JP2020105430A - Polyphenylene ether resin composition and silane-modified copolymer - Google Patents

Polyphenylene ether resin composition and silane-modified copolymer Download PDF

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JP2020105430A
JP2020105430A JP2018246853A JP2018246853A JP2020105430A JP 2020105430 A JP2020105430 A JP 2020105430A JP 2018246853 A JP2018246853 A JP 2018246853A JP 2018246853 A JP2018246853 A JP 2018246853A JP 2020105430 A JP2020105430 A JP 2020105430A
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polyphenylene ether
silane
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JP6988786B2 (en
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宗直 廣神
Munenao Hirokami
宗直 廣神
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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Abstract

To provide a polyphenylene ether resin composition which gives a cured product having excellent dielectric characteristics and improved adhesion to a copper foil.SOLUTION: The polyphenylene ether resin composition contains a polyphenylene ether resin and a silane-modified copolymer represented by the following formula (1) (where each R1 independently represents a C1-10 alkyl group or a C6-10 aryl group; each R2 independently represents a C1-10 alkyl group or a C6-10 aryl group; e, f, g and h each independently represent a number greater than 0; and m represents an integer of 1-3; provided that the order of each repeating unit is arbitrary).SELECTED DRAWING: None

Description

本発明は、シラン変性共重合体を配合したポリフェニレンエーテル樹脂組成物に関し、さらに詳述すると、ポリブタジエン骨格およびポリスチレン骨格を有するシラン変性共重合体を配合したポリフェニレンエーテル樹脂組成物に関する。 The present invention relates to a polyphenylene ether resin composition containing a silane-modified copolymer, and more specifically to a polyphenylene ether resin composition containing a silane-modified copolymer having a polybutadiene skeleton and a polystyrene skeleton.

近年、接合、実装技術の向上とともに、電子機器に搭載される半導体デバイスの高集積化とパッケージの精緻化、プリント配線板の高密度配線化に伴い、電子機器は継続して進展しており、特に、移動体通信のような高周波数帯を利用する電子機器においては、進展が著しい。この種の電子機器を構成するプリント配線板では、多層化と微細配線化が同時進行している。情報処理の高速化に要求される信号伝達速度の高速化には材料の誘電率を低減することが有効であり、また、伝送時の損失を低減するためには誘電正接（誘電損失）の少ない材料を使用することが効果的である。 In recent years, with the improvement of bonding and mounting technology, along with the high integration of semiconductor devices mounted on electronic equipment, the sophistication of packages, and the high density wiring of printed wiring boards, electronic equipment has continued to advance, In particular, progress has been remarkable in electronic devices that utilize high frequency bands such as mobile communications. In a printed wiring board that constitutes an electronic device of this type, multilayering and fine wiring are simultaneously progressing. It is effective to reduce the dielectric constant of the material to increase the signal transmission speed required for high-speed information processing, and the dielectric loss tangent (dielectric loss) is small to reduce the loss during transmission. It is effective to use materials.

ポリフェニレンエーテル（ＰＰＥ）は、誘電率や誘電正接等の誘電特性が優れるため、基板材料として検討されている。変性させたポリフェニレンエーテルを用いた樹脂組成物も提案されている（特許文献１，２）。
ポリフェニレンエーテルを用いた樹脂組成物により成形された基板は、誘電特性に優れるものの、銅箔との密着性が不足する課題があった。 Polyphenylene ether (PPE) has been studied as a substrate material because it has excellent dielectric properties such as dielectric constant and dielectric loss tangent. Resin compositions using a modified polyphenylene ether have also been proposed (Patent Documents 1 and 2).
A substrate molded from a resin composition using polyphenylene ether has excellent dielectric properties, but has a problem of insufficient adhesion to a copper foil.

一方、ポリブタジエン骨格、ポリスチレン骨格等を有するシラン変性共重合体は、フィラー充填ゴム組成物の成分として有用であることは報告されているが（特許文献３，４）、ポリフェニレンエーテル樹脂組成物には使用されていなかった。 On the other hand, it has been reported that a silane-modified copolymer having a polybutadiene skeleton, a polystyrene skeleton, etc. is useful as a component of a filler-filled rubber composition (Patent Documents 3 and 4), but a polyphenylene ether resin composition It was never used.

特開２００４−３３９３２８号公報JP, 2004-339328, A 国際公開第２０１４／０３４１０３号International Publication No. 2014/034103 米国特許第３７５９８６９号明細書U.S. Pat. No. 3,759,869 特開２０１７−８３０１号公報JP, 2017-8301, A

本発明は、上記事情に鑑みなされたもので、誘電特性に優れ、しかも銅箔との密着性が向上した硬化物を与えるポリフェニレンエーテル樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyphenylene ether resin composition that provides a cured product having excellent dielectric properties and improved adhesion to a copper foil.

本発明者は、上記課題を解決すべく鋭意検討した結果、ポリブタジエン骨格およびポリスチレン骨格を有するシラン変性共重合体が、ポリフェニレンエーテル樹脂組成物の硬化物の銅箔との密着性を向上させることを見出し、本発明を完成した。 The present inventors have conducted extensive studies to solve the above problems, and as a result, a silane-modified copolymer having a polybutadiene skeleton and a polystyrene skeleton has been found to improve the adhesion to a copper foil of a cured product of a polyphenylene ether resin composition. Heading, the present invention was completed.

