JP7328801B2 - 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 of 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, as well as low dielectric constant and low heat resistance. 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 therefore suitable as a printed wiring board material that meets the above requirements. For example, in the PPE-containing resin composition described in Patent Document 1, the average number of phenolic hydroxyl groups per PPE molecule is controlled within a specific range, or the content of a plurality of PPEs with different molecular weights is specified. This is intended to improve moldability, heat resistance, adhesiveness, and electrical properties.

WO2012/081705

Resin compositions containing PPE are required to have good resin fluidity during heat molding, etc., and cured products that can achieve excellent electrical properties, excellent heat resistance, and excellent flame retardancy. It is also required to be able to provide However, the PPE-containing resin composition described in Patent Literature 1 still has room for investigation from the viewpoint of meeting all these requirements.

Accordingly, an object of the present invention is to provide a PPE-containing resin composition having excellent electrical properties, and an electronic circuit board material, resin film, prepreg and laminate 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である｝
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；
を含む熱硬化性樹脂に対して、更に、
（ｄ）リン化合物を含む難燃剤；
を含む樹脂組成物。
［２］
（ｅ）下記式（４Ａ）；

｛式中、ＲａとＲｂはＣ_１－７のアルキル基であり、Ｍは、アルカリ金属、アルミニウム、亜鉛、鉄又はホウ素であり、ｃとｄは１～３の整数であり、ｄは、Ｍの正電荷の数であり、そしてｃは、Ｍに対応するホスフィン酸アニオンの数である｝
で表される化合物を、前記熱硬化性樹脂１００質量部に対して５質量部以上３０量部以下で含み、更に、
前記リン化合物として
（ｄ１）下記式（５Ａ）：

｛式中、ｍは３～２５の整数を表し、そしてＲ^１は、各々独立に有機基を有していてもよいアリール基である｝
で表される化合物を、前記熱硬化性樹脂１００質量部に対して５質量部以上４５質量部以下；及び／又は
（ｄ２）下記式（６Ａ）：

｛式中、Ｒ_１、Ｒ_２、及びＲ_３は、水素原子又は有機基である｝
で表される化合物を、前記熱硬化性樹脂１００質量部に対して１質量部以上３０質量部以下；
で含む、［１］に記載の樹脂組成物。
［３］
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：前記架橋剤の質量比が、２５：７５～９５：５である、［１］又は［２］に記載の樹脂組成物。
［４］
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、［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１分間半減期温度が、１５５℃～１８５℃である、［１］～［４］のいずれか１項に記載の樹脂組成物。
［６］
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、［１］～［５］のいずれか１項に記載の樹脂組成物。
［７］
前記樹脂組成物が、熱可塑性樹脂を更に含み、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、［１］～［６］のいずれか１項に記載の樹脂組成物。
［８］
前記熱可塑性樹脂の重量平均分子量が、１０，０００～３００，０００である、［７］に記載の樹脂組成物。
［９］
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、［７］又は［８］に記載の樹脂組成物。
［１０］
［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］
［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、［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、［１２］に記載のプリプレグ。
［１４］
［１１］に記載の樹脂フィルム、又は［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。 As a result of intensive research to solve the above problems, the present inventors have identified the structure and molecular weight of PPE in a resin composition containing PPE, a cross-linking agent, and an organic peroxide, and The inventors have found that the electrical properties of the cured product of the resin composition can be improved by containing a flame retardant, and have completed the present invention. That is, the present invention is as follows.
[1]
(a) the following formula (1):

{Wherein, X is an 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 is each independently 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;
Further, for thermosetting resins containing
(d) a flame retardant comprising a phosphorus compound;
A resin composition comprising:
[2]
(e) the following formula (4A);

{Wherein, Ra and Rb are C _1-7 alkyl groups, M is an alkali metal, aluminum, zinc, iron or boron, c and d are integers of 1 to 3, and d is M and c is the number of phosphinate anions corresponding to M}
contains a compound represented by 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the thermosetting resin,
As the phosphorus compound (d1) the following formula (5A):

{wherein m represents an integer of 3 to 25, and R ¹ is each independently an aryl group optionally having an organic group}
and/or (d2) the following formula (6A):

