JP6988786B2 - Polyphenylene ether resin composition and silane-modified copolymer - Google Patents

Polyphenylene ether resin composition and silane-modified copolymer Download PDF

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JP6988786B2
JP6988786B2 JP2018246853A JP2018246853A JP6988786B2 JP 6988786 B2 JP6988786 B2 JP 6988786B2 JP 2018246853 A JP2018246853 A JP 2018246853A JP 2018246853 A JP2018246853 A JP 2018246853A JP 6988786 B2 JP6988786 B2 JP 6988786B2
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polyphenylene ether
silane
ether resin
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JP2020105430A (en
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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
    • 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
    • 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
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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 particularly 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, along with the improvement of joining and mounting technology, the electronic equipment has been continuously progressing with the high integration of semiconductor devices mounted on the electronic equipment, the refinement of the package, and the high-density wiring of the printed wiring board. In particular, remarkable progress has been made in electronic devices that use high frequency bands such as mobile communication. In printed wiring boards that make up this type of electronic device, multi-layering and fine wiring are progressing at the same time. It is effective to reduce the dielectric constant of the material to increase the signal transmission speed required for high-speed information processing, and to reduce the loss during transmission, the dielectric loss tangent (dielectric loss) is small. It is effective to use the material.

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) is being studied as a substrate material because it has excellent dielectric properties such as dielectric constant and dielectric loss tangent. Resin compositions using modified polyphenylene ether have also been proposed (Patent Documents 1 and 2).
Although the substrate formed of the resin composition using polyphenylene ether has excellent dielectric properties, there is a problem that the adhesion to the copper foil is insufficient.

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 the polyphenylene ether resin composition has a polyphenylene ether resin composition. It was not used.

特開２００４−３３９３２８号公報Japanese Unexamined Patent Publication No. 2004-339328 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Japanese Unexamined Patent Publication No. 2017-8301

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 gives 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。 As a result of diligent studies to solve the above problems, the present inventor has found that the silane-modified copolymer having a polybutadiene skeleton and a polystyrene skeleton improves the adhesion of the cured product of the polyphenylene ether resin composition to the copper foil. Find out and complete the invention.

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 0006988786
（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 0006988786
 （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
1. 1. A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane-modified copolymer represented by the following formula (1).
Figure 0006988786
 (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms independently of each other, and R 2 represents an alkyl group having 1 to 10 carbon atoms independently of each other. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number greater than 0, and m represents an integer of 1 to 3, where each repeating unit is represented. The order is arbitrary.)
2. 2. The polyphenylene ether resin composition according to claim 1, wherein in the formula (1), f / (e + f + g + h) is 0.22 or more.
3. 3. A silane-modified copolymer represented by the following formula (1),
Figure 0006988786
 (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms independently of each other, and R 2 represents an alkyl group having 1 to 10 carbon atoms independently of each other. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and 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. However, 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 silane-modified copolymer having a polybutadiene skeleton, a polystyrene skeleton, and a hydrolyzable silyl group, and a cured product is obtained by using this silane-modified copolymer. Adhesion with 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 is preferably modified, and is preferably a polyphenylene ether resin terminally modified with a substituent having a carbon-carbon unsaturated double bond. .. As such a polyphenylene ether resin, a commercially available product can be used, and examples thereof include Noyl SA9000 (manufactured by SABIC Innovative Plastics Co., Ltd.) and the like. Even if it is not a commercially available product, a modified polyphenylene ether resin having a vinyl group, a styryl group, a methacrylic group, an acrylic group or the like introduced therein can also be used by using a polyphenylene ether modified with a terminal hydroxyl group.

［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 the formula (1), the order of each repeating unit is arbitrary.

Figure 0006988786
Figure 0006988786

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 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms independently of each other, and R 2 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 6 to 10 carbon atoms independently of each other. Represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number greater 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 groups And so on.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, α-naphthyl, β-naphthyl group and the like.

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.
Further, as R 2 , a linear alkyl group is preferable, and a methyl group and an ethyl group are more preferable.

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。 The f / (e + f + g + h) is preferably 0.2 or more, more preferably 0.22 or more, further preferably 0.25 or more, and particularly preferably 0.30 or more. The upper limit is not particularly limited, but is preferably 1 or less, and 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) is composed of 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 co-catalyst.

