivity, low dielectric properties, good fluidity and moldability, and excellent heat resistance, so it is suitable for use as a material for various electric and electronic devices. In particular, it can be suitably used for producing prepregs for electric/electronic parts (printed wiring board substrates, etc.). PPE-A may be used as a single resin in the resin composition, may be used in combination with polyphenylene ether having another structure, or may be used in combination with various known additives. The content of PPE-A in the resin composition can be, for example, 0.5% by mass to 95% by mass.

Polyphenylene ether component B (PPE-B)
In addition to the polyphenylene ether component A having a number average molecular weight of 500 to 8,000 described above, the resin composition according to the present embodiment has an average number of phenolic hydroxyl groups per molecule of 1.2 or more and a number of It is preferable to include a polyphenylene ether component B having an average molecular weight of 8,000 or more and 50,000 or less. The polyphenylene ether component B is stable in its production process and has excellent dielectric properties and heat resistance, so it tends to improve the electrical properties of the cured product of the resin composition without hindering the polyphenylene ether component A. be.

Polyphenylene ether component B (PPE-B) can be distinguished from polyphenylene ether component A (PPE-A) and has an average number of phenolic hydroxyl groups per molecule of 1.2 or more and a number average molecular weight of 8,000. Any polyphenylene ether (PPE) that meets ~50,000 will suffice. From the viewpoint of combined use with PPE-A, the number average molecular weight of PPE-B is preferably more than 8,000 and 50,000 or less. When PPE-A and PPE-B are used together in the resin composition, from the viewpoint of the stability and heat resistance of the resin composition, the total mass of PPE-A and PPE-B is 100% by mass, and the PPE It is preferable that the content of -A is 1% by mass to 99.9% by mass and the content of PPE-B is 0.1% to 99% by mass, more preferably PPE-A content The amount of PPE-B is 20% to 98% by mass, and the content of PPE-B is 2% to 80% by mass, more preferably the content of PPE-A is 40% to 95% by mass, and PPE The content of -B is 5% by mass to 60% by mass.

Cross-Linking Agents Any cross-linking agent capable of undergoing or promoting a cross-linking reaction can be used in this embodiment. 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 resin composition can be suppressed, and good resin fluidity during heat molding can be obtained. The number average molecular weight may be measured by a general molecular weight measuring method, and specific examples include values measured using GPC.

The cross-linking agent preferably has an average of two or more carbon-carbon unsaturated double bonds per molecule from the viewpoint of cross-linking reaction. The cross-linking agent may be composed of one type of compound, or may be composed of two or more types of compounds. As used herein, the term "carbon-carbon unsaturated double bond" refers to a double bond located at the end branched from the main chain when the cross-linking agent is a polymer or oligomer. Carbon-carbon unsaturated double bonds include, for example, 1,2-vinyl bonds in polybutadiene.

When the number average molecular weight of the cross-linking agent is less than 600, the number (average value) of carbon-carbon unsaturated double bonds per molecule of the cross-linking agent is preferably 2-4. When the number average molecular weight of the cross-linking agent is 600-1500, the number (average value) of carbon-carbon unsaturated double bonds per molecule of the cross-linking agent is preferably 4-26. When the number average molecular weight of the cross-linking agent is 1,500 to 4,000, the number (average value) of carbon-carbon unsaturated double bonds per molecule of the cross-linking agent is preferably 26 to 60. . 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 a specific value or more, so that the resin composition according to the present embodiment has the reactivity of the cross-linking agent. This further increases the cross-linking density of the cured product of the resin composition, and as a result, it is possible to impart even better heat resistance. 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 not more than a specific value, so that even better resin fluidity can be imparted during hot molding. .

Examples of cross-linking agents include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), triallyl cyanurate compounds such as triallyl cyanurate (TAC), and polyfunctional methacrylates 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, vinylbenzyl compounds such as divinylbenzene having a vinylbenzyl group in the molecule , 4,4′-bismaleimidediphenylmethane, and other polyfunctional maleimide compounds having two or more maleimide groups in the molecule. These cross-linking agents are used singly or in combination of two or more. Among these, the cross-linking agent preferably contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. When the cross-linking agent contains at least one compound described above, the cross-linking density is further increased during the curing reaction (cross-linking reaction), thereby further improving the heat resistance of the cured product of the resin composition. There is a tendency.

