JP2004231729A - Curable resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable resin composition excellent in heat resistance and electrical characteristics. <P>SOLUTION: A cured product is obtained by curing the resin composition comprising a combination of a bifunctional phenylene ether oligomer and a cyanic ester resin, and has a high glass transition temperature, a low dielectric constant, and a low dielectric dissipation factor, and well-balanced properties inheriting excellent properties of the polyphenylene ether skeleton and the cyanic ester resin. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

（式中、−（Ｏ−Ｘ−Ｏ）−は構造式（２）で示され、Ｒ１，Ｒ２， Ｒ７，Ｒ８は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ３，Ｒ４，Ｒ５，Ｒ６は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ａは、炭素数２０以下の直鎖状あるいは、分岐状あるいは、環状の炭化水素である。−（Ｙ−Ｏ）−は構造式（３）で定義される１種類の構造、または構造式（３）で定義される２種類以上の構造がランダムに配列したものである。Ｒ９，Ｒ１０は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ１１，Ｒ１２は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。ａ，ｂは、少なくともいずれか一方が０でない、０〜３０の整数を示す。）
【０００８】
【発明実施の形態】
以下、本発明を詳細に説明する。一般式（１）で表される化合物において、Ｒ１，Ｒ２， Ｒ７，Ｒ８は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ３，Ｒ４，Ｒ５，Ｒ６は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ａは、炭素数２０以下の直鎖状あるいは、分岐状あるいは、環状の炭化水素である。−（Ｙ−Ｏ）−は構造式（３）で定義される１種類の構造、または構造式（３）で定義される２種類以上の構造がランダムに配列したものである。Ｒ９，Ｒ１０は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ１１，Ｒ１２は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。ａ，ｂは、少なくともいずれか一方が０でない、０〜３０の整数を示す。これらのなかでも好ましくは、Ｒ１，Ｒ２， Ｒ７，Ｒ８は炭素数３以下のアルキル基、Ｒ３，Ｒ４，Ｒ５，Ｒ６は水素原子または炭素数３以下のアルキル基、Ｒ９，Ｒ１０は炭素数３以下のアルキル基、Ｒ１１，Ｒ１２は水素原子または炭素数３以下のアルキル基である。分子量は小さすぎるとフェニレンエーテル骨格の有する耐熱性、電気特性が得られず、また、大きすぎると汎用溶剤への溶解性が低下することから、好ましくは数平均分子量が５００〜３０００である。
【０００９】
一般式（１）で表される２官能性フェニレンエーテルオリゴマーの製法は、特に限定されず、いかなる方法で製造してもよい。例えば、特願２００２−０１８５０８に記載の方法で、２官能フェノール化合物と１官能フェノール化合物を銅、アミン存在下、酸化カップリングにより製造することができる。
【００１０】
本発明で使用される多官能シアン酸エステル化合物（ｂ）は下記一般式（６）で示される。
一般式 ： Ｒ−（Ｏ−ＣＮ）_ｍ…（６）
（式中のｍは２以上、通常５以下の整数であり、Ｒは芳香族性の有機基であって、上記のシアネート基は該有機基Ｒの芳香環に直接結合しているもの）
【００１１】
具体的に例示すると、１，３−または１，４−ジシアナトベンゼン、１，３，５−トリシアナトベンゼン、１，３−、１，４−、１，６−、１，８−、２，６−または２，７−ジシアナトナフタレン、１，３、６−トリシアナトナフタレン、４，４’−ジシアナトビフェニル、ビス（４−シアナトフェニル）メタン、ビス（３，５−ジメチル−４−シアナトフェニル）メタン、２，２−ビス（４−シアナトフェニル）プロパン、２，２−ビス（３，５−ジブロモ−４−シアナトフェニル）プロパン、ビス（４−シアナトフェニル）エーテル、ビス（４−シアナトフェニル）チオエーテル、ビス（４−シアナトフェニル）スルホン、トリス（４−シアナトフェニル）ホスファイト、トリス（４−シアナトフェニル）ホスフェート、およびノボラック樹脂とハロゲン化シアンとの反応により得られるシアネート類、特願２００２−０４００６３、特願２００２−０４１３２１に記載のＰＰＥ骨格を有するシアン酸エステル樹脂等である。
【００１２】
また、これらの多官能シアン酸エステル樹脂のシアネート基を三量化することによって形成されるトリアジン環を有するプレポリマーも使用できる。このプレポリマーは、上記の多官能シアン酸エステル樹脂モノマーを、例えば、鉱酸、ルイス酸などの酸、ナトリウムアルコラート、第三級アミン類などの塩基、炭酸ナトリウムなどの塩類を触媒として重合させることにより得られる。
【００１３】