Figure 0006988786
（式中、Ｒ1、Ｒ2、ｅ、ｆ、ｇ、ｈおよびｍは、上記と同じ意味を表す。）
Figure 0006988786
 (In the formula, R 1 , R 2 , e, f, g, h and m have the same meanings as 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, but can also be obtained as a commercially available product, for example. , Rion100, Ricon181, Ricon184 (above, manufactured by Polymery), L-SBR-820, L-SBR-841 (above, manufactured by Claret) are on the market.

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 between the copolymer of formula (2) and the compound of formula (3) is:-[CH 2 = CH-(CH = CH 2 )] f + g -repeating unit 1 mol in the formula (2). 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 platinum chloride, an alcohol solution of platinum chloride, and platinum-1,3-divinyl-1,1. , 3,3-Tetramethyldisiloxane complex in toluene or xylene, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadien platinum, etc., platinum-carbon , Platinum-alumina, platinum-silica and other supported catalysts.
From the viewpoint of selectivity during 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 the organic silicon compound represented by the formula (3) contains 1 platinum atom. An amount of × 10 -7 to 1 × 10 −2 mol is preferable, and an amount of 1 × 10 -7 to 1 × 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 one or more 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 ammonium sulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diaphosphate, ammonium carbonate, and hydrogen carbonate. 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 hydrogencarbonate 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, fumalamide, benzamide, phthalamide, palmitate amide, stearate amide and the like. Can be mentioned.

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 include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, glycolic acid and the like, and among these, formic acid, acetic acid and lactic acid. Is preferable, and acetic acid is more preferable.

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 1 × 10 -5 to 5 × 10 per mol of the organosilicon compound represented by the formula (3) from the viewpoint of reactivity, selectivity, cost and the like. -1 mol is preferable, and 1 × 10 -4 to 1 × 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。 Although the above reaction proceeds without a solvent, a solvent can also be used.
Specific examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like. Ester-based solvents; aprotonic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon-based solvents such as dichloromethane and chloroform, and the like, even if one of these solvents is used alone, 2 A mixture of seeds or more may be used.

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 hydrosilylation reaction is not particularly limited and 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, and 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, preferably 1,000 to 20, It is more preferably 000.
The number average molecular weight is a polystyrene-equivalent value obtained 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 blending 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-mentioned components. Examples of other components include 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 polymer include polybutadiene, a butadiene-styrene copolymer other than the formula (1), a (meth) acrylic copolymer 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 a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a polyfunctional methacrylate compound having two or more methacrylic groups in the molecule, and a polyfunctional acrylate 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 a polyphenylene ether resin in a solvent according to a conventional method, and then mixing a silane-modified copolymer and other components. 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 obtained by gel permeation chromatography (GPC) measurement. The viscosity is a value at 25 ° C. measured using a rotary 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 to 5 to 1-8]
[1] Production of silane-modified copolymer [Example 1-1]
In a 2L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, Ricon100 (e = 19, (f + g) = 44, h = 11 in the above formula (2); number average molecular weight 4,500; .. Cray Vally Co. hereinafter the same) 1,000 g, toluene 200 g, a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of a toluene solution (3.1 × 10 platinum atoms - 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 the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, the mixture 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 structure obtained from the molecular weight of the product and the 1 H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 40, g = 4, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.54. This is referred to as a 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]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 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, 244 g (2.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After 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 structure obtained from the molecular weight of the product and the 1 H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 36, g = 8, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.49. This is referred to as a 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]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 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, 366 g (3.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After 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 obtained from the molecular weight of the product and the 1 H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 31, g = 13, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.42. This is referred to as a 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]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 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, 610 g (5.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, 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 of the product and the 1 H-NMR spectrum 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 referred to as a 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 2L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, Ricon181 (e = 30, (f + g) = 13, h = 9 in the above formula (2); number average molecular weight 3,200; .. Cray Vally Co. hereinafter the same) 1,000 g, toluene 200 g, a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of a toluene solution (0.5 × 10 platinum atoms - 4 mol) and 0.4 g (0.5 × 10 −2 mol) of acetic acid 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 the mixture was stirred at 80 ° C. for 1 hour.
After the stirring was completed, the mixture 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 structure obtained from the molecular weight of the product and the 1 H-NMR spectrum 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 referred to as a 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]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 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 the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, 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 obtained from the molecular weight of the product and the 1 H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 9, g = 35, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.12. Let it be a silane-modified copolymer F.