The weight ratio of PPE:crosslinking agent is preferably 25:75 to 95:5, more preferably 25:75 to 95:5, from the viewpoint of balancing the low dielectric constant and low dielectric loss tangent at the time of curing with the crosslink density of the crosslinked structure. , 32:68 to 85:15. Also, the weight ratio of PPE-A:crosslinking agent is preferably 25:75 to 95:5, more preferably 32:68 to 85:15 from the same viewpoint.

Organic Peroxide Any organic peroxide capable of promoting the polymerization reaction of the resin composition comprising the polyphenylene ether and the crosslinker can be used in this embodiment. Examples of organic peroxides include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butyl peroxide), oxy)hexyne-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, trimethylsilyltriphenylsilylperoxide and the like. A radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition. Among them, 2,5-dimethyl-2,5-di(t-butylperoxy ) hexyne-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°C or higher and 185°C or lower, more preferably 160°C to 180°C or 165°C to 175°C. As used herein, the 1-minute half-life temperature is the temperature at which it takes 1 minute for the organic peroxide to decompose and its amount of active oxygen to halve. The 1-minute half-life temperature is obtained by dissolving an organic peroxide in a solvent inert to radicals, such as benzene, to a concentration of 0.05 mol/L to 0.1 mol/L, and obtaining an organic peroxide solution. is a value confirmed by a method of thermally decomposing in a nitrogen atmosphere.

Since the 1-minute half-life temperature of the organic peroxide is 155° C. or higher, when the PPE-containing resin composition is subjected to heat and pressure molding, the reaction with the cross-linking agent is started after the PPE is sufficiently melted. Therefore, it tends to be excellent in moldability. On the other hand, since the 1-minute half-life temperature of the organic peroxide is 185°C or less, the decomposition rate of the organic peroxide under normal heat and pressure molding conditions (for example, the maximum temperature of 200°C) is sufficient. Since the cross-linking reaction with the cross-linking agent can proceed efficiently and slowly, it is possible to form a cured product having good electrical properties (especially dielectric loss tangent).

Examples of organic peroxides having a 1-minute half-life temperature in the range of 155° C. to 185° C. include t-hexylperoxyisopropyl monocarbonate (155.0° C.), t-butylperoxy-3,5,5 -trimethylhexanoate (166.0°C), t-butyl peroxylaurate (159.4°C), t-butylperoxyisopropyl monocarbonate (158.8°C), t-butylperoxy 2-ethylhexyl monocarbonate (161.4°C), t-hexylperoxybenzoate (160.3°C), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (158.2°C), t-butylperoxyacetate (159.9°C), 2,2-di-(t-butylperoxy)butane (159.9°C), t-butyl peroxybenzoate (166.8°C), n-butyl 4,4-di- (t-butylperoxy)valerate (172.5°C), di(2-t-butylperoxyisopropyl)benzene (175.4°C), dicumyl peroxide (175.2°C), di-t-hexylper oxide (176.7°C), 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (179.8°C), and t-butylcumyl peroxide (173.3°C). be done.

The content of the organic peroxide is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass, based on the total of 100 parts by mass of the PPE and the cross-linking agent, from the viewpoint that the reaction rate can be increased. part or more, or 1 part by mass or more, more preferably 1.5 parts by mass or more, and from the viewpoint that the dielectric constant and dielectric loss tangent of the resulting cured product can be kept low, preferably 5 parts by mass or less, more preferably It is 4.5 parts by mass or less. Also, from the same viewpoint, the content of the organic peroxide is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0 parts by mass, based on the total of 100 parts by mass of PPE-A and the cross-linking agent. .5 parts by mass or more and 4.5 parts by mass or less, more preferably 1 part by mass or more and 4.5 parts by mass or less, or 1.5 parts by mass or more and 4.5 parts by mass or less.

Thermoplastic resin The resin composition preferably contains a thermoplastic resin. The thermoplastic resin is a block copolymer of a vinyl aromatic compound and an olefinic alkene compound and its hydrogenated product (a hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefinic alkene compound). block copolymers) and homopolymers of vinyl aromatic compounds. The content of the units derived from the vinyl aromatic compound in the block copolymer or its hydrogenation is preferably 20% by mass or more, more preferably 22% by mass or more, and 99% by mass or less. be able to. When the content of units derived from the vinyl aromatic compound in the block copolymer or its hydrogenation is 20% by mass or more, the compatibility with polyphenylene ether is further improved, and the adhesion strength with the metal foil is further improved. tend to improve.

A vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. The olefinic 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. Among them, thermoplastic resins are styrene-butadiene block copolymers, styrene-ethylene-butadiene block copolymers, styrene-ethylene-butylene block copolymers, styrene -butadiene-butylene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, styrene-isobutylene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-ethylene - from the group consisting of hydrogenated butadiene block copolymers, hydrogenated styrene-butadiene-butylene block copolymers, hydrogenated styrene-isoprene block copolymers, and homopolymers of styrene (polystyrene) It is preferably at least one selected, more preferably one or more selected from the group consisting of a styrene-butadiene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, and polystyrene. .

The hydrogenation rate in the hydrogenated product is not particularly limited, and a part of the carbon-carbon unsaturated double bonds derived from the olefinic alkene compound may remain.

The weight average molecular weight of the thermoplastic resin is preferably 10,000 to 300,000, more preferably 20,000 to 290,000, still more preferably 30,000 to 280,000. When the weight-average molecular weight is 10,000 or more, the resin composition of the present embodiment tends to be more excellent in heat resistance when cured. When the weight average molecular weight is 300,000 or less, the resin composition of the present embodiment tends to have better resin fluidity during heat molding. The weight average molecular weight is determined by the method described in Examples below.

The content of the thermoplastic resin is preferably 2 parts by mass to 20 parts by mass, more preferably 3 parts by mass to 19 parts by mass, based on the total of 100 parts by mass of the PPE and the cross-linking agent. When the content is 2 parts by mass or more, the resin composition of the present embodiment tends to be even more excellent in low dielectric constant properties, low dielectric loss tangent properties, and adhesion to metal foil when cured. When the content is 20 parts by mass or less, the resin composition of the present embodiment tends to have even better resin fluidity during heat molding. Also, from the same viewpoint, the content of the thermoplastic resin is preferably 2 parts by mass to 20 parts by mass, more preferably 3 parts by mass to 19 parts by mass, based on the total of 100 parts by mass of PPE-A and the cross-linking agent. is.

Flame Retardant The resin composition of the present embodiment preferably contains a flame retardant. From the viewpoint of improving heat resistance, the flame retardant is not particularly limited as long as it is incompatible with other components in the resin composition after the resin composition is cured. Preferably, the flame retardant is incompatible with the PPE and/or crosslinker in the resin composition after curing of the resin composition. Examples of flame retardants 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; phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate; These flame retardants are used singly or in combination of two or more. Among these, the flame retardant is preferably decabromodiphenylethane from the viewpoint of further excellent low dielectric constant and low dielectric loss tangent when the resin composition is cured.

The content of the flame retardant is not particularly limited, but from the viewpoint of maintaining the flame retardancy of the UL standard 94V-0 level, the total 100 parts by mass of the polyphenylene ether (PPE) resin and the crosslinking agent, preferably It is 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. In addition, from the viewpoint of maintaining low dielectric constant and dielectric loss tangent of the obtained cured product, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less. .

Silica Filler The resin composition of the present embodiment may contain silica filler. Silica fillers include, for example, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica. The content of the silica filler can be 10 parts by mass to 100 parts by mass with respect to the total of 100 parts by mass of the polyphenylene ether (PPE) resin and the cross-linking agent. In addition, the silica filler may have a surface treated with a silane coupling agent or the like.

The resin composition of the present embodiment may further contain additives such as heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, solvents, etc., in addition to the flame retardant and silica filler. When the resin composition of the present embodiment contains a solvent, it can be in the form of a varnish in which solid components in the resin composition are dissolved or dispersed in the solvent. Moreover, a resin film can be formed from the resin composition of this embodiment.

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

Prepreg The prepreg of the present embodiment includes a substrate and the resin composition of the present embodiment impregnated or applied to the substrate. The prepreg is obtained by, for example, impregnating a base material such as a glass cloth with the varnish and then removing the solvent by drying with a hot air dryer or the like.

Various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat, etc.; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; wholly aromatic polyamide fiber, wholly aromatic polyester Woven or non-woven fabric obtained from liquid crystal fiber such as fiber, polybenzoxazole fiber; Natural fiber cloth such as cotton cloth, hemp cloth, felt; Cloth obtained from carbon fiber cloth, kraft paper, cotton paper, paper-glass mixed yarn, etc. natural cellulosic substrates; polytetrafluoroethylene porous films; These substrates are used singly or in combination of two or more.