{wherein R ₁ , R ₂ and R ₃ are hydrogen atoms or organic groups}
1 part by mass or more and 30 parts by mass or less of the compound represented by 100 parts by mass of the thermosetting resin;
The resin composition according to [1], comprising:
[3]
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 [1] or [2], wherein the mass ratio of is 25:75 to 95:5.
[4]
The resin composition according to any one of [1] to [3], wherein the cross-linking agent contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.
[5]
The resin composition according to any one of [1] to [4], wherein the organic peroxide has a 1-minute half-life temperature of 155°C to 185°C.
[6]
Any of [1] to [5], 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. 1. The resin composition according to claim 1.
[7]
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. [1] to [6], at least one selected from the group consisting of: The resin composition according to any one of.
[8]
The resin composition according to [7], wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000.
[9]
The resin composition according to [7] or [8], 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. thing.
[10]
An electronic circuit board material comprising the resin composition according to any one of [1] to [9].
[11]
A resin film comprising the resin composition according to any one of [1] to [9].
[12]
A prepreg, which is a composite of a substrate and the resin composition according to any one of [1] to [9].
[13]
The prepreg according to [12], wherein the base material is glass cloth.
[14]
A laminate of the resin film according to [11] or the cured product of the prepreg according to [12] or [13] and a metal foil.

According to the present invention, excellent electrical properties (e.g., reduction of dielectric constant and dielectric loss tangent), excellent heat resistance (e.g., securing a high glass transition temperature (Tg)), and excellent flame retardancy It is possible to provide a PPE-containing resin composition capable of realizing a feasible cured product and having good resin fluidity during heat molding and the like.
Further, according to the present invention, it is possible to provide an electronic circuit board material, a resin film, a prepreg, and a laminate produced using such a PPE-containing resin composition.

1 is the result of ¹ H-NMR measurement of modified polyphenylene ether 1 (modified PPE1) obtained in Production 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.
In the present specification, unless otherwise specified, the term "~" means including the numerical values at both ends as upper and lower limits. Moreover, in this specification, the upper limit value and the lower limit value of the numerical range can be arbitrarily combined.

Resin composition The PPE-containing resin composition (hereinafter also simply referred to as "resin composition") according to the present embodiment contains PPE, a cross-linking agent, an organic peroxide, and further contains a phosphorus-based flame retardant. . If desired, the resin composition according to the present embodiment may further contain a flame retardant other than the phosphorus-based flame retardant, other additives, a thermoplastic resin, a silica filler, a solvent, and the like. The constituent elements of the resin composition according to this embodiment will be described below.

PPE
Generally, PPE have a repeating structure composed of substituted or unsubstituted phenylene ether units. As used herein, the term "polyphenylene ether (PPE)" 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 greater 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ＰＰＥ－Ａを含む。 PPE Component A (PPE-A)
The resin composition according to the present embodiment has the following formula (1) as a PPE component:

and a PPE-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 elements 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. may

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 and tert-amyl group. , 2,2-dimethylpropyl groups or structures having phenyl groups at their ends. 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.

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 and the like, more preferably a methyl group or an ethyl group, 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 a substituent as long as the conditions for C _1-6 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, a hydroxyl group, a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydroxyalkyl group. Each R ³² is independently a C _1-30 hydrocarbon group. R ³³ is each independently hydrogen, hydroxyl, C _1-30 hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, hydroxyalkyl group, vinyl group or ^isopropenyl group; At least one 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-dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl , 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl- 2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methylpentyl, 1-(2-methylpropyl)butyl, 1-(2-methylpropyl) -2-methylbutyl, 1,1-(2-methylpropyl)ethyl, 1,1-(2-methylpropyl)ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl -2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5 -dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl , 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl and the like.

Hydrocarbon groups for R 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 and the like, more preferably methyl, ethyl, n-propyl, 2 -propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2- methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl , decyl, isodecyl, undecyl, dodecyl, 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, 6-methyl-1,7- heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecyl methylene, 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, etc. is.

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

The structure represented by formula (1) can take various branched structures depending on the value of the valence a of X. For example, when a = 3 in formula (1), the following formula:
{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 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 a carbon-carbon double bond and/or an epoxy bond. R ² is hydrogen or a hydrocarbon group having a C _1-8 chain or cyclic structure. 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.

Specific examples of the hydrocarbon group for Z include structures represented by the following formulas.
In the 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.