これらの多官能シアン酸エステル樹脂、多官能シアン酸エステル樹脂プレポリマーは１種または２種以上混合して用いることができる。また、２官能性ポリフェニレンエーテルオリゴマーとシアン酸エステル樹脂の配合比は２官能性ポリフェニレンエーテルオリゴマーの水酸基のモル（Ａ）とシアン酸エステル樹脂のシアネート基のモル（Ｂ）のモル比（Ｂ／Ａ）が２〜１００になるように配合するのが好ましい。
【００１４】
次に、本発明の硬化性樹脂組成物は必要に応じて、硬化促進剤、エポキシ樹脂、オキセタン樹脂、重合可能な不飽和基を有する化合物を添加することも可能である。
【００１５】
多官能シアン酸エステル樹脂の硬化促進剤としては、一般に公知のものが使用できる。例えば、オクチル酸亜鉛、オクチル酸錫、ナフテン酸コバルト、ナフテン酸亜鉛、アセチルアセトン鉄などの有機金属錯体、塩化アルミニウム、塩化錫、塩化亜鉛などの金属塩、トリエチルアミン、ジメチルベンジルアミン等のアミン類が挙げられるが、これらに限定されない。これらの硬化促進剤は１種または２種以上混合して用いることができる。これらの硬化促進剤の使用量は、２官能性フェニレンエーテルオリゴマーと多官能シアン酸エステル樹脂の合計重量に対して、好ましくは、０．００１ｗｔ％〜０．５ｗｔ％であり、さらに、好ましくは、０．０１ｗｔ％〜０．２ｗｔ％である。
【００１６】
エポキシ樹脂としては、一般に公知のものが使用できる。例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、キシレンノボラック型エポキシ樹脂、トリグリシジルイソシアヌレート、脂環式エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、特願２００１−３５３１９４、特願２００２−０１８５０８に示されるＰＰＥ骨格を有するエポキシ樹脂等が挙げられる。これらのエポキシ樹脂は１種あるいは２種以上混合して用いられる。
【００１７】
オキセタン樹脂としては、一般に公知のものが使用できる。例えば、オキセタン、２−メチルオキセタン、２，２−ジメチルオキセタン、３−メチルオキセタン、３，３−ジメチルオキセタン、等のアルキルオキセタン、３−メチル−３−メトキシメチルオキセタン、３，３’−ジ（トリフルオロメチル）パーフルオキセタン、２−クロロメチルオキセタン、３，３−ビス（クロロメチル）オキセタン、ＯＸＴ−１０１（東亞合成製商品名）、ＯＸＴ−１２１（東亞合成製商品名）等が挙げられる。これらのオキセタン樹脂は１種あるいは２種以上混合して用いられる。
【００１８】
本発明の硬化性樹脂組成物にエポキシ樹脂および／またはオキセタン樹脂を使用する場合にはエポキシ樹脂硬化剤および／またはオキセタン樹脂硬化剤を使用することができる。該エポキシ樹脂硬化剤としては、一般に公知のものが使用でき、例えば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール等のイミダゾール誘導体、ジシアンジアミド、ベンジルジメチルアミン、４−メチル−Ｎ，Ｎ−ジメチルベンジルアミン等のアミン化合物、ホスフィン系はホスホニウム系のリン化合物を挙げることができる。該オキセタン樹脂硬化剤としては公知のカチオン重合開始剤が使用できる。例えば、市販のものではサンエードＳＩ−６０Ｌ、サンエードＳＩ−８０Ｌ、サンエードＳＩ−１００Ｌ（三新化学工業製）、ＣＩ−２０６４（日本曹達製）、イルガキュア２６１（チバスペシャリティーケミカル製）、アデカオプトマーＳＰ−１７０、アデカオプトマーＳＰ−１５０（旭電化製）、サイラキュアーＵＶＩ−６９９０（ＵＣＣ製）等が挙げられる。カチオン重合開始剤はエポキシ樹脂硬化剤としても使用できる。これらの硬化剤は１種あるいは２種以上組み合わせて使用される。
【００１９】
重合可能な不飽和基を有する化合物としては、一般に公知のものが使用できる。例えば、エチレン、プロピレン、スチレン等のビニル化合物、メチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の１価または多価アルコールの（メタ）アクリレート類、ビスフェノールＡ型エポキシ（メタ）アクリレート、ビスフェノールＦ型エポキシ（メタ）アクリレート、特願２００１−３８７９６８、特願２００２−０３８１５６に示されるＰＰＥ骨格を有するエポキシ（メタ）アクリレート等のエポキシ（メタ）アクリレート類、特願２００２−０５３６５３、特願２００２−０５５７６５に示されるＰＰＥ骨格を有する（メタ）アクリレート、特願２００２−２１６７２４、特願２００２−２２４９３７に示されるＰＰＥ骨格を有するビニル化合物、ベンゾシクロブテン樹脂等が挙げられる。これらの不飽和基を有する化合物は１種あるいは２種以上混合して用いられる。
【００２０】
不飽和基を有する化合物を用いる場合は必要に応じて、公知の光および／または熱重合開始剤をもちいることができる。
【００２１】
さらに本発明の硬化性樹脂組成物を製造する際には、必要に応じて、溶剤、ガラス繊維、有機基材、無機充填剤、着色顔料、消泡剤、表面調整剤、難燃剤、紫外線吸収剤、酸化防止剤、重合禁止剤、流動調整剤、熱可塑樹脂等の公知の添加剤を添加することができる。無機充填剤としては、例えば、天然シリカ、溶融シリカ、アモルファスシリカ等のシリカ類、ホワイトカーボン、チタンホワイト、アエロジル、アルミナ、タルク、天然マイカ、合成マイカ、カオリン、クレー、水酸化アルミニウム、硫酸バリウム、Ｅ−ガラス、Ａ−ガラス、Ｃ−ガラス、Ｌ−ガラス、Ｄ−ガラス、Ｓ−ガラス、ＮＥ−ガラス、Ｍ−ガラスＧ２０等が挙げられる。このようにして得られた硬化性樹脂組成物は、半導体封止材、電気絶縁材料、銅張り積層板用樹脂、レジスト、電子部品の封止用樹脂、液晶のカラーフィルター用樹脂、塗料、各種コーティング剤、接着剤、ビルドアップ積層板材料、ＦＲＰ等の各種用途に有用である。
【００２２】
本発明の硬化物は、前述の方法で得られた本発明の硬化性樹脂組成物を、公知の方法、例えば、電子線、紫外線および熱による硬化方法に従って硬化することにより得られる。