The solid content of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the 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, the mechanical properties such as bending elastic modulus tend to be more excellent in applications such as electronic substrates.

Metal-clad laminate The metal-clad laminate of the present embodiment is obtained by laminating and curing the resin composition or resin film of the present embodiment, or the prepreg of the present embodiment, and a metal foil. The metal-clad laminate preferably has a form in which a cured prepreg (also referred to as a "cured composite") and a metal foil are laminated and adhered to each other, and is suitably used as a material for electronic substrates. 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 composite to be combined with the metal foil may be one sheet or a plurality of sheets, and depending on the application, the metal foil is laminated on one side or both sides of the composite and processed into a laminate. As a method for producing a laminate, for example, a composite (for example, the above-mentioned prepreg) composed of a thermosetting resin composition and a base material is formed, and after stacking this with a metal foil, a thermosetting resin A method of obtaining a laminate in which a cured product laminate and a metal foil are laminated by curing the composition may be mentioned. One of the particularly preferred uses of said laminates is printed wiring boards. At least part of the metal foil is preferably removed from the metal-clad laminate of the printed wiring board.

Printed Wiring Board In the printed wiring board of the present embodiment, part of the metal foil is removed from the metal-clad laminate. The printed wiring board of the present embodiment can typically be formed using the prepreg of the present invention described above by a method of pressurizing and heating molding. Substrates include those described above with respect to prepregs. By containing the resin composition of the present embodiment, the printed wiring board of the present embodiment has excellent heat resistance and electrical properties (low dielectric constant and low dielectric loss tangent). Fluctuation can be suppressed, and furthermore, it has excellent insulation reliability and mechanical properties.

EXAMPLES The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited to the examples.

Synthetic Reaction of Polyphenylene Ether The following reaction was carried out under an inert gas atmosphere. Solvents used in the reaction are commercially available reagents. The raw materials and reagents used are as follows.

1. Solvent toluene: Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as it was.
Methyl ethyl ketone: Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as is.
Methanol: Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as is.
2. Initiator:
Nyper BMT: NOF products were used as they were.
3. Raw material polyphenylene ether S202A (number average molecular weight in terms of polystyrene: 16,000): A product manufactured by Asahi Kasei Corporation was used as it was.
S202A has the following structure.

4. Raw material phenol (polyfunctional/bifunctional phenol)
4-1. Phenols 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane with valence a (a=3 to 6) containing partial structure of formula (2): ADEKA Corporation The product (ADEKA STAB AO-30) was used as is.

4-2. Tris(4-hydroxyphenyl)ethane, a phenol with a valence of 3 not containing the partial structure of formula (2): Asahi Organic Chemicals product was used as it was.

5. Raw material of modifying group: methacrylic anhydride: Aldrich's reagent product was used as received.
Dimethylaminopyridine: Aldrich reagent was used as received.

Identification and analysis of polyphenylene ether 1. Number average molecular weight measurement Number average molecular weight measurement was performed by GPC under chloroform solvent. The number average molecular weight was obtained by a polystyrene conversion method based on a calibration curve using standard polystyrene.
2. NMR measurement A sample was dissolved in deuterated chloroform to a concentration of 5% by mass, and NMR measurement was performed. The progress of the reaction was confirmed by the decrease in the hydroxyl group peak from the ratio of the aromatic peak of the polyfunctional phenol unit and the proton peak of the hydroxyl group.
3. Melt Viscosity 200 ml of a 20% by mass methyl ethyl ketone solution of the sample was placed in a beaker, and the viscosity was measured at 25° C. and 30 rpm using a B-type rotational viscometer.

4. Average Terminal Functional Group Number The average terminal functional group number per PPE molecule was obtained by the following method. That is, a sample obtained by adding a tetramethylammonium hydroxide solution to a methylene chloride solution of PPE in accordance with the method described in "Kobunshi Ronbunshu, Vol. 51, No. 7 (1994), p. 480". Absorbance change at a wavelength of 318 nm was measured with a UV-visible spectrophotometer. From this measured value, the number of phenolic hydroxyl groups before and after terminal modification of PPE was determined. Also, the number average molecular weight of the PPE obtained by the above method 1 and the mass of the PPE were used to determine the number of molecules of the PPE (number average molecular number).
From these values, the average number of phenolic hydroxyl groups per molecule of PPE before and after modification was determined according to the following formula (1). :
Average number of phenolic hydroxyl groups per molecule = number of phenolic hydroxyl groups/number average number of molecules (1)
The average terminal functional group number after modification was determined according to the following formula (2). :
Average number of terminal functional groups per molecule = average number of phenolic hydroxyl groups before modification - average number of phenolic hydroxyl groups after modification (2)