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

The modified PPE having the structure of formula (1) in the present embodiment is produced, for example, by preparing a PPE by a redistribution reaction method using a phenylene ether polymer with a higher molecular weight and introducing a group A to the end thereof. be able to. In the case of production of PPE 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 PPE and the polyfunctional phenol compound may be adjusted according to the desired molecular weight.

Further, the method of introducing the substituent A in formula (1), for example, the functional group represented by formulas (4) to (7), to the terminal of the obtained PPE polymer is not limited, and the type of functional group Various known methods may be employed depending on the requirements. 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. The introduction of the functional group having the structure of formula (5) is a reaction to form an ester bond between a hydroxyl group at the end of the PPE polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid). Forming methods are available.

PPE-A has high curing reactivity, low dielectric properties, good fluidity and moldability, and excellent heat resistance. - It can be suitably used for the production of prepregs for 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 PPE having other structures, 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.

PPE Component B (PPE-B)
In addition to PPE-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 average It preferably contains PPE-B with a molecular weight of 8,000 or more and 50,000 or less. PPE-B is stable in the 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 inhibiting PPE-A. .

PPE-B can be distinguished from PPE-A and can be any arbitrary PPE-B as long as it satisfies the average number of phenolic hydroxyl groups per molecule of 1.2 or more and the number average molecular weight of 8,000 to 50,000. PPE is fine. 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 in combination in the resin composition, from the viewpoint of stability and heat resistance of the resin composition, the total mass of PPE-A and PPE-B is 100% by mass as a reference, The content of PPE-A is preferably 1% by mass to 99.9% by mass, and the content of PPE-B is preferably 0.1% by mass to 99% by mass, more preferably PPE-A. The content 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 The content of PPE-B is 5% 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.

PPE-A: The mass ratio of the cross-linking agent is 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 cross-linking density of the cross-linked structure. More preferably, it is 32:68 to 85:15.

Organic Peroxide Any organic peroxide capable of promoting the polymerization reaction of the resin composition containing the PPE 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-butyl Peroxy)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 the organic peroxide decomposes and the amount of active oxygen halves in 1 minute. 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 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 0.5 parts by mass, based on the total of 100 parts by mass of the PPE and the cross-linking agent. 1 part 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.

Flame retardant (1) phosphorus-based flame retardant (compound represented by formula (5A))
The resin composition of the present embodiment contains a resin (also referred to as a "thermosetting resin") containing the above PPE, a cross-linking agent, and an organic peroxide, and a phosphorus-based flame retardant containing a phosphorus compound.
By containing such a phosphorus-based flame retardant, the resin composition of the present embodiment has good resin fluidity during heat molding and the like, and has excellent electrical properties (for example, dielectric constant and dielectric loss tangent reduction ), excellent heat resistance (for example, securing a high glass transition temperature (Tg)), and excellent flame retardance can be realized.

｛式中、ｍは３～２５の整数を表し、そしてＲ^１は、各々独立に有機基を有していてもよいアリール基である｝
で表される化合物が挙げられる。この式（５Ａ）で表される化合物は、上記のＰＰＥ、架橋剤、及び有機過酸化物を含む熱硬化性樹脂と非相溶性である。つまり、式（５Ａ）で表されるリン化合物は、樹脂組成物の硬化後に、樹脂組成物中のＰＰＥ、架橋剤、及び有機過酸化物と相溶しない。ここでの「非相溶性」については以下のように定義される。すなわち、樹脂と難燃剤とを例えばトルエンに溶解又は均一混合させた後、溶媒を除去した混合物に対して、示差走査熱量測定（ＤＳＣ測定）を行い、単体のＴｇに由来する２つのピークの間の温度に単一のＴｇが観察された場合を「相溶性」、一方で単体のＴｇに由来する２つのピークが各々観察された場合を「非相溶性」、とすることができる。 Specific examples of the phosphorus compound contained in the phosphorus-based flame retardant of the present embodiment include the following formula (5A);

{wherein m represents an integer of 3 to 25, and R ¹ is each independently an aryl group optionally having an organic group}
The compound represented by is mentioned. The compound represented by this formula (5A) is incompatible with thermosetting resins containing PPE, crosslinkers, and organic peroxides described above. That is, the phosphorus compound represented by formula (5A) is incompatible with the PPE, cross-linking agent, and organic peroxide in the resin composition after the resin composition is cured. "Incompatible" here is defined as follows. That is, after dissolving or homogeneously mixing the resin and the flame retardant in, for example, toluene, the mixture obtained by removing the solvent is subjected to differential scanning calorimetry (DSC measurement), and between the two peaks derived from the Tg of the single substance When a single Tg is observed at the temperature of "compatible", on the other hand, when two peaks derived from the Tg of a single substance are observed respectively, it can be regarded as "incompatible".