すなわち、本発明は、
１． ポリフェニレンエーテル樹脂及び下記式（１）で表されるシラン変性共重合体を含有するポリフェニレンエーテル樹脂組成物、

Figure 2020105430
（式中、Ｒ1は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ2は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｍは、１〜３の整数を表す。ただし、各繰り返し単位の順序は任意である。）
２． 式（１）において、ｆ／（ｅ＋ｆ＋ｇ＋ｈ）が０．２２以上である請求項１記載のポリフェニレンエーテル樹脂組成物、
３． 下記式（１）で表されるシラン変性共重合体、
Figure 2020105430
 （式中、Ｒ1は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ2は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｆ／（ｅ＋ｆ＋ｇ＋ｈ）が０．２２以上であり、ｍは、１〜３の整数を表す。ただし、各繰り返し単位の順序は任意である。）
を提供する。 That is, the present invention is
1. A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane-modified copolymer represented by the following formula (1):
Figure 2020105430
 (In the formula, R 1 independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 independently represents an alkyl group having 1 to 10 carbon atoms. Or represents an aryl group having 6 to 10 carbon atoms, e, f, g and h each independently represent a number larger than 0, and m represents an integer of 1 to 3. However, in each repeating unit The order is arbitrary.)
2. The polyphenylene ether resin composition according to claim 1, wherein f/(e+f+g+h) in the formula (1) is 0.22 or more.
3. A silane-modified copolymer represented by the following formula (1),
Figure 2020105430
 (In the formula, R 1 independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 independently represents an alkyl group having 1 to 10 carbon atoms. Or an aryl group having 6 to 10 carbon atoms, e, f, g and h each independently represent a number larger than 0, f/(e+f+g+h) is 0.22 or more, and m is 1 ~ Represents an integer of 3, provided that the order of each repeating unit is arbitrary.)
I will provide a.

本発明のポリフェニレンエーテル樹脂組成物は、ポリブタジエン骨格と、ポリスチレン骨格と、加水分解性シリル基とを有するシラン変性共重合体を含有しており、このシラン変性共重合体を用いることにより硬化物の銅箔との密着性を向上させることができる。 The polyphenylene ether resin composition of the present invention contains a polybutadiene skeleton, a polystyrene skeleton, and a silane-modified copolymer having a hydrolyzable silyl group. By using this silane-modified copolymer, a cured product can be obtained. The adhesion with the copper foil can be improved.

以下、本発明について具体的に説明する。
［ポリフェニレンエーテル樹脂］
本発明のポリフェニレンエーテル樹脂組成物で用いるポリフェニレンエーテル樹脂は、特に限定されないが、変性されているものが好ましく、炭素−炭素不飽和二重結合を有する置換基により末端変性されたポリフェニレンエーテル樹脂が好ましい。このようなポリフェニレンエーテル樹脂としては市販品を用いることができ、例えばＮｏｒｙｌ ＳＡ９０００（ＳＡＢＩＣイノベーティブプラスチックス社製）等がある。市販品でなくとも、末端水酸基で変性されたポリフェニレンエーテルを用いて、ビニル基、スチリル基、メタクリル基、アクリル基等を導入した変性ポリフェニレンエーテル樹脂を用いることもできる。 Hereinafter, the present invention will be specifically described.
[Polyphenylene ether resin]
The polyphenylene ether resin used in the polyphenylene ether resin composition of the present invention is not particularly limited, but a modified one is preferable, and a polyphenylene ether resin end-modified with a substituent having a carbon-carbon unsaturated double bond is preferable. .. As such a polyphenylene ether resin, a commercially available product can be used, and examples thereof include Noryl SA9000 (manufactured by SABIC Innovative Plastics). It is also possible to use a modified polyphenylene ether resin having a vinyl group, a styryl group, a methacrylic group, an acrylic group or the like introduced by using a polyphenylene ether modified with a terminal hydroxyl group, even if it is not a commercially available product.

［シラン変性共重合体］
本発明のポリフェニレンエーテル樹脂組成物に含まれるシラン変性共重合体は、式（１）で表される。なお、式（１）において、各繰り返し単位の順序は任意である。 [Silane modified copolymer]
The silane-modified copolymer contained in the polyphenylene ether resin composition of the present invention is represented by the formula (1). In addition, in Formula (1), the order of each repeating unit is arbitrary.

Figure 2020105430
Figure 2020105430

ここで、Ｒ1は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ2は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｍは、１〜３の整数を表す。 Here, R 1 independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 independently represents an alkyl group having 1 to 10 carbon atoms or Represents an aryl group having 6 to 10 carbon atoms, e, f, g and h each independently represent a number larger than 0, and m represents an integer of 1 to 3.

Ｒ1およびＲ2の炭素数１〜１０のアルキル基としては、直鎖状、環状、分枝状のいずれでもよく、その具体例としては、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｓ−ブチル、ｔ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｎ−ノニル、ｎ−デシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル基等が挙げられる。
炭素数６〜１０のアリール基の具体例としては、フェニル、α−ナフチル、β−ナフチル基等が挙げられる。 The alkyl group having 1 to 10 carbon atoms of R 1 and R 2 may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl and n. -Butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl group Etc.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, α-naphthyl and β-naphthyl groups.

これらの中でも、Ｒ1としては、直鎖のアルキル基が好ましく、メチル基、エチル基がより好ましい。
また、Ｒ2としては、直鎖のアルキル基が好ましく、メチル基、エチル基がより好ましい。 Among these, as R 1 , a linear alkyl group is preferable, and a methyl group and an ethyl group are more preferable.
R 2 is preferably a linear alkyl group, more preferably a methyl group or an ethyl group.