｛式中、ｌ、ｍ及びｎは、下記数平均分子量を満たすように任意に選択される数である｝
で表されるような構造を有するポリフェニレンエーテル（以下、ＰＰＥ１という）であると確認できた。ＧＰＣ測定の結果、得られたＰＰＥ１のポリスチレン換算での分子量はＭｎ＝１，５００であった。また、ＰＰＥ１の２０％メチルエチルケトン溶媒中での溶液粘度は１２５ｃＰｏｉｓｅであった。 Production example 1
Synthesis of Polyphenylene Ether 1 (PPE1) A 500 ml three-necked flask was equipped with a three-way cock, and further equipped with a Dimroth and an equal pressure dropping funnel. After purging the inside of the flask with nitrogen, 100 g of the raw polyphenylene ether S202A, 200 g of toluene, and 12.8 g of 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane as a polyfunctional phenol were added. rice field. A thermometer was installed in the flask, and while stirring with a magnetic stirrer, the flask was heated to 90°C in an oil bath to dissolve the starting polyphenylene ether. As an initiator, 37.5 g of a 40% meta-xylene solution of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluyl peroxide (manufactured by NOF Corporation: Nyper BMT) was diluted with 87.5 g of toluene and was added dropwise at equal pressure. loaded into a funnel. After the temperature inside the flask was lowered to 80° C., the initiator solution was started dropping into the flask to initiate the reaction. The initiator was added dropwise over 2 hours, and after the dropwise addition, the temperature was raised to 90° C. again and stirring was continued for 4 hours. After the reaction, the polymer solution was added dropwise to methanol for reprecipitation, and then separated from the solution by filtration to recover the polymer. It was then dried under vacuum at 100° C. for 3 hours. By ¹ H-NMR, it was confirmed that the low-molecular-weight phenol was incorporated into the polymer and the hydroxyl group peak disappeared. From the results of this ¹ H-NMR measurement, the obtained polymer has the following formula:

{Wherein, l, m and n are numbers arbitrarily selected to satisfy the following number average molecular weight}
It was confirmed to be a polyphenylene ether (hereinafter referred to as PPE1) having a structure represented by. As a result of GPC measurement, the obtained PPE1 had a molecular weight of Mn=1,500 in terms of polystyrene. Also, the solution viscosity of PPE1 in a 20% methyl ethyl ketone solvent was 125 cPoise.

｛式中、ｌ、ｍ及びｎは、下記数平均分子量を満たすように任意に選択される数である｝
で表されるような構造を有する変性ポリフェニレンエーテル（以下、変性ＰＰＥ１という）であると確認できた。
また、ＧＰＣ測定の結果、得られた変性ＰＰＥ１のポリスチレン換算での分子量はＭｎ＝１，６００であった。また、変性ＰＰＥ１の平均末端官能基数は、上記数式（２）に従って、２．５以上であることが算出された。さらに、変性ＰＰＥ１の２０％メチルエチルケトン溶媒中での溶液粘度は１３１ｃＰｏｉｓｅであった。 Synthesis of modified polyphenylene ether 1 (modified PPE1) 80 g of toluene and 26 g of PPE1 synthesized above were mixed and heated to about 85°C. 0.55 g of dimethylaminopyridine was added to the heated mixture. When all the solids appeared to have dissolved, 4.9 g of methacrylic anhydride was slowly added to the melt. The resulting solution was maintained at 85° C. for 3 hours with continuous mixing. The solution was then cooled to room temperature to obtain a toluene solution of methacrylate-modified polyphenylene ether.
A portion of the solution was sampled, dried and then subjected to ¹ H-NMR measurement. Since the peak derived from the hydroxyl group of the polyphenylene ether had disappeared, it was determined that the reaction was progressing, and the purification operation was started. 120 g of the toluene solution of the above methacrylate-modified polyphenylene ether was added dropwise over 30 minutes into 360 g of methanol vigorously stirred with a magnetic stirrer in a 1 L beaker. The resulting precipitate was filtered under reduced pressure with a membrane filter and then dried to obtain 38 g of polymer. ¹ H-NMR measurement results of the dried polymer are shown in FIG. It was confirmed that the peak derived from the hydroxyl group of the polyphenylene ether disappeared around 4.5 ppm and the peak derived from the olefin of the methacrylic group appeared around 5.75 ppm. In addition, by GC measurement, the peaks derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid have almost disappeared, so the peak derived from the methacrylic group in NMR is the methacrylic group bonded to the end of the polyphenylene ether. It was judged. From this result, the resulting polymer has the following formula:

{Wherein, l, m and n are numbers arbitrarily selected to satisfy the following number average molecular weight}
It was confirmed to be a modified polyphenylene ether (hereinafter referred to as modified PPE1) having a structure represented by
Further, as a result of GPC measurement, the molecular weight of the obtained modified PPE1 in terms of polystyrene was Mn=1,600. In addition, the average terminal functional group number of modified PPE1 was calculated to be 2.5 or more according to the above formula (2). Furthermore, the solution viscosity of modified PPE1 in 20% methyl ethyl ketone solvent was 131 cPoise.

Material PPE used to form the resin composition and its cured product
- Modified polyphenylene ether 1 obtained above (modified PPE1)
・Terminal methacrylic group-modified PPE "product name SA9000"
(manufactured by Sabic Innovative Plastics, Mn: 2756, number of terminal functional groups: 2.0)
・ "PPE S201A" (manufactured by Asahi Kasei Corporation, high molecular weight PPE, Mn22,000)

Cross-linking agent TAIC (Nippon Kasei Co., Ltd., molecular weight: 249.7, number of unsaturated double bonds: 3)
・Polybutadiene “Product name B-1000”
(manufactured by Nippon Soda Co., Ltd., Mn: 1200, number of unsaturated double bonds: 18.4)

Organic peroxide Bis (1-tert-butylperoxy-1-methylethyl) benzene “product name Perbutyl P” (manufactured by NOF Corporation)

Thermoplastic resin Hydrogenated styrene thermoplastic resin (SEBS) “Product name Tuftec H1517”
(Made by Asahi Kasei Corporation, melt flow rate MFR according to ISO1133 under conditions of 230°C and 2.16 kgf: 3.0, Mw: about 50,000, styrene unit content: 43% by mass)
・Hydrogenated styrenic thermoplastic resin (SEBS) “Product name Tuftec N504”
(Made by Asahi Kasei Corporation, melt flow rate MFR according to ISO 1133 under conditions of 230 ° C. and 2.16 kgf: No Flow, Mw: about 200,000, styrene unit content: 32% by mass)

Flame retardant Decabromodiphenylethane “product name SAYTEX8010” (manufactured by Albemarle)

Filler ・Spherical silica (manufactured by Tatsumori Co., Ltd.)

Base material L glass cloth (manufactured by Asahi Schwebel, style: 2116)

Evaluation method 1. Number average molecular weight of PPE, weight average molecular weight of thermoplastic resin Using GPC analysis, the number average molecular weight of PPE and the weight average molecular weight of thermoplastic resin were determined by comparison with the elution time of standard polystyrene with a known molecular weight. Specifically, after preparing a measurement sample with a sample concentration of 0.2 w / vol% (solvent: chloroform), HLC-8220GPC (manufactured by Tosoh Corporation) was used as the measurement device, and the column was Shodex GPC KF-405L HQx. 3 (manufactured by Showa Denko KK), eluent: chloroform, injection volume: 20 μL, flow rate: 0.3 mL/min, column temperature: 40° C., detector: RI.

2. Varnish Viscosity 200 ml of a resin varnish (solid content: 53% by mass) prepared from each resin composition and toluene was placed in a beaker, and the viscosity was measured using a B-type rotational viscometer at 25° C., 30 rpm, and 30 seconds. . The measured viscosity was evaluated in 5 stages.
5: 50 mPa·s to 150 mPa·s
4: 150 mPa・s to 200 mPa・s
3: 200 mPa・s to 300 mPa・s
2: 300 mPa·s to 500 mPa·s
1: 500 mPa・s to 1000 mPa・s