【００２３】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明は以下の実施例により特に限定されるものではない。なお、数平均分子量および重量平均分子量の測定にゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により求めた。
【００２４】
（２官能性フェニレンエーテルオリゴマー体の合成）
（合成例１）
撹拌装置、温度計、空気導入管、じゃま板のついた２Ｌの縦長反応器にＣｕＣｌ１．３ ｇ（０．０１２ ｍｏｌ）、ジ−ｎ−ブチルアミン７０．７ｇ（０．５５ ｍｏｌ）、メチルエチルケトン ４００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ８００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−（１−メチルエチリデン）ビス（２，６−ジメチルフェノール）４５．４ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール５８．６ｇ（０．４８ｍｏｌ）を２ Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２ Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂イを９８．８ｇ得た。樹脂イの数平均分子量は８４５、重量平均分子量１１０６、水酸基当量が４５１であった。
【００２５】
（合成例２）
撹拌装置、温度計、空気導入管、じゃま板のついた２Ｌの縦長反応器にＣｕＣｌ１．３ ｇ（０．０１２ ｍｏｌ）、ジ−ｎ−ブチルアミン７０．７ｇ（０．５５ ｍｏｌ）、メチルエチルケトン ４００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ８００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−シクロヘキシリデンビス（２，６−ジメチルフェノール）５１．８ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール５８．６ｇ（０．４８ｍｏｌ）を２Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２ Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂ロを１０２．６ｇ得た。樹脂ロの数平均分子量は８７７、重量平均分子量１１８３、水酸基当量が４７７であった。
【００２６】
（合成例３）
撹拌装置、温度計、空気導入管、じゃま板のついた２Ｌの縦長反応器にＣｕＣｌ１．３ ｇ（０．０１２ ｍｏｌ）、ジ−ｎ−ブチルアミン７０．７ｇ（０．５５ ｍｏｌ）、メチルエチルケトン ４００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ８００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−メチリデンビス（２，３，６−トリメチルフェノール）４５．４ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール５８．６ｇ（０．４８ｍｏｌ）を２ Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２ Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂ハを９７．４ｇ得た。樹脂ハの数平均分子量は８５２、重量平均分子量１１３３、水酸基当量が４６０であった。
【００２７】
（合成例４）
撹拌装置、温度計、空気導入管、じゃま板のついた２Ｌの縦長反応器にＣｕＣｌ１．３ ｇ（０．０１２ ｍｏｌ）、ジ−ｎ−ブチルアミン７０．７ｇ（０．５５ ｍｏｌ）、メチルエチルケトン ４００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ８００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビス（２，３，６−トリメチルフェノール）６８．８ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール５８．６ｇ（０．４８ｍｏｌ）を２ Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２ Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂ニを１１４．６ｇ得た。樹脂ニの数平均分子量は９３４、重量平均分子量１２２３、水酸基当量が４９６であった。
（合成例５）
撹拌装置、温度計、空気導入管、じゃま板のついた２Ｌの縦長反応器にＣｕＣｌ１．３ ｇ（０．０１２ ｍｏｌ）、ジ−ｎ−ブチルアミン７０．７ｇ（０．５５ ｍｏｌ）、メチルエチルケトン ４００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ８００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−メチレンビス（２，６−ジメチルフェノール）４１．０ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール５８．６ｇ（０．４８ｍｏｌ）を２ Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２ Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂ホを９４．６ｇ得た。樹脂ホの数平均分子量は８０１、重量平均分子量１０８１、水酸基当量が４５５であった。
【００２８】
（合成例６）