ｅは、好ましくは１〜５００であり、より好ましくは５〜３００である。
ｆは、好ましくは１〜５００であり、より好ましくは５〜３００である。
ｇは、好ましくは１〜５００であり、より好ましくは２〜１００である。
ｈは、好ましくは１〜５００であり、より好ましくは５〜３００である。 e is preferably 1 to 500, more preferably 5 to 300.
f is preferably 1 to 500, more preferably 5 to 300.
g is preferably 1 to 500, more preferably 2 to 100.
h is preferably 1 to 500, more preferably 5 to 300.

ｆ／（ｅ＋ｆ＋ｇ＋ｈ）としては、０．２以上であることが好ましく、０．２２以上がより好ましく、０．２５以上がさらに好ましく、０．３０以上であることが特に好ましい。上限は特に制限されないが、１以下が好ましく、より好ましくは０．８以下である。 As f/(e+f+g+h), 0.2 or more is preferable, 0.22 or more is more preferable, 0.25 or more is further preferable, and 0.30 or more is particularly preferable. The upper limit is not particularly limited, but is preferably 1 or less, more preferably 0.8 or less.

式（１）で表されるシラン変性共重合体は、下記スキームに示されるように、式（２）で表されるブタジエン−スチレンコポリマーと、式（３）で表される有機ケイ素化合物とを白金化合物含有触媒の存在下、好ましくは白金化合物含有触媒および助触媒の存在下でヒドロシリル化することで得ることができる。 The silane-modified copolymer represented by the formula (1) comprises a butadiene-styrene copolymer represented by the formula (2) and an organosilicon compound represented by the formula (3), as shown in the following scheme. It can be obtained by hydrosilylation in the presence of a platinum compound-containing catalyst, preferably in the presence of a platinum compound-containing catalyst and a cocatalyst.

Figure 2020105430
（式中、Ｒ1、Ｒ2、ｅ、ｆ、ｇ、ｈおよびｍは、上記と同じ意味を表す。）
Figure 2020105430
 (In the formula, R 1 , R 2 , e, f, g, h and m have the same meanings as described above.)

式（２）で表されるブタジエン−スチレンコポリマーは、ブタジエンとスチレンを原料モノマーとし、乳化重合や溶液重合等の公知の手法で合成することができるが、市販品として入手することもでき、例えば、Ｒｉｃｏｎ１００、Ｒｉｃｏｎ１８１、Ｒｉｃｏｎ１８４（以上、Ｃｒａｙ Ｖａｌｌｙ社製）、Ｌ−ＳＢＲ−８２０、Ｌ−ＳＢＲ−８４１（以上、クラレ社製）が上市されている。 The butadiene-styrene copolymer represented by the formula (2) can be synthesized by a known method such as emulsion polymerization or solution polymerization using butadiene and styrene as raw material monomers, or can be obtained as a commercial product, for example, , Ricon100, Ricon181, Ricon184 (above, Cray Valley company made), L-SBR-820, L-SBR-841 (all made by Kuraray company) are marketed.

一方、式（３）で表される有機ケイ素化合物としては、トリメトキシシラン、メチルジメトキシシラン、ジメチルメトキシシラン、トリエトキシシラン、メチルジエトキシシラン、ジメチルエトキシシラン等が挙げられる。 On the other hand, examples of the organosilicon compound represented by the formula (3) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

式（２）のコポリマーと式（３）の化合物の反応割合は、式（２）中の−［ＣＨ2＝ＣＨ−（ＣＨ＝ＣＨ2）］f+g−繰り返し単位１モルに対して、式（３）の化合物を１モル未満が好ましく、より好ましくは０．８モル以下である。下限は特に制限されないが、０．０１モル以上が好ましい。 The reaction ratio of the compound of the copolymer and the formula (3) in equation (2) has the formula (2) in the - with respect to the repeating units 1 mole, - [CH 2 = CH- ( CH = CH 2)] f + g The amount of the compound of the formula (3) is preferably less than 1 mol, more preferably 0.8 mol or less. The lower limit is not particularly limited, but 0.01 mol or more is preferable.

上記ヒドロシリル化反応に用いられる白金化合物含有触媒としては、特に限定されるものではなく、その具体例としては、塩化白金酸、塩化白金酸のアルコール溶液、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエンまたはキシレン溶液、テトラキストリフェニルホスフィン白金、ジクロロビストリフェニルホスフィン白金、ジクロロビスアセトニトリル白金、ジクロロビスベンゾニトリル白金、ジクロロシクロオクタジエン白金等や、白金−炭素、白金−アルミナ、白金−シリカ等の担持触媒などが挙げられる。
ヒドロシリル化の際の選択性の面から、０価の白金錯体が好ましく、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエンまたはキシレン溶液がより好ましい。
白金化合物含有触媒の使用量は特に限定されるものではないが、反応性や、生産性等の点から、式（３）で示される有機ケイ素化合物１モルに対し、含有される白金原子が１×１０-7〜１×１０-2モルとなる量が好ましく、１×１０-7〜１×１０-3モルとなる量がより好ましい。 The platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples thereof include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and platinum-1,3-divinyl-1,1. , 3,3-Tetramethyldisiloxane complex in toluene or xylene, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and platinum-carbon Supported catalysts such as platinum-alumina and platinum-silica.
From the viewpoint of selectivity at the time of hydrosilylation, a 0-valent platinum complex is preferable, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferable.
The amount of the platinum compound-containing catalyst used is not particularly limited, but from the viewpoint of reactivity, productivity, etc., 1 mol of platinum atom is contained for 1 mol of the organosilicon compound represented by the formula (3). The amount of x10 -7 to 1 x 10 -2 mol is preferable, and the amount of 1 x 10 -7 to 1 x 10 -3 mol is more preferable.