Specifically, the compound represented by formula (5A) is preferably
phenoxycyclophosphazene (m=3, R ₁ =phenyl group);
cyanophenoxycyclophosphazene (m=3, R ₄ =cyanobenzyl group); and the like.

In the present embodiment, for the thermosetting resin containing the PPE, the cross-linking agent, and the organic peroxide, the compound (alkylphosphinate) represented by the formula (4A) and the compound represented by the formula (5A) It is preferred to use the compounds described above in combination in specific proportions. Although the details of its action and effect are not clear, it is speculated that by using both in combination in a specific ratio, it becomes easier to increase the delamination strength of the resin composition, and synergistically it is easier to achieve a good flame retardant effect. be done.
In addition, by using a combination of both in a specific ratio, the viscosity of the entire resin composition can be appropriately adjusted, and a resin composition having excellent moldability can be provided. A resin composition with excellent moldability is preferable from the viewpoint of ensuring excellent Tg and significantly improving the electrical properties of the substrate after molding.
Therefore, the compound represented by formula (5A) is preferably contained in an amount of 5 parts by mass or more and 45 parts by mass or less, and is contained in an amount of 7 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the thermosetting resin. more preferably 10 parts by mass or more and 30 parts by mass or less. It is preferable that the content of the compound represented by formula (5A) in the thermosetting resin is 5 parts by mass or more from the viewpoint of securing the proportion of the phosphorus compound in the resin composition. On the other hand, setting the content of the compound represented by formula (5A) in the thermosetting resin to 40 parts by mass or less makes it easier to exhibit a synergistic effect with the compound represented by formula (4A). preferable from this point of view.

｛式中、Ｒ_１、Ｒ_２、及びＲ_３は、水素原子又は有機基である｝
で表される化合物（９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド誘導体）が挙げられる。 (Compound represented by formula (6A))
Another specific example of the phosphorus compound contained in the phosphorus-based flame retardant of the present embodiment is the following formula (6A);

{wherein R ₁ , R ₂ and R ₃ are hydrogen atoms or organic groups}
and a compound represented by (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative).

In the present embodiment, for the thermosetting resin containing the PPE, the cross-linking agent, and the organic peroxide, the compound (alkylphosphinate) represented by the formula (4A) and the compound represented by the formula (6A) It is preferred to use the compounds described above in combination in specific proportions. Although the details of the action and effect are not clear, by using both in combination at a specific ratio, the melt viscosity of the resin composition can be reduced, the dispersibility of the flame retardant in the cured product is improved, and synergistic It is speculated that a good flame retardant effect can be realized in
In addition, by using a combination of both in a specific ratio, the viscosity of the entire resin composition can be appropriately adjusted, and a resin composition having excellent moldability can be provided. As described above, a resin composition with excellent moldability is preferable from the viewpoint of ensuring excellent Tg and significantly improving the electrical properties of the substrate after molding.
Therefore, the compound represented by formula (6A) is preferably contained in an amount of 1 part by mass or more and 30 parts by mass or less, and is contained in an amount of 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the thermosetting resin. more preferably 10 parts by mass or more and 20 parts by mass or less. It is preferable that the content of the compound represented by the formula (6A) in the thermosetting resin is 5 parts by mass or more from the viewpoint of securing the proportion of the phosphorus compound in the resin composition. On the other hand, setting the content of the compound represented by formula (6A) in the thermosetting resin to 40 parts by mass or less makes it easier to exhibit a synergistic effect with the compound represented by formula (4A). preferable from this point of view.