撹拌装置、温度計、空気導入管、じゃま板のついた５Ｌの縦長反応器にＣｕＣ２７．１ｇ（０．０２８ ｍｏｌ）、ジ−ｎ−ブチルアミン１６９．７ｇ（１．３２ ｍｏｌ）、メチルエチルケトン １０００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ１９００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−メチレンビス（２，６−ジメチルフェノール）４１．０ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール１９５．３ｇ（１．６ｍｏｌ）を２ Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂ヘを２１２．５ｇ得た。樹脂ヘの数平均分子量は１６１３、重量平均分子量２４２０、水酸基当量が８３４であった。
【００２９】
（合成例７）
撹拌装置、温度計、空気導入管、じゃま板のついた５Ｌの縦長反応器にＣｕＣ３７．９ｇ（０．０３９ｍｏｌ）、ジ−ｎ−ブチルアミン２３７．５ｇ（１．８４ ｍｏｌ）、メチルエチルケトン １３００ｇを仕込み、反応温度４０℃にて撹拌を行い、あらかじめ１７００ｇのメチルエチルケトンに溶解させた２価のフェノール４，４’−メチレンビス（２，６−ジメチルフェノール）４１．０ｇ（０．１６ｍｏｌ）と２，６−ジメチルフェノール２９２．９ｇ（２．４ｍｏｌ）を２ Ｌ／ｍｉｎの空気のバブリングを行いながら１２０分かけて滴下し、さらに滴下終了後６０分間、２Ｌ／ｍｉｎの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で３回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、上記一般式（１）で示される樹脂トを３０５ｇ得た。樹脂トの数平均分子量は２１５０、重量平均分子量３２５６、水酸基当量が１０９３であった。
【００３０】
（実施例１〜９）
合成例１〜７で得られた樹脂イ〜トとシアン酸エステル樹脂、硬化促進剤を表１の通り配合し、１５０℃で１０分攪拌し溶融させ、脱気、注型した後、２３０℃１０時間硬化させて、硬化物を得た。
【００３１】
（比較例１、２）
シアン酸エステル樹脂と硬化促進剤を表１の通り配合し、１３０℃で１０分攪拌し溶融させ、脱気、注型した後、２３０℃１０時間硬化させて、硬化物を得た。
【００３２】
【表１】

ＡｒｏｃｙＢ−１０：２，２−ビス（４−シアナトフェニル）プロパン
ＡｒｏｃｙＭ−１０：ビス（３，５−ジメチル−４−シアナトフェニル）メタン
【００３３】
実施例１〜９、比較例１〜２で得られた硬化物の特性を以下の方法により評価した。
ガラス転移温度（Ｔｇ）：動的粘弾性測定（ＤＭＡ）により求めた。振動周波数１０Ｈｚで測定を行った。
誘電率、誘電正接：空洞共振摂動法により求めた。
【００３４】
以上の物性の評価結果を表２に示す。
【表２】

【００３５】
【発明の効果】
本発明の硬化性樹脂組成物は、高いガラス転移温度を有し、低誘電率、低誘電正接である硬化物を与えることから、高機能性高分子材料として極めて有用であり、熱的、電気的に優れた材料として半導体封止材、電気絶縁材料、銅張り積層板用樹脂、レジスト、電子部品の封止用樹脂、液晶のカラーフィルター用樹脂、塗料、各種コーティング剤、接着剤、ビルドアップ積層板材料、ＦＲＰなどの幅広い用途に使用することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a curable resin composition comprising a combination of a bifunctional phenylene ether oligomer having a specific structure and a polyfunctional cyanate resin, and a cured product thereof. The curable resin composition of the present invention is capable of obtaining a polymer material having excellent heat resistance and low dielectric properties by being cured. Use in a wide range of applications, including materials, resins for copper-clad laminates, resists, resins for sealing electronic components, resins for liquid crystal color filters, paints, various coating agents, adhesives, build-up laminate materials, and FRP. Can be.
[0002]
[Prior art]
Conventionally, a cyanate resin has been used as a raw material for a functional polymer material. In recent years, with the advancement of required performance in these application fields, physical properties required as functional polymer materials have become increasingly severe. As such physical properties, for example, heat resistance, weather resistance, chemical resistance, low water absorption, high fracture toughness, low dielectric constant, low dielectric loss tangent, and the like are required.