上記反応における助触媒としては、無機酸のアンモニム塩、酸アミド化合物およびカルボン酸から選ばれる１種以上を用いることが好ましい。
無機酸のアンモニウム塩の具体例としては、塩化アンモニウム、硫酸アンモニウム、アミド硫酸アンモニウム、硝酸アンモニウム、リン酸二水素一アンモニウム、リン酸水素二アンモニウム、リン酸三アンモニウム、ジ亜リン酸アンモニウム、炭酸アンモニウム、炭酸水素アンモニウム、硫化アンモニウム、ホウ酸アンモニウム、ホウフッ化アンモニウム等が挙げられるが、中でも、ｐＫａが２以上の無機酸のアンモニウム塩が好ましく、炭酸アンモニウム、炭酸水素アンモニウムがより好ましい。 As the co-catalyst in the above reaction, it is preferable to use at least one selected from an ammonium salt of an inorganic acid, an acid amide compound and a carboxylic acid.
Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium amidosulfate, ammonium nitrate, diammonium dihydrogenphosphate, diammonium hydrogenphosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, hydrogencarbonate. Examples thereof include ammonium, ammonium sulfide, ammonium borate, and ammonium borofluoride. Among them, ammonium salts of inorganic acids having a pKa of 2 or more are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.

酸アミド化合物の具体例としては、ホルムアミド、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、プロピオンアミド、アクリルアミド、マロンアミド、スクシンアミド、マレアミド、フマルアミド、ベンズアミド、フタルアミド、パルミチン酸アミド、ステアリン酸アミド等が挙げられる。 Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitic acid amide, stearic acid amide and the like. Are listed.

カルボン酸の具体例としては、ギ酸、酢酸、プロピオン酸、酪酸、メトキシ酢酸、ペンタン酸、カプロン酸、ヘプタン酸、オクタン酸、乳酸、グリコール酸等が挙げられ、これらの中でも、ギ酸、酢酸、乳酸が好ましく、酢酸がより好ましい。 Specific examples of the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid and the like, among these, formic acid, acetic acid, lactic acid Is preferred, and acetic acid is more preferred.

助触媒の使用量は特に限定されるものではないが、反応性、選択性、コスト等の観点から式（３）で示される有機ケイ素化合物１モルに対して１×１０-5〜５×１０-1モルが好ましく、１×１０-4〜１×１０-1モルがより好ましい。 The amount of the co-catalyst used is not particularly limited, but from the viewpoint of reactivity, selectivity, cost, etc., 1×10 −5 to 5×10 5 relative to 1 mol of the organosilicon compound represented by the formula (3). -1 mol is preferable, and 1 x 10 -4 to 1 x 10 -1 mol is more preferable.

なお、上記反応は無溶媒でも進行するが、溶媒を用いることもできる。
使用可能な溶媒の具体例としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；Ｎ，Ｎ−ジメチルホルムアミド等の非プロトン性極性溶媒；ジクロロメタン、クロロホルム等の塩素化炭化水素系溶媒などが挙げられ、これらの溶媒は、１種を単独で用いても、２種以上を混合して用いてもよい。 The above reaction proceeds even without solvent, but a solvent can also be used.
Specific examples of usable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, xylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane; ethyl acetate, butyl acetate, etc. Ester solvents; aprotic polar solvents such as N,N-dimethylformamide; chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or 2 You may use it in mixture of 2 or more types.

上記ヒドロシリル化反応における反応温度は特に限定されるものではなく、０℃から加熱下で行うことができるが、０〜２００℃が好ましい。
適度な反応速度を得るためには加熱下で反応させることが好ましく、このような観点から、反応温度は４０〜１１０℃がより好ましく、４０〜９０℃がより一層好ましい。
また、反応時間も特に限定されるものではなく、通常、１〜６０時間程度であるが、１〜３０時間が好ましく、１〜２０時間がより好ましい。 The reaction temperature in the above hydrosilylation reaction is not particularly limited, and it can be carried out from 0°C under heating, but 0 to 200°C is preferable.
In order to obtain an appropriate reaction rate, the reaction is preferably carried out under heating. From such a viewpoint, the reaction temperature is more preferably 40 to 110°C and even more preferably 40 to 90°C.
The reaction time is not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, more preferably 1 to 20 hours.

本発明のポリフェニレンエーテル樹脂組成物の取扱い性を考慮すると、式（１）で表されるシラン変性共重合体の数平均分子量は５００〜１００，０００であることが好ましく、１，０００〜２０，０００であることがより好ましい。
なお、数平均分子量は、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値である。 Considering the handleability of the polyphenylene ether resin composition of the present invention, the number average molecular weight of the silane-modified copolymer represented by the formula (1) is preferably 500 to 100,000, and 1,000 to 20, It is more preferably 000.
The number average molecular weight is a polystyrene conversion value by gel permeation chromatography.

本発明のポリフェニレンエーテル樹脂組成物における式（１）で表されるシラン変性共重合体の配合量は、銅箔に対する接着性の観点から、組成物中の樹脂成分（ポリフェニレンエーテル樹脂）１００質量部に対して０．００１〜２０質量部であることが好ましく、０．１〜５質量部であることがより好ましい。 The compounding amount of the silane-modified copolymer represented by the formula (1) in the polyphenylene ether resin composition of the present invention is 100 parts by mass of the resin component (polyphenylene ether resin) in the composition from the viewpoint of adhesiveness to the copper foil. It is preferably 0.001 to 20 parts by mass, and more preferably 0.1 to 5 parts by mass.