3. Impregnability A resin varnish (solid content: 53% by mass) prepared with each resin composition and toluene is placed in a vat, and an L glass cloth (manufactured by Asahi Schwebel Co., Ltd., style: 2116) cut into 50 mm squares is placed on top of it. The impregnation of the glass cloth with the resin varnish was visually observed. Evaluation was made on a 5-point scale according to the ability of the glass cloth to be impregnated with the resin varnish.
5: When the entire glass cloth is impregnated with the resin varnish within 1 minute 4: When the entire glass cloth is impregnated with the resin varnish within 2 minutes 3: When the entire glass cloth is impregnated with the resin varnish within 3 minutes 2: When the entire glass cloth is impregnated with resin varnish within 5 minutes 1: When the impregnation is not completed even after 5 minutes

4. Dielectric constant and dielectric loss tangent of laminate (electrical properties)
The dielectric constant and dielectric loss tangent of the laminate at 10 GHz were measured by cavity resonance method. Measurement was performed using a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator CP series) manufactured by Kanto Denshi Applied Development Co., Ltd. as measurement devices. A laminate having a thickness of about 0.5 mm, which was produced by the method described below, was cut into a size of about 2 mm in width and 50 mm in length so that the warp of the glass cloth was on the long side. Next, it was placed in an oven at 105° C.±2° C. and dried for 2 hours, and then allowed to stand in an environment of 23° C. and relative humidity of 50±5% for 96±5 hours. After that, the dielectric constant and the dielectric loss tangent were measured by using the above-described measuring apparatus under an environment of 23° C. and a relative humidity of 50±5%, and evaluated on a scale of 5.
5: Dielectric constant 3.0 or more and 3.3 or less and dielectric loss tangent 0.0020 or more and 0.0024 or less 4: Dielectric constant 3.0 or more and 3.3 or less and dielectric loss tangent 0.0024 or more and 0.0026 or less 3: Dielectric constant 3.0 or more and 3.3 or less and dielectric loss tangent 0.0026 or more and 0.0030 or less 2: Dielectric constant 3.0 or more and 3.3 or less and dielectric loss tangent 0.0030 or more and 0.0035 or less 1: Dielectric constant greater than 3.3 and dielectric loss tangent greater than 0.0035

5. Glass transition temperature of laminate (heat resistance)
The dynamic viscoelasticity of the laminate was measured, and the temperature at which tan δ was maximum was determined as the glass transition temperature (Tg). A dynamic viscoelasticity device (RHEOVIBRON model DDV-01FP, manufactured by ORIENTEC) was used as a measuring device. A laminate having a thickness of about 0.3 mm prepared by the method described later is cut into a test piece having a length of about 35 mm and a width of about 5 mm so that the warp of the glass cloth is on the long side. Measurement was performed under the condition of 10 rad/s.
The Tg value was evaluated in 5 stages.
5: Over 200°C 4: Over 190°C and up to 200°C 3: Over 180°C up to 190°C 2: Over 170°C up to 180°C 1: Over 160°C up to 170°C

6. Copper foil peeling strength of laminate (peel strength N/mm)
The stress was measured when the copper foil of the copper-clad laminate was peeled off at a constant speed. A copper clad laminate using a 35 μm thick copper foil (manufactured by Furukawa Electric Co., Ltd., GTS-MP foil) produced by the method described later was cut into a size of 15 mm in width × 150 mm in length, and autograph (AG- 5000D, manufactured by Shimadzu Corporation), the average value of the load when the copper foil is peeled off at an angle of 90 ° C with respect to the removed surface at a speed of 50 mm / min is measured, and the average value of 5 measurements is and evaluated on a 5-point scale.
5:1. Over N/mm 4: Over 0.80 N/mm and up to 1.0 N/mm 3: Over 0.70 N/mm and up to 0.80 N/mm 2: Over 0.5 N/mm and up to 0.70 N/mm 1: 0. 5N/mm or less

Example 1
According to the composition and solvent shown in Table 1, a thermoplastic resin is added to 287 parts by mass of toluene, stirred and dissolved, and then the flame retardant, spherical silica, and modified PPE1 are added, and the modified PPE1 is dissolved. Stirring was continued until (the solid content concentration was 53% by mass). Next, a cross-linking agent and an organic peroxide were added to the melt and thoroughly stirred to obtain a varnish. After impregnating this varnish with an L glass cloth, it was passed through a predetermined slit to scrape off excess varnish, dried in a drying oven at 105° C. for a predetermined time, and toluene was removed to obtain a prepreg. . This prepreg was cut into a predetermined size, and the solid content of the resin composition in the prepreg was calculated by comparing the weight of the prepreg with the weight of glass cloth of the same size, and found to be 58% 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 superimposed on both sides of the prepreg, and vacuum press is performed to obtain copper clad. A laminate was obtained. In this vacuum press process, first, the pressure was 10 kg/cm ² while heating from room temperature at a temperature increase rate of 3°C/min. A pressure of 40 kg/cm ² was adopted while heating. After the temperature reached 200°C, the conditions of pressure 40 kg/cm ² and time 60 minutes were adopted while maintaining the temperature at 200°C. Next, a laminate was obtained by removing the copper foil from the copper-clad laminate by etching.