｛式中、ｎは１以上の整数であり、Ｒ_４は、フェニル基、直鎖若しくは分枝鎖のアルキ
ル基、アルケニル基、アルキニル基又は水素原子である。｝
で表される化合物である。 The compound represented by formula (6A) preferably has the following formula (7A) from the viewpoint of good electrical properties:

{In the formula, n is an integer of 1 or more, and _R4 is a phenyl group, a linear or branched alkyl group, an alkenyl group, an alkynyl group, or a hydrogen atom. }
It is a compound represented by

Specifically, the compound represented by formula (7A) is preferably
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (n=1, _R = hydrogen atom: phosphaphenanthrene);
10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (n=10, _R = phenyl group); or 10-methyl-9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide (n=10, R ₄ =methyl group);

The phosphorus compound contained in the phosphorus-based flame retardant of the present embodiment is a compound represented by formula (5A) and/or a compound represented by formula (6A). Therefore, the phosphorus-based flame retardant of the present embodiment can contain both the compound represented by the formula (5A) and the compound represented by the formula (6A), and the compound represented by the formula (5A) Only either one of the compound and the compound represented by formula (6A) can be included.
When the phosphorus-based flame retardant of the present embodiment contains both the compound represented by the formula (5A) and the compound represented by the formula (6A), the thermosetting resin 100 parts by mass, the formula (5A) The total amount of the compound represented by and the compound represented by Formula (6A) is 75 parts by mass or less, preferably 45 parts by mass or less, and more preferably 30 parts by mass or less.

｛式中、ＲａとＲｂはＣ_１－７のアルキル基であり、Ｍは、アルカリ金属、アルミニウム、亜鉛、鉄又はホウ素であり、ｃとｄは１～３の整数であり、ｄは、Ｍの正電荷の数であり、そしてｃは、Ｍに対応するホスフィン酸アニオンの数である｝
で表される化合物（アルキルホスフィン酸塩）を含むことが好ましい。 (2) Alkyl sulfonate-based flame retardant The resin composition of the present embodiment has the following formula (4A) from the viewpoint of exhibiting a synergistic effect with the phosphorus-based flame retardant.

{Wherein, Ra and Rb are C _1-7 alkyl groups, M is an alkali metal, aluminum, zinc, iron or boron, c and d are integers of 1 to 3, and d is M and c is the number of phosphinate anions corresponding to M}
It is preferable to contain a compound represented by (alkylphosphinate).

Specifically, the compound represented by formula (4A) is preferably
aluminum diethylphosphinate (Ra and Rb=ethyl group, M=aluminum, d=3, c=3); and the like.

The compound represented by formula (4A) is preferably contained in an amount of 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the thermosetting resin containing the PPE, the cross-linking agent, and the organic peroxide. . It is preferable that the content of the compound represented by the formula (4A) in the thermosetting resin is 5 parts by mass or more from the viewpoint of ensuring the proportion of the alkylphosphinate in the resin composition. On the other hand, setting the content of the compound represented by formula (4A) in the thermosetting resin to 30 parts by mass or less is preferable from the viewpoint of controlling the fluidity of the resin within an appropriate range.
Therefore, from the same viewpoint as above, the compound represented by formula (4A) is preferably contained in an amount of 7 parts by mass or more and 28 parts by mass or less with respect to 100 parts by mass of the thermosetting resin, and 10 parts by mass or more. More preferably, it is contained in an amount of 25 parts by mass or less.

A preferable ratio of the compound represented by formula (4A) to 100 parts by mass of the thermosetting resin containing the above PPE, cross-linking agent and organic peroxide may vary depending on the type of phosphorus compound.

(3) Other flame retardants The resin composition of the present embodiment includes the compound represented by formula (4A), the compound represented by formula (5A), and the compound represented by formula (6A). Flame retardants (other flame retardants) containing compounds not applicable may be included.
Other flame retardants include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromo flame retardants containing aromatic bromine compounds such as phthalimide; a flame retardant containing a phosphorus compound that does not fall under any of the compounds listed above), and the like. These flame retardants are used singly or in combination of two or more.

Thermoplastic resin The resin composition can include a thermoplastic resin. In the present embodiment, the thermoplastic resin is not necessarily essential, but the case where the resin composition contains a thermoplastic resin will be described below as an example.
When the thermoplastic resin 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 vinyl aromatic compound and an olefinic alkene compound It is preferably at least one selected from the group consisting of hydrogenated block copolymers obtained by hydrogenating 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 PPE is further improved, and the adhesion strength with the metal foil is further improved. tend to

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, the thermoplastic resin is a styrene-butadiene block copolymer, a styrene-ethylene-butadiene block copolymer, a styrene-ethylene-butylene block copolymer, a 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- selected 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) more preferably at least one selected from the group consisting of styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, and polystyrene.