[0003]
For example, in the field of printed wiring boards, there is a demand for a substrate material having low dielectric properties due to the problem of signal attenuation accompanying higher frequency signals. Cyanate ester resins are excellent in heat resistance and low dielectric properties among thermosetting resins, and so far, for example, a composition comprising a cyanate ester resin and an epoxy resin (for example, see Patent Document 1), bis A method using a composition comprising a maleimide, a cyanate ester resin and an epoxy resin (for example, see Patent Document 2), a method of combining a polyfunctional phenol compound and a cyanate ester resin (for example, see Patent Document 3), monofunctional A method of combining a phenol compound and a cyanate ester resin (for example, see Patent Document 4) has been proposed.
[0004]
However, the method of combining a polyfunctional phenol compound and a cyanate ester resin exemplified in Patent Document 3 is insufficient for high-frequency applications because the dielectric properties in the GHz band deteriorate. Further, although the combination of the monofunctional phenol and the cyanate ester resin of Patent Document 4 is excellent in high-frequency characteristics, the use of the monofunctional compound has a problem that the crosslink density is reduced and the heat resistance is reduced.
[0005]
[Patent Document 1] Japanese Patent Publication No. 46-41112 (pages 1-8)
[Patent Document 2] Japanese Patent Publication No. 52-31279 (pages 1-11)
[Patent Document 3] Japanese Patent Publication No. 7-47637 (pages 1-5)
[Patent Document 4] Japanese Patent No. 3261061 (pages 1 to 7)
[0006]
[Problems to be solved by the present invention]
An object of the present invention is to provide a curable resin composition which gives a cured product having excellent heat resistance and a low dielectric constant and a low dielectric loss tangent, and a cured product thereof.
[0007]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a bifunctional phenylene ether oligomer having a number-average molecular weight of 500 to 3000 and a specific structure, which inherits the excellent dielectric properties and heat resistance of the PPE skeleton, is used. The inventors have found that a cured product having excellent heat resistance and low dielectric properties can be obtained by combining and curing a functional cyanate ester resin, thereby completing the present invention. That is, the present invention relates to a curable resin composition comprising a combination of a bifunctional phenylene ether oligomer having a specific structure represented by the general formula (1) and a polyfunctional cyanate resin, and further comprising curing the composition. The present invention relates to a cured product.
Embedded image

(In the formula,-(OXO)-is represented by the structural formula (2), and R1, R2, R7, and R8 may be the same or different, and include a halogen atom or an alkyl group having 6 or less carbon atoms or R3, R4, R5, and R6 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a straight chain having 20 or less carbon atoms. -(YO)-is one type of structure defined by the structural formula (3) or two or more types defined by the structural formula (3). R9 and R10 may be the same or different and are a halogen atom or an alkyl group or a phenyl group having 6 or less carbon atoms, and R11 and R12 may be the same or different; Hydrogen atom, A halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and a and b each represent an integer of 0 to 30 in which at least one of them is not 0.)
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. In the compound represented by the general formula (1), R1, R2, R7, and R8 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R3, R4, R5 and R6 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. A is a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms. -(YO)-is one type of structure defined by Structural Formula (3) or two or more types of structures defined by Structural Formula (3) randomly arranged. R9 and R10 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R11 and R12 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. a and b represent an integer of 0 to 30, at least one of which is not 0. Of these, R1, R2, R7, and R8 are preferably an alkyl group having 3 or less carbon atoms, R3, R4, R5, and R6 are a hydrogen atom or an alkyl group having 3 or less carbon atoms, and R9 and R10 are 3 or less carbon atoms. R11 and R12 are a hydrogen atom or an alkyl group having 3 or less carbon atoms. If the molecular weight is too small, the heat resistance and electrical properties of the phenylene ether skeleton cannot be obtained, and if it is too large, the solubility in a general-purpose solvent is reduced. Therefore, the number average molecular weight is preferably 500 to 3,000.
[0009]
The method for producing the bifunctional phenylene ether oligomer represented by the general formula (1) is not particularly limited, and may be produced by any method. For example, a bifunctional phenol compound and a monofunctional phenol compound can be produced by oxidative coupling in the presence of copper and an amine by the method described in Japanese Patent Application No. 2002-018508.
[0010]
The polyfunctional cyanate compound (b) used in the present invention is represented by the following general formula (6).
General formula: R- (O-CN) _m (6)
(M in the formula is an integer of 2 or more, usually 5 or less, R is an aromatic organic group, and the above cyanate group is directly bonded to the aromatic ring of the organic group R)
[0011]
Specific examples include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, , 6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4) -Cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether , Bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and novolak Cyanates obtained by the reaction of a cyanide resin with a cyanogen halide, and cyanate ester resins having a PPE skeleton described in Japanese Patent Application Nos. 2002-040063 and 2002-041321.