［その他の成分］
本発明のポリフェニレンエーテル樹脂組成物は、上記した成分以外の成分をさらに含んでもよい。他の成分としては、例えば、高分子量体、無機充填剤、難燃剤、添加剤、硬化剤、反応開始剤が挙げられる。 [Other ingredients]
The polyphenylene ether resin composition of the present invention may further contain components other than the above components. Other components include, for example, high molecular weight substances, inorganic fillers, flame retardants, additives, curing agents, and reaction initiators.

高分子量体としては、ポリブタジエン、式（１）以外のブタジエン−スチレン共重合体、（メタ）アクリル共重合体等を挙げることができる。
無機充填剤としては、例えば、球状シリカ、硫酸バリウム、酸化ケイ素粉、破砕シリカ、焼成タルク、チタン酸バリウム、酸化チタン、クレー、アルミナ、マイカ、ベーマイト等を挙げることができる。
硬化剤としては、例えば、トリアリルイソシアヌレート（ＴＡＩＣ）等のトリアルケニルイソシアヌレート化合物、分子中にメタクリル基を２個以上有する多官能メタクリレート化合物、分子中にアクリル基を２個以上有する多官能アクリレート化合物、及び分子中にビニルベンジル基を有するスチレン、ジビニルベンゼン等のビニルベンジル化合物等が挙げられる。 Examples of the high molecular weight material include polybutadiene, butadiene-styrene copolymers other than formula (1), (meth)acrylic copolymers, and the like.
Examples of the inorganic filler include spherical silica, barium sulfate, silicon oxide powder, crushed silica, calcined talc, barium titanate, titanium oxide, clay, alumina, mica, boehmite, and the like.
Examples of the curing agent include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), polyfunctional methacrylate compounds having two or more methacrylic groups in the molecule, and polyfunctional acrylates having two or more acrylic groups in the molecule. Examples thereof include compounds and vinylbenzyl compounds such as styrene and divinylbenzene having a vinylbenzyl group in the molecule.

［組成物の製造方法］
本発明の組成物は、常法に従い、ポリフェニレンエーテル樹脂を溶媒に溶解させた後、シラン変性共重合体およびその他の成分を混合することで製造することができる。溶媒としては、トルエン、キシレン等の芳香族系溶媒；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；テトラヒドロフラン等のエーテル系溶媒が好ましく、これらの中でも、トルエン、キシレンがより好ましい。 [Method for producing composition]
The composition of the present invention can be produced by dissolving the polyphenylene ether resin in a solvent and then mixing the silane-modified copolymer and other components according to a conventional method. As the solvent, aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran are preferable, and among these, toluene and xylene are more preferable.

以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）測定により求めたポリスチレン換算の数平均分子量である。粘度は、回転粘度計を用いて測定した２５℃における値である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The molecular weight is a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography (GPC) measurement. The viscosity is a value measured at 25° C. using a rotational viscometer.

［実施例１−１〜１−４、参考例１−５〜１−８］
［１］シラン変性共重合体の製造
［実施例１−１］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１００（上記式（２）におけるｅ＝１９、（ｆ＋ｇ）＝４４、ｈ＝１１；数平均分子量４，５００；Ｃｒａｙ Ｖａｌｌｙ社製。以下同じ。）１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として３．１×１０-4モル）、および酢酸０．２ｇ（３．１×１０-3モル）を納めた。この中に、トリメトキシシラン１２２ｇ（１．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で３時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度６００，０００ｍＰａ・ｓ、数平均分子量５，０００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝１９、ｆ＝４０、ｇ＝４、ｈ＝１１で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．５４である。これをシラン変性共重合体Ａとする。 [Examples 1-1 to 1-4, Reference examples 1-5 to 1-8]
[1] Production of silane-modified copolymer [Example 1-1]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, Ricon 100 (e=19 in the above formula (2), (f+g)=44, h=11; number average molecular weight 4,500; Cray Valley Co., Ltd., the same applies hereinafter) 1,000 g, toluene 200 g, toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3.1×10 − as platinum atom). 4 mol) and 0.2 g of acetic acid (3.1×10 −3 mol) were charged. 122 g (1.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85°C over 2 hours, and then stirred at 80°C for 3 hours.
After the completion of stirring, the solution was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 600,000 mPa·s and a number average molecular weight of 5,000.
The average molecular structure obtained from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by the formula (1), e=19, f=40, g=4, and h=11. .. f/(e+f+g+h) is 0.54. This is designated as silane-modified copolymer A.

［実施例１−２］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１００を１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として３．１×１０-4モル）、および酢酸０．２ｇ（３．１×１０-3モル）を納めた。この中に、トリメトキシシラン２４４ｇ（２．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で３時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度６５０，０００ｍＰａ・ｓ、数平均分子量５，６００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝１９、ｆ＝３６、ｇ＝８、ｈ＝１１で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．４９である。これをシラン変性共重合体Ｂとする。 [Example 1-2]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane. A toluene solution of the complex (3.1×10 −4 mol as platinum atom) and 0.2 g of acetic acid (3.1×10 −3 mol) were charged. 244 g (2.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85° C. over 2 hours, and then stirred at 80° C. for 3 hours.
After the completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 650,000 mPa·s and a number average molecular weight of 5,600.
The average molecular structure obtained from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by e=19, f=36, g=8, and h=11 in the above formula (1). .. f/(e+f+g+h) is 0.49. This is designated as silane-modified copolymer B.