The degree of hydrogenation in the hydrogenated product is not particularly limited, and a portion 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 may be 2 parts by mass to 20 parts by mass, or 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 can be 2 parts by mass to 20 parts by mass based on the total of 100 parts by mass of the PPE and the cross-linking agent, and 3 parts by mass to 19 parts by mass. can be part of

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 100 parts by mass of the total of the 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.

In addition to other flame retardants, thermoplastic resins, and silica fillers, the resin composition of the present embodiment further contains additives such as heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, and solvents. may contain. 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 may be 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 cloths, cloths, chopped mats, surfacing mats; asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; wholly aromatic polyamide fibers, wholly aromatic polyesters. 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 product 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). It can suppress variation in properties, and 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.

PPE Synthesis Reactions The following reactions were carried out under an atmosphere of inert gas. 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 it was.
2. Initiator Nyper BMT: NOF product was used as is.
3. raw material PPE
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 PPE1. 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 obtain 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)

Production example 1
Synthesis of PPE1 A 500 ml three-necked flask was equipped with a 3-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 S202A as raw material PPE, 200 g of toluene, and 12.8 g of 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane as polyfunctional phenol were added. added. 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 raw material PPE. 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 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.

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 PPE.
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 PPE 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 PPE 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 PPE around 4.5 ppm disappeared and the peak derived from the olefin of the methacrylic group appeared around 5.75 ppm. In addition, GC measurement shows that the peaks derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid have almost disappeared, so the NMR peak derived from the methacrylic group was determined to be the methacrylic group bound to the end of the PPE. did. 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 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 PPE1 obtained above

Cross-linking agent TAIC (Nippon Kasei Co., Ltd., molecular weight: 249.7, number of unsaturated double bonds: 3)

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

Flame retardant (1) Phosphorus-based flame retardant Phosphaphenanthrene (HCA)
・Phenoxycyclophosphazene (Fushimi Pharmaceutical Co., Ltd., FP110)
(2) Alkyl sulfonate-based flame retardant Aluminum diethylphosphinate (3) Other flame retardants 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. Resin Fluidity A 150 mm square prepreg impregnated with IPC style 2116 glass cloth was used as a test piece so that the resin composition had a PPE content of 60±2%. A 12 μm-thick copper foil (F2-WS foil manufactured by Furukawa Electric Co., Ltd.) is layered on both sides of two prepreg layers, and the pressure is 10 kg/cm ² while heating from room temperature at a temperature increase rate of 3 ° C./min. Vacuum pressing is performed, and when the temperature reaches 130° C., the pressure is 40 kg/cm ² while heating at a temperature increase rate of 3° C./min. cm ² and molded for 60 minutes. A laminate is obtained by removing the resin that has flowed out from the 150 mm square portion. The mass of this laminate was determined and defined as the mass (g) of the laminate. Using the mass (g) of the laminate precursor and the mass (g) of the laminate, the amount of resin flow (%) during curing of the curable resin composition was determined according to the following formula.
Cured resin flow amount (% by mass) = (mass of laminate precursor (g) - mass of laminate (g))/mass of laminate precursor (g) x 100
In the table below, when the resin flow amount is 2% by mass or more and 10% by mass or less, it is marked as "◯", and when the resin flow amount is 5% by mass or more and 10% by mass or less, it is marked as "◎", less than 2% by mass. Or when it was 10% or more, it was evaluated as "x".

3. Combustibility 18 μm thick copper foil (GTS-MP foil manufactured by Furukawa Electric Co., Ltd.) is layered on both sides of eight layers of prepreg, and heat-pressed at 200° C. and 40 kg/cm ² for 60 minutes. A copper-clad laminate having a thickness of 1.2 mm was produced. An evaluation sample of 125 mm×13 mm was cut out from the laminate obtained by removing the copper foil by etching, and evaluated by a method according to the UL-94 flame retardancy test.

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, it was evaluated by using the above measuring device under an environment of 23° C. and a relative humidity of 50±5%.

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.