［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]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 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, 854 g (7.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, the mixture 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 obtained from the molecular weight of the product and the 1 H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 13, g = 31, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.18. It is 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]
1,000 g of Ricon181, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 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 the mixture was stirred at 80 ° C. for 1 hour.
After the stirring was completed, the mixture 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 average structure obtained from the molecular weight of the product and the 1 H-NMR spectrum was a silane-modified copolymer represented by e = 30, f = 6, g = 7, and h = 9 in the above formula (1). .. f / (e + f + g + h) is 0.12. It 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 (Noyl SA9000: manufactured by SABIC Innovative Plastics Co., Ltd.)
(High molecular weight body)
High molecular weight body having a methacryl skeleton (ARUFON UP-1080; weight average molecular weight 6,000: manufactured by Toagosei Co., Ltd.)
(Crosslink type curing agent)
Triallyl Isocyanurate (TAIC: manufactured by Nihon Kasei Corporation)
(Inorganic filler)
Silica surface-treated with vinylsilane (SC2300-SVJ: manufactured by Admatex Co., Ltd.)
(Reaction initiator)
1,3-Bis (t-butylperoxydiisopropyl) benzene (Perbutyl P: manufactured by 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) and toluene were mixed, and the mixture was dissolved by heating to 80 ° C. to obtain a 50% by mass toluene solution. Then, in the obtained toluene solution, a high molecular weight substance (ARUFON UP-1080), a cross-linking agent (TAIC), and a silane-modified copolymer A to so that the ratios (parts by mass) shown in Tables 1 and 2 are obtained. After adding H, it was completely dissolved by stirring for 30 minutes. Further, an inorganic filler (SC2300-SVJ) and a reaction initiator (perbutyl P) were added and dispersed by a bead mill to obtain a varnish-like 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 prepared using the above varnish and used for later evaluation.
For the prepreg, a glass cloth of # 1078 type, WEA1078 manufactured by Nitto Boseki Co., Ltd. was used as the woven fabric base material. Then, the woven fabric base material was impregnated with the above resin varnish so as to have a thickness of 60 μm after curing, and this was heated and dried at 120 ° C. for 3 minutes until it became a semi-cured state 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。 (Laminated board)
A 12 μm-thick copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) was placed on both sides of one of the above prepregs to form a pressure-bearing body, and under vacuum conditions, the temperature was 220 ° C. and the pressure was 40 kgf / cm 2. The evaluation laminated plate 1 having a thickness of 84 μm was obtained by heating and pressurizing for 90 minutes under the above conditions and having copper foil adhered to both sides.
Further, the above 12 prepregs are stacked, copper foils are arranged on the uppermost surface and the lowermost surface, and heat molding is performed by the same method as described above. An evaluation laminated plate 2 having a thickness 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 boards 1 and 2 prepared as described above were evaluated by the methods shown below.
(Copper foil adhesive strength)
In the evaluation laminated board 1, the peeling 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, 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 used as the copper foil adhesive force. (Adhesion strength). The measurement unit 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 dielectric loss tangent))
The relative permittivity and the dielectric loss tangent of the evaluation substrate at 10 GHz were measured by the cavity resonator perturbation method. The above-mentioned evaluation laminated board 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 0006988786
Figure 0006988786

Figure 0006988786

＊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 0006988786
* 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 0006988786
 （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 0006988786
 (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms independently of each other, and R 2 represents an alkyl group having 1 to 10 carbon atoms independently of each other. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number greater than 0, and m represents an integer of 1 to 3, where each repeating unit is represented. 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 in the formula (1), f / (e + f + g + h) is 0.22 or more. 上記式（１）で表されるシラン変性共重合体の配合量が、ポリフェニレンエーテル樹脂１００質量部に対して０．００１〜２０質量部である請求項１または２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 or 2, wherein the blending amount of the silane-modified copolymer represented by the above formula (1) is 0.001 to 20 parts by mass with respect to 100 parts by mass of the polyphenylene ether resin .
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JP6183497B2 (en) * 2016-05-23 2017-08-23 信越化学工業株式会社 Rubber composition

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