[0012]
Further, a prepolymer having a triazine ring formed by trimerizing the cyanate group of these polyfunctional cyanate ester resins can also be used. This prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate resin monomer with, for example, an acid such as a mineral acid or a Lewis acid, a base such as sodium alcoholate or a tertiary amine, or a salt such as sodium carbonate as a catalyst. Is obtained by
[0013]
These polyfunctional cyanate ester resins and polyfunctional cyanate ester resin prepolymers can be used alone or in combination of two or more. The mixing ratio of the bifunctional polyphenylene ether oligomer to the cyanate ester resin is such that the molar ratio of the hydroxyl group (A) of the bifunctional polyphenylene ether oligomer to the cyanate group of the cyanate ester resin (B) is (B / A). ) Is preferably 2 to 100.
[0014]
Next, the curable resin composition of the present invention may optionally contain a curing accelerator, an epoxy resin, an oxetane resin, and a compound having a polymerizable unsaturated group.
[0015]
As a curing accelerator for the polyfunctional cyanate ester resin, generally known ones can be used. Examples thereof include organometallic complexes such as zinc octylate, tin octylate, cobalt naphthenate, zinc naphthenate, and iron acetylacetone; metal salts such as aluminum chloride, tin chloride and zinc chloride; and amines such as triethylamine and dimethylbenzylamine. But not limited to these. These curing accelerators can be used alone or in combination of two or more. The use amount of these curing accelerators is preferably 0.001 wt% to 0.5 wt% with respect to the total weight of the bifunctional phenylene ether oligomer and the polyfunctional cyanate ester resin, and more preferably, It is 0.01 wt% to 0.2 wt%.
[0016]
As the epoxy resin, a generally known epoxy resin can be used. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, xylene novolak epoxy resin, triglycidyl isocyanurate, alicyclic epoxy resin, dicyclo Pentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, epoxy resin having a PPE skeleton shown in Japanese Patent Application Nos. 2001-353194 and 2002-018508, and the like are exemplified. These epoxy resins are used alone or in combination of two or more.
[0017]
As the oxetane resin, generally known ones can be used. For example, alkyl oxetane such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3,3-dimethyl oxetane, etc., 3-methyl-3-methoxymethyl oxetane, 3,3′-di ( (Trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, OXT-101 (trade name, manufactured by Toagosei), OXT-121 (tradename, manufactured by Toagosei), and the like. . These oxetane resins are used alone or in combination of two or more.
[0018]
When an epoxy resin and / or an oxetane resin is used for the curable resin composition of the present invention, an epoxy resin curing agent and / or an oxetane resin curing agent can be used. As the epoxy resin curing agent, generally known ones can be used, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- Imidazole derivatives such as 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, dicyandiamide, benzyldimethylamine, 4-methyl-N , N-dimethylbenzylamine and the like, and phosphine-based compounds include phosphonium-based phosphorus compounds. As the oxetane resin curing agent, a known cationic polymerization initiator can be used. For example, commercially available products include Sanade SI-60L, Sanade SI-80L, Sanade SI-100L (manufactured by Sanshin Chemical Industry), CI-2064 (manufactured by Nippon Soda), Irgacure 261 (manufactured by Ciba Specialty Chemical), and Adeka Optomer. SP-170, Adeka Optomer SP-150 (manufactured by Asahi Denka), Cyracure UVI-6990 (manufactured by UCC) and the like. The cationic polymerization initiator can also be used as an epoxy resin curing agent. These curing agents are used alone or in combination of two or more.
[0019]
As the compound having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, and styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropanedi (meth) ) (Meth) acrylates of monohydric or polyhydric alcohols such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and bisphenol A type epoxy (meth) Acrylate, bisphenol F type epoxy (meth) acrylate, epoxy (meth) acrylate having a PPE skeleton described in Japanese Patent Application No. 2001-389968 and Japanese Patent Application No. 2002-038156. (Meth) acrylates having a PPE skeleton shown in Japanese Patent Application Nos. 2002-053653 and 2002-055765, and having a PPE skeleton shown in Japanese Patent Application Nos. 2002-216724 and 2002-224937. Examples include vinyl compounds and benzocyclobutene resins. These compounds having an unsaturated group are used alone or in combination of two or more.
[0020]
When a compound having an unsaturated group is used, a known light and / or thermal polymerization initiator can be used as necessary.
[0021]
Further, when producing the curable resin composition of the present invention, if necessary, a solvent, a glass fiber, an organic base material, an inorganic filler, a coloring pigment, a defoaming agent, a surface conditioner, a flame retardant, and an ultraviolet absorber Known additives such as an agent, an antioxidant, a polymerization inhibitor, a flow regulator, and a thermoplastic resin can be added. Examples of the inorganic filler include natural silica, fused silica, silicas such as amorphous silica, white carbon, titanium white, aerosil, alumina, talc, natural mica, synthetic mica, kaolin, clay, aluminum hydroxide, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, NE-glass, M-glass G20 and the like. The curable resin composition thus obtained can be used as a semiconductor sealing material, an electrical insulating material, a resin for a copper-clad laminate, a resist, a resin for sealing an electronic component, a resin for a color filter of a liquid crystal, a paint, It is useful for various uses such as coating agents, adhesives, build-up laminate materials, and FRP.