Example 1
According to the composition and solvent shown in Table 1, 287 parts by mass of toluene was stirred and dissolved, then the flame retardant, spherical silica, and modified PPE1 were added, and stirring was continued until modified PPE1 was dissolved ( Solid content concentration 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 mass with the mass of glass cloth of the same size, which was 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 2-10 and Comparative Examples 1 and 2
Resin compositions, varnishes, and prepregs were obtained and evaluated in Examples 2 to 10 and Comparative Examples 1 and 2, respectively, according to the same method as in Example 1, except that the resin composition was changed as shown in Table 1. .

From the results shown in Table 1, in Examples 1 to 10, all resin fluidity was good, Tg was as high as 170 ° C. or higher, the evaluation result of electrical properties was 0.005 or less, and flame retardancy was V-0. was found to show From the above, it was confirmed that in Examples 1 to 10, laminates were obtained that fully exhibited the excellent performance of PPE.
On the other hand, in Comparative Examples 1-2 using decabromodiphenylethane (a so-called halogen-based flame retardant) instead of a specific phosphorus-based flame retardant as in Examples 1-10 as a flame retardant, good It was found that the resin fluidity was not obtained (Comparative Example 1), and the flame retardancy remained at V-1 (Comparative Example 2).
As described above, in Examples 1 to 10, compared to Comparative Examples 1 and 2, excellent electrical properties (e.g., reduction in dielectric constant and dielectric loss tangent), excellent heat resistance (e.g., excellent glass transition temperature (Tg) It was confirmed that it is possible to provide a cured product that can achieve both high flame retardancy and excellent flame retardancy, and that it is possible to provide a resin composition that has good resin fluidity during heat molding and the like.

Claims (11)

(a) the following formula (1):

{Wherein, X is an 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, and R ¹³ is , a hydrogen atom, a C _1-8 alkyl group or a phenyl group, and the alkyl group, alkylene group and phenyl group may have substituents to the extent that the conditions for C _1-8 are satisfied)
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 is each independently 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;
Further, for thermosetting resins containing
(d) a flame retardant comprising a phosphorus compound;
and
(e) the following formula (4A);

{Wherein, Ra and Rb are C _1-7 alkyl groups, M is an alkali metal, aluminum, zinc, iron or boron, c and d are integers of 1 to 3, and d is M and c is the number of phosphinate anions corresponding to M}
contains a compound represented by 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the thermosetting resin, in addition,
As the phosphorus compound (d1) the following formula (5A):

{wherein m represents an integer of 3 to 25, and R ¹ is each independently an aryl group optionally having an organic group}
and/or (d2) the following formula (6A):

{wherein R ₁ , R ₂ and R ₃ are hydrogen atoms or organic groups}
1 part by mass or more and 30 parts by mass or less of the compound represented by 100 parts by mass of the thermosetting resin;
contains in
The cross-linking agent contains at least one compound selected from the group consisting of triallyl cyanurate and triallyl isocyanurate, the number average molecular weight of the cross-linking agent is 4,000 or less, and the polyphenylene ether component A : A resin composition in which the weight ratio of the cross-linking agent is from 25:75 to 95:5. The resin composition according to claim 1, wherein the organic peroxide has a 1-minute half-life temperature of 155°C to 185°C. 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 according to claim 1 or 2. Composition. The resin composition further contains a thermoplastic resin, and the thermoplastic resin is a block copolymer of a vinyl aromatic compound and an olefin or a diolefin , a hydrogenated product thereof, and a homopolymer of a vinyl aromatic compound. 4. Any one of claims 1 to 3, wherein the vinyl aromatic compound-derived unit content of the block copolymer or the hydrogenated block copolymer is at least one selected from the group consisting of 20% by mass or more. 1. The resin composition according to claim 1. 5. The resin composition according to claim 4, wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000. The resin composition according to claim 4 or 5, wherein the content of said thermoplastic resin is 2 parts by mass to 20 parts by mass based on 100 parts by mass of the total mass of said polyphenylene ether component A and said crosslinking agent. An electronic circuit board material comprising the resin composition according to any one of claims 1 to 6. A resin film comprising the resin composition according to any one of claims 1 to 6. A prepreg, which is a composite of a substrate and the resin composition according to any one of claims 1 to 6. The prepreg according to claim 9, wherein the base material is glass cloth. A laminate of the resin film according to claim 8 or the cured product of the prepreg according to claim 9 or 10 and a metal foil.

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