［実施例１−３］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１００を１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として３．１×１０-4モル）、および酢酸０．２ｇ（３．１×１０-3モル）を納めた。この中に、トリメトキシシラン３６６ｇ（３．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で３時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度７００，０００ｍＰａ・ｓ、数平均分子量６，１００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝１９、ｆ＝３１、ｇ＝１３、ｈ＝１１で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．４２である。これをシラン変性共重合体Ｃとする。 [Example 1-3]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane. A toluene solution of the complex (3.1×10 −4 mol as platinum atom) and 0.2 g of acetic acid (3.1×10 −3 mol) were charged. After 366 g (3.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85°C over 2 hours, the mixture was stirred at 80°C for 3 hours.
After the completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 700,000 mPa·s and a number average molecular weight of 6,100.
The average structure determined from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by the formula (1), e=19, f=31, g=13, and h=11. .. f/(e+f+g+h) is 0.42. This is designated as silane-modified copolymer C.

［実施例１−４］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１００を１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として３．１×１０-4モル）、および酢酸０．２ｇ（３．１×１０-3モル）を納めた。この中に、トリメトキシシラン６１０ｇ（５．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で３時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度８００，０００ｍＰａ・ｓ、数平均分子量７，２００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝１９、ｆ＝２２、ｇ＝２２、ｈ＝１１で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．２９である。これをシラン変性共重合体Ｄとする。 [Example 1-4]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane. A toluene solution of the complex (3.1×10 −4 mol as platinum atom) and 0.2 g of acetic acid (3.1×10 −3 mol) were charged. After 610 g (5.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85°C over 2 hours, the mixture was stirred at 80°C for 3 hours.
After the completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 800,000 mPa·s and a number average molecular weight of 7,200.
The average structure obtained from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by e=19, f=22, g=22, and h=11 in the above formula (1). .. f/(e+f+g+h) is 0.29. This is designated as silane-modified copolymer D.

［参考例１−５］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１８１（上記式（２）におけるｅ＝３０、（ｆ＋ｇ）＝１３、ｈ＝９；数平均分子量３，２００；Ｃｒａｙ Ｖａｌｌｙ社製。以下同じ。）１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として０．５×１０-4モル）、および酢酸０．４ｇ（０．５×１０-2モル）を納めた。この中に、トリメトキシシラン７３ｇ（０．６モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で１時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度１２，５００ｍＰａ・ｓ、数平均分子量３，４００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝３０、ｆ＝１１、ｇ＝２、ｈ＝９で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．２１である。これをシラン変性共重合体Ｅとする。 [Reference Example 1-5]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, Ricon181 (e=30 in the above formula (2), (f+g)=13, h=9; number average molecular weight 3,200; Cray Valley Co., Ltd., same below) 1,000 g, toluene 200 g, toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.5×10 − as platinum atom). 4 mol) and 0.4 g of acetic acid (0.5×10 -2 mol) were charged. 73 g (0.6 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85°C over 2 hours, and then stirred at 80°C for 1 hour.
After the completion of stirring, the solution was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 12,500 mPa·s and a number average molecular weight of 3,400.
The average molecular structure determined from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by e=30, f=11, g=2, and h=9 in the above formula (1). .. f/(e+f+g+h) is 0.21. This is designated as silane-modified copolymer E.

［参考例１−６］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１００を１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として３．１×１０-4モル）、および酢酸０．２ｇ（３．１×１０-3モル）を納めた。この中に、トリメトキシシラン９７６ｇ（８．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で３時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度１，２００，０００ｍＰａ・ｓ、数平均分子量８，９００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝１９、ｆ＝９、ｇ＝３５、ｈ＝１１で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．１２である。シラン変性共重合体Ｆとする。 [Reference Example 1-6]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane. A toluene solution of the complex (3.1×10 −4 mol as platinum atom) and 0.2 g of acetic acid (3.1×10 −3 mol) were charged. To this, 976 g (8.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85°C over 2 hours, and then stirred at 80°C for 3 hours.
After the completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 1,200,000 mPa·s and a number average molecular weight of 8,900.
The average structure determined from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by the formula (1), e=19, f=9, g=35, and h=11. .. f/(e+f+g+h) is 0.12. The silane-modified copolymer F is used.

［参考例１−７］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１００を１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として３．１×１０-4モル）、および酢酸０．２ｇ（３．１×１０-3モル）を納めた。この中に、トリメトキシシラン８５４ｇ（７．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で３時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度１，１００，０００ｍＰａ・ｓ、数平均分子量８，３００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝１９、ｆ＝１３、ｇ＝３１、ｈ＝１１で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．１８である。シラン変性共重合体Ｇとする。 [Reference Example 1-7]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane. A toluene solution of the complex (3.1×10 −4 mol as platinum atom) and 0.2 g of acetic acid (3.1×10 −3 mol) were charged. Trimethoxysilane (854 g, 7.0 mol) was added dropwise thereto at an internal temperature of 75 to 85° C. over 2 hours, and then stirred at 80° C. for 3 hours.
After the completion of stirring, the solution was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 1,100,000 mPa·s and a number average molecular weight of 8,300.
The average structure determined from the molecular weight and 1 H-NMR spectrum of the product was a silane-modified copolymer represented by e=19, f=13, g=31, and h=11 in the above formula (1). .. f/(e+f+g+h) is 0.18. It is referred to as a silane-modified copolymer G.