[0022]
The cured product of the present invention can be obtained by curing the curable resin composition of the present invention obtained by the above-described method according to a known method, for example, a curing method using an electron beam, ultraviolet light, and heat.
[0023]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not particularly limited to the following Examples. In addition, the number average molecular weight and the weight average molecular weight were determined by gel permeation chromatography (GPC).
[0024]
(Synthesis of bifunctional phenylene ether oligomer)
(Synthesis example 1)
1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine, and 400 g of methyl ethyl ketone were placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate. The mixture was charged and stirred at a reaction temperature of 40 ° C., and 45.4 g (0.4 g) of divalent phenol 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol) previously dissolved in 800 g of methyl ethyl ketone. 16 mol) and 58.6 g (0.48 mol) of 2,6-dimethylphenol were added dropwise over 120 minutes while bubbling air at 2 L / min. Stirring was performed while bubbling was continued. An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated by an evaporator, and further dried under reduced pressure to obtain 98.8 g of a resin A represented by the general formula (1). Resin A had a number average molecular weight of 845, a weight average molecular weight of 1106, and a hydroxyl equivalent of 451.
[0025]
(Synthesis example 2)
1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine, and 400 g of methyl ethyl ketone were placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate. The mixture was charged and stirred at a reaction temperature of 40 ° C., and 51.8 g (0.16 mol) of divalent phenol 4,4′-cyclohexylidenebis (2,6-dimethylphenol) dissolved in 800 g of methyl ethyl ketone in advance was added. 58.6 g (0.48 mol) of 2,6-dimethylphenol was added dropwise over 120 minutes while bubbling air at 2 L / min, and after completion of the dropwise addition, bubbling of air at 2 L / min was continued for 60 minutes. Stirring was performed. An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator, and further dried under reduced pressure to obtain 102.6 g of a resin resin represented by the above general formula (1). The resin B had a number average molecular weight of 877, a weight average molecular weight of 1183, and a hydroxyl equivalent of 477.
[0026]
(Synthesis example 3)
1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine, and 400 g of methyl ethyl ketone were placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate. The mixture was charged and stirred at a reaction temperature of 40 ° C., and 45.4 g (0.16 mol) of divalent phenol 4,4′-methylidenebis (2,3,6-trimethylphenol) dissolved in 800 g of methyl ethyl ketone in advance was added. , 6-dimethylphenol (58.6 g, 0.48 mol) was added dropwise over 120 minutes while bubbling air at 2 L / min, and after completion of the dropwise addition, bubbling with 2 L / min air was continued for 60 minutes. Stirring was performed. An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated by an evaporator, and further dried under reduced pressure to obtain 97.4 g of a resin C represented by the above general formula (1). Resin C had a number average molecular weight of 852, a weight average molecular weight of 1133, and a hydroxyl equivalent of 460.
[0027]
(Synthesis example 4)
1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine, and 400 g of methyl ethyl ketone were placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate. Charged and stirred at a reaction temperature of 40 ° C., and divalent phenol 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bis (2,3,6) previously dissolved in 800 g of methyl ethyl ketone. 68.8 g (0.16 mol) and 58.6 g (0.48 mol) of 2,6-dimethylphenol were added dropwise over 120 minutes while bubbling air at 2 L / min. Stirring was continued for 60 minutes while bubbling air at 2 L / min. An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator, and further dried under reduced pressure to obtain 114.6 g of a resin D represented by the general formula (1). The resin d had a number average molecular weight of 934, a weight average molecular weight of 1223, and a hydroxyl equivalent of 496.
(Synthesis example 5)
1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine, and 400 g of methyl ethyl ketone were placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate. The mixture was stirred at a reaction temperature of 40 ° C., and 41.0 g (0.16 mol) of divalent phenol 4,4′-methylenebis (2,6-dimethylphenol) dissolved in 800 g of methyl ethyl ketone and 2,6 -58.6 g (0.48 mol) of dimethylphenol was added dropwise over 120 minutes while bubbling air at 2 L / min, and after completion of the addition, stirring was continued for 60 minutes while bubbling air at 2 L / min. went. An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated by an evaporator and further dried under reduced pressure to obtain 94.6 g of a resin resin represented by the above general formula (1). The resin (e) had a number average molecular weight of 801, a weight average molecular weight of 1081, and a hydroxyl equivalent of 455.