Examples 2 and 3 and Comparative Examples 1 and 2
A resin composition, a varnish and a prepreg were obtained in Example 2 and Comparative Examples 1 and 2 according to the same method as in Example 1, except that the resin composition and/or base material were changed as shown in Table 1, and evaluated. bottom.

Claims (14)

(a) the following formula (1):

{In the formula,
X is any a-valent linking group, a is a number of 2.5 or more,
Each R ⁵ is independently an optional substituent, each k is independently an integer of 1 to 4, and at least one of k R ⁵ is represented by the following formula (2):

(wherein each R ¹¹ is independently a C _1-8 alkyl group, each R ¹² is independently a C _1-8 alkylene group, each b is independently 0 or 1, and R ¹³ represents either a hydrogen atom, a C _1-8 alkyl group or a phenyl group, and the alkyl group, alkylene group and phenyl group have substituents to the extent that the conditions for C _1-8 are satisfied; good)
contains a substructure represented by
Y is each independently represented by the following formula (3):

(wherein R ²¹ is each independently a C _1-6 saturated or unsaturated hydrocarbon group, R ²² is each independently a hydrogen atom or a C _1-6 saturated or unsaturated hydrocarbon group and the saturated or unsaturated hydrocarbon group may have a substituent to the extent that the conditions for C _1-6 are satisfied)
is a divalent linking group having a structure represented by n represents the number of repetitions of Y, each independently an integer of 1 to 200,
L is any divalent linking group or single bond, and A each independently represents a substituent containing a carbon-carbon double bond and/or an epoxy bond}
A polyphenylene ether component A having a structure represented by and a number average molecular weight of 500 to 8,000;
(b) a cross-linking agent; and (c) an organic peroxide;
A resin composition comprising: The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds per molecule, the number-average molecular weight of the cross-linking agent is 4,000 or less, and the polyphenylene ether component A: the cross-linking agent The resin composition according to claim 1, wherein the weight ratio of is from 25:75 to 95:5. 3. The resin composition according to claim 1, wherein the cross-linking agent contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. The resin composition according to any one of claims 1 to 3, wherein the organic peroxide has a 1-minute half-life temperature of 155°C to 185°C. Any one of claims 1 to 4, wherein the content of the organic peroxide is 0.05 parts by mass to 5 parts by mass based on the total mass of 100 parts by mass of the polyphenylene ether component A and the cross-linking agent. The resin composition according to Item. The resin composition further contains a thermoplastic resin, and the thermoplastic resin is a block copolymer of a vinyl aromatic compound and an olefinic alkene compound, a hydrogenated product thereof, and a homopolymer of a vinyl aromatic compound. 6. Any one of claims 1 to 5, wherein the vinyl aromatic compound-derived unit content of the block copolymer or the hydrogenated block copolymer thereof is at least one selected from the group consisting of 20% by mass or more. 1. The resin composition according to claim 1. 7. The resin composition according to claim 6, wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000. The resin composition according to claim 6 or 7, wherein the content of said thermoplastic resin is 2 parts by mass to 20 parts by mass based on the total mass of 100 parts by mass of said polyphenylene ether component A and said crosslinking agent. 9. Any one of claims 1 to 8, wherein the resin composition further comprises a flame retardant, and the flame retardant is incompatible with other ingredients in the resin composition after curing of the resin composition. The resin composition according to . An electronic circuit board material comprising the resin composition according to any one of claims 1 to 9. A resin film comprising the resin composition according to any one of claims 1 to 9. A prepreg, which is a composite of a substrate and the resin composition according to any one of claims 1 to 9. The prepreg according to claim 12, wherein the substrate is glass cloth. A laminate of the resin film according to claim 11 or the cured product of the prepreg according to claim 12 or 13 and a metal foil.

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