［参考例１−８］
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２Ｌセパラブルフラスコに、Ｒｉｃｏｎ１８１を１，０００ｇ、トルエン２００ｇ、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金原子として０．５×１０-4モル）、および酢酸０．４ｇ（０．５×１０-2モル）を納めた。この中に、トリメトキシシラン２４４ｇ（２．０モル）を内温７５〜８５℃で２時間かけて滴下した後、８０℃で１時間撹拌した。
撹拌終了後、減圧濃縮および濾過し、粘度１４，５００ｍＰａ・ｓ、数平均分子量３，９００の黄色透明液体を得た。
生成物の分子量および1Ｈ−ＮＭＲスペクトルから求めた平均構造は、上記式（１）においてｅ＝３０、ｆ＝６、ｇ＝７、ｈ＝９で表されるシラン変性共重合体であった。ｆ／（ｅ＋ｆ＋ｇ＋ｈ）は、０．１２である。シラン変性共重合体Ｈとする。 [Reference Example 1-8]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 1,000 g of Ricon181, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane. A toluene solution of the complex (0.5×10 −4 mol as platinum atom) and 0.4 g (0.5×10 −2 mol) of acetic acid were charged. To this, 244 g (2.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85°C over 2 hours, and then stirred at 80°C for 1 hour.
After the completion of stirring, the solution was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 14,500 mPa·s and a number average molecular weight of 3,900.
The molecular weight of the product and the average structure determined from the 1 H-NMR spectrum were silane-modified copolymers represented by e=30, f=6, g=7, and h=9 in the above formula (1). .. f/(e+f+g+h) is 0.12. This is a silane-modified copolymer H.

［実施例２−１〜２−８、比較例２−１〜２−５］
［２］ポリフェニレンエーテル樹脂組成物の製造
（ポリフェニレンエーテル）
末端をメタクリル基で変性した変性ポリフェニレンエーテル（Ｎｏｒｙｌ ＳＡ９０００：ＳＡＢＩＣイノベーティブプラスチックス社製）
（高分子量体）
メタクリル骨格を有する高分子量体（ＡＲＵＦＯＮ ＵＰ−１０８０；重量平均分子量６，０００：東亜合成（株）製）
（架橋型硬化剤）
トリアリルイソシアヌレート（ＴＡＩＣ：日本化成（株）製）
（無機充填剤）
ビニルシランで表面処理されたシリカ（ＳＣ２３００−ＳＶＪ：（株）アドマテックス製）
（反応開始剤）
１，３−ビス（ｔ−ブチルパーオキシジイソプロピル）ベンゼン（パーブチルＰ：日油（株）製） [Examples 2-1 to 2-8, Comparative examples 2-1 to 2-5]
[2] Production of polyphenylene ether resin composition (polyphenylene ether)
Modified polyphenylene ether whose terminal is modified with a methacrylic group (Noryl SA9000: manufactured by SABIC Innovative Plastics)
(High molecular weight material)
Polymer having a methacryl skeleton (ARUFON UP-1080; weight average molecular weight 6,000: manufactured by Toagosei Co., Ltd.)
(Crosslinking type curing agent)
Triallyl isocyanurate (TAIC: manufactured by Nippon Kasei Co., Ltd.)
(Inorganic filler)
Silica surface-treated with vinylsilane (SC2300-SVJ: manufactured by Admatechs Co., Ltd.)
(Reaction initiator)
1,3-Bis(t-butylperoxydiisopropyl)benzene (Perbutyl P: NOF Corporation)

［調製方法］
（ワニス）
まず、変性ポリフェニレンエーテル（Ｎｏｒｙｌ ＳＡ９０００）とトルエンとを混合して、その混合液を８０℃になるまで加熱することによって溶解させて、５０質量％トルエン溶液を得た。その後、得られたトルエン溶液に、表１，表２に記載の割合（質量部）になるように、高分子量体（ＡＲＵＦＯＮ ＵＰ−１０８０）、架橋剤（ＴＡＩＣ）、シラン変性共重合体Ａ〜Ｈを添加した後、３０分間攪拌することによって、完全に溶解させた。そして、さらに、無機充填剤（ＳＣ２３００−ＳＶＪ）、反応開始剤（パーブチルＰ）を添加して、ビーズミルで分散させることによって、ワニス状の樹脂組成物を得た。 [Preparation method]
(varnish)
First, modified polyphenylene ether (Noryl SA9000) was mixed with toluene, and the mixed solution was heated to 80° C. to be dissolved to obtain a 50 mass% toluene solution. Then, in the obtained toluene solution, a high molecular weight product (ARUFON UP-1080), a cross-linking agent (TAIC), and a silane-modified copolymer A to Table 1 and Table 2 were prepared so as to have the ratios (parts by mass). After H was added, it was completely dissolved by stirring for 30 minutes. Then, an inorganic filler (SC2300-SVJ) and a reaction initiator (perbutyl P) were further added and dispersed by a bead mill to obtain a varnish resin composition.

（プリプレグ）
上記ワニスを用いてプリプレグを作製し、後の評価に用いた。
プリプレグには、織布基材として、日東紡績（株）製の♯１０７８タイプ、ＷＥＡ１０７８のガラスクロスを用いた。そして、上記の樹脂ワニスを織布基材に硬化後の厚みが６０μｍとなるように含浸させると共に、これを半硬化状態となるまで１２０℃で３分間加熱乾燥することによってプリプレグを得た。 (Prepreg)
A prepreg was produced using the above varnish and used for the subsequent evaluation.
For the prepreg, a glass cloth of #1078 type, WEA1078 manufactured by Nitto Boseki Co., Ltd. was used as a woven fabric substrate. Then, the above resin varnish was impregnated into a woven fabric substrate so that the thickness after curing was 60 μm, and this was heated and dried at 120° C. for 3 minutes until a semi-cured state was obtained to obtain a prepreg.