[0028]
(Synthesis example 6)
A 2 L vertical reactor having a stirrer, a thermometer, an air inlet tube, and a baffle plate was charged with 27.1 g (0.028 mol) of CuC, 169.7 g (1.32 mol) of di-n-butylamine, and 1000 g of methyl ethyl ketone. The mixture was stirred at a reaction temperature of 40 ° C., and 41.0 g (0.16 mol) of divalent phenol 4,4′-methylenebis (2,6-dimethylphenol) previously dissolved in 1900 g of methyl ethyl ketone and 2,6- 195.3 g (1.6 mol) of dimethylphenol was added dropwise over 120 minutes while bubbling air at 2 L / min. After the completion of the addition, stirring was continued for 60 minutes while bubbling air at 2 L / min. . An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 212.5 g of a resin represented by the above general formula (1). The resin had a number average molecular weight of 16,13, a weight average molecular weight of 2420, and a hydroxyl equivalent of 834.
[0029]
(Synthesis example 7)
In a 5 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate, 37.9 g (0.039 mol) of CuC, 237.5 g (1.84 mol) of di-n-butylamine, and 1300 g of methyl ethyl ketone were charged. The mixture was stirred at a reaction temperature of 40 ° C., and 41.0 g (0.16 mol) of divalent phenol 4,4′-methylenebis (2,6-dimethylphenol) previously dissolved in 1700 g of methyl ethyl ketone and 2,6-dimethyl Phenol 292.9 g (2.4 mol) was added dropwise over 120 minutes while bubbling air at 2 L / min, and after completion of the addition, stirring was continued for 60 minutes while bubbling air at 2 L / min. An aqueous solution of disodium dihydrogen ethylenediaminetetraacetate was added thereto to stop the reaction. Thereafter, the substrate was washed three times with a 1 M aqueous hydrochloric acid solution, and then washed with ion-exchanged water. The obtained solution was concentrated by an evaporator and further dried under reduced pressure to obtain 305 g of a resin represented by the above general formula (1). The resin had a number average molecular weight of 2150, a weight average molecular weight of 3256, and a hydroxyl equivalent of 1093.
[0030]
(Examples 1 to 9)
After blending the resin (I) obtained in Synthesis Examples 1 to 7, the cyanate ester resin, and the curing accelerator as shown in Table 1, stirring at 150 ° C. for 10 minutes to melt, degassing, casting, and then 230 ° C. After curing for 10 hours, a cured product was obtained.
[0031]
(Comparative Examples 1 and 2)
The cyanate ester resin and the curing accelerator were blended as shown in Table 1, stirred at 130 ° C. for 10 minutes, melted, deaerated, cast, and then cured at 230 ° C. for 10 hours to obtain a cured product.
[0032]
[Table 1]

ArocyB-10: 2,2-bis (4-cyanatophenyl) propane ArocyM-10: bis (3,5-dimethyl-4-cyanatophenyl) methane
The properties of the cured products obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated by the following methods.
Glass transition temperature (Tg): determined by dynamic viscoelasticity measurement (DMA). The measurement was performed at a vibration frequency of 10 Hz.
Dielectric constant and dielectric tangent: determined by the cavity resonance perturbation method.
[0034]
Table 2 shows the evaluation results of the above physical properties.
[Table 2]

[0035]
【The invention's effect】
The curable resin composition of the present invention has a high glass transition temperature, provides a cured product having a low dielectric constant and a low dielectric loss tangent, and is therefore extremely useful as a high-functional polymer material, Excellent materials include semiconductor encapsulants, electrical insulating materials, resins for copper-clad laminates, resists, resins for electronic components, resins for liquid crystal color filters, paints, various coatings, adhesives, and build-up. It can be used for a wide range of applications such as laminate materials and FRP.

Claims (4)

A curable resin composition comprising a bifunctional phenylene ether oligomer having a specific structure represented by the general formula (1) and having a number average molecular weight of 500 to 3000, and a polyfunctional cyanate ester resin

(In the formula,-(OXO)-is represented by the structural formula (2), and R1, R2, R7, and R8 may be the same or different, and include a halogen atom or an alkyl group having 6 or less carbon atoms or R3, R4, R5, and R6 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a straight chain having 20 or less carbon atoms. -(YO)-is one type of structure defined by the structural formula (3) or two or more types defined by the structural formula (3). R9 and R10 may be the same or different and are a halogen atom or an alkyl group or a phenyl group having 6 or less carbon atoms, and R11 and R12 may be the same or different; Hydrogen atom, A halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and a and b each represent an integer of 0 to 30 in which at least one of them is not 0.) In the structural formula (2) of — (O—X—O) —, R1, R2, R7, and R8 are methyl groups, and — (YO) — is a structural formula (4) or a structural formula (5). Alternatively, the curable resin composition according to claim 1, wherein the curable resin composition has a structure in which the structural formulas (4) and (5) are randomly arranged.

The mole ratio (B / A) of the mole (A) of the hydroxyl group of the bifunctional phenylene ether oligomer to the mole (B) of the cyanate group of the polyfunctional cyanate ester resin is from 2 to 100. Curable resin composition as described A cured product obtained by curing the curable resin composition according to claim 1 or claim 2.