（積層板）
上記のプリプレグ１枚を、その両面に厚さ１２μｍの銅箔（古河電気工業（株）製ＧＴ−ＭＰ）を配置して被圧体とし、真空条件下、温度２２０℃、圧力４０ｋｇｆ／ｃｍ2の条件で９０分加熱・加圧して両面に銅箔が接着された、厚み８４μｍの評価積層板１を得た。
また、上記のプリプレグ１２枚を重ね、最上面と最下面に銅箔を配置して前記と同様の方法で加熱成形し、銅張積層板を得た後、銅箔を剥がして除去し、厚み７２０μｍの評価積層板２を得た。 (Laminate board)
A copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 μm is arranged on both surfaces of one sheet of the above prepreg to be a pressure-receiving body, and the temperature is 220° C. and the pressure is 40 kgf/cm 2 under vacuum conditions. By heating and pressurizing for 90 minutes under the conditions described above, an evaluation laminated plate 1 having a thickness of 84 μm and having a copper foil adhered to both surfaces thereof was obtained.
In addition, 12 pieces of the above prepregs are stacked, copper foils are arranged on the uppermost surface and the lowermost surface and heat-formed in the same manner as above to obtain a copper-clad laminate, and then the copper foil is peeled off and removed. An evaluation laminated plate 2 of 720 μm was obtained.

［評価方法］
上記のように調製された評価積層板１，２を、以下に示す方法により評価を行った。
（銅箔接着力）
評価積層板１において、絶縁層からの銅箔の引き剥がし強さをＪＩＳ Ｃ ６４８１：１９９６に準拠して測定した。幅１０ｍｍ、長さ１００ｍｍのパターンを形成し、引っ張り試験機により５０ｍｍ／分の速度で引き剥がし、そのときの引き剥がし強さ（ピール強度）を測定し、得られたピール強度を銅箔接着力（密着力）とした。測定単位はｋＮ／ｍである。 [Evaluation method]
The evaluation laminated plates 1 and 2 prepared as described above were evaluated by the method described below.
(Copper foil adhesion)
In the evaluation laminated plate 1, the peel strength of the copper foil from the insulating layer was measured according to JIS C 6481:1996. A pattern with a width of 10 mm and a length of 100 mm is formed, and is peeled off at a speed of 50 mm/min by a tensile tester, the peeling strength (peel strength) at that time is measured, and the obtained peel strength is the copper foil adhesive strength. (Adhesion). The unit of measurement is kN/m.

（誘電特性（比誘電率及び誘電正接））
１０ＧＨｚにおける評価基板の比誘電率及び誘電正接を、空洞共振器摂動法で測定した。評価基板には、上記の評価積層板２を用いた。具体的には、ネットワーク・アナライザ（Ｎ５２３０Ａ：アジレント・テクノロジー（株）製）を用い、１０ＧＨｚにおける評価基板の比誘電率（ＤＫ）及び誘電正接（Ｄｆ）を測定した。 (Dielectric properties (relative permittivity and loss tangent))
The relative permittivity and dielectric loss tangent of the evaluation substrate at 10 GHz were measured by the cavity resonator perturbation method. The evaluation laminate 2 was used as the evaluation substrate. Specifically, a network analyzer (N5230A: manufactured by Agilent Technologies, Inc.) was used to measure the relative permittivity (DK) and the dielectric loss tangent (Df) of the evaluation substrate at 10 GHz.

Figure 2020105430
Figure 2020105430

Figure 2020105430

＊１ 有機ケイ素化合物Ｉ：ビニルトリメトキシシラン（信越化学工業（株）製ＫＢＭ−１００３）
＊２ 有機ケイ素化合物Ｊ：３−メタクリルプロピルトリメトキシシラン（信越化学工業（株）製ＫＢＭ−５０３）
Figure 2020105430
*1 Organosilicon compound I: vinyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.)
*2 Organosilicon compound J: 3-methacrylpropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims (3)

ポリフェニレンエーテル樹脂及び下記式（１）で表されるシラン変性共重合体を含有するポリフェニレンエーテル樹脂組成物。
Figure 2020105430
 （式中、Ｒ1は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ2は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｍは、１〜３の整数を表す。ただし、各繰り返し単位の順序は任意である。） A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane-modified copolymer represented by the following formula (1).
Figure 2020105430
 (In the formula, R 1 independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 independently represents an alkyl group having 1 to 10 carbon atoms. Or represents an aryl group having 6 to 10 carbon atoms, e, f, g and h each independently represent a number larger than 0, and m represents an integer of 1 to 3. However, in each repeating unit The order is arbitrary.) 式（１）において、ｆ／（ｅ＋ｆ＋ｇ＋ｈ）が０．２２以上である請求項１記載のポリフェニレンエーテル樹脂組成物。 The polyphenylene ether resin composition according to claim 1, wherein f/(e+f+g+h) in the formula (1) is 0.22 or more. 下記式（１）で表されるシラン変性共重合体。
Figure 2020105430
 （式中、Ｒ1は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ2は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｆ／（ｅ＋ｆ＋ｇ＋ｈ）が０．２２以上であり、ｍは、１〜３の整数を表す。ただし、各繰り返し単位の順序は任意である。） A silane-modified copolymer represented by the following formula (1).
Figure 2020105430
 (In the formula, R 1 independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 independently represents an alkyl group having 1 to 10 carbon atoms. Or an aryl group having 6 to 10 carbon atoms, e, f, g and h each independently represent a number larger than 0, f/(e+f+g+h) is 0.22 or more, and m is 1 ~ Represents an integer of 3, provided that the order of each repeating unit is arbitrary.)
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