JP3615742B2 - Curable vinylbenzyl compound and method for producing the same - Google Patents

Description

【０００８】
（式中、Ｒ１、Ｒ２、Ｒ３はビニルベンジル基、水素原子、炭素数１〜５の同じでも異なっていてもよいアルキル基、アルコキシ基、チオアルコキシ基およびアリール基から選択される基を示すが、少なくとも１つはビニルベンジル基である。Ｒ４は水素原子、ハロゲン原子、炭素数１〜５の同じでも異なっていてもよいアルキル基、アルコキシ基、チオアルコキシ基、チオアリールオキシ基およびアリール基から選択される１種以上の基を示す）
【０００９】
請求項２の発明は、下記一般式で示される硬化性ビニルベンジル化合物である。
（一般式２）
【００１０】
【化７】

【００１１】
（式中、Ｒ５は炭素数２〜２０の２価の有機基を示し、Ｒ６はビニルベンジル基、水素原子、炭素数１〜５の同じでも異なっていてもよいアルキル基、アルコキシ基、チオアルコキシ基およびアリール基から選択される基を示すが、少なくとも１つはビニルベンジル基である。ａ、ｂ、ｃは０〜２０の整数を示し、Ｒ４は水素原子、ハロゲン原子、炭素数１〜５の同じでも異なっていてもよいアルキル基、アルコキシ基、チオアルコキシ基、チオアリールオキシ基およびアリール基から選択される１種以上の基を示す）
【００１２】
請求項３の発明は、下記一般式３で示されるインデン化合物の１種または２種以上、フルオレン化合物、ビニルベンジルハライドおよび炭素数２〜２０のジハロメチル化合物を、アルカリ存在下で反応させて得られる硬化性ビニルベンジル化合物である。
（一般式３）
【００１３】
【化８】

【００１４】
（式中、Ｒ４は水素原子、ハロゲン原子、炭素数１〜５の同じでも異なっていてもよいアルキル基、アルコキシ基、チオアルコキシ基、チオアリールオキシ基およびアリール基から選択される１種以上の基を示す）
【００１５】
請求項４の発明は、下記一般式３で示されるインデン化合物の１種または２種以上とビニルベンジルハライドとを、アルカリ存在下で反応させることを特徴とする請求項１記載の硬化性ビニルベンジル化合物を製造する方法である。
（一般式３）
【００１６】
【化９】

【００１７】
（式中、Ｒ４の定義は前記に同じである。）
【００１８】
請求項５の発明は、下記一般式３で示されるインデン化合物の１種または２種以上、ビニルベンジルハライドおよび炭素数２〜２０のジハロメチル化合物を、アルカリ存在下で反応させることを特徴とする請求項２記載の硬化性ビニルベンジル化合物を製造する方法である。
（一般式３）
【００１９】
【化１０】

【００２０】
（式中、Ｒ４の定義は前記に同じである。）
【００２１】
請求項６の発明は、ビニルベンジルハライドが、ｍ−ビニルベンジルクロライドおよび／またはｐ−ビニルベンジルクロライドである請求項４または５に記載の製造方法である。
【００２２】
請求項７の発明は、ビニルベンジルハライドのハロメチル基と炭素数２〜２０のジハロメチル化合物のハロメチル基との当量比を、前者：後者として０．９：０．１〜０．１：０．９となるように調整して反応に供する請求項５または６に記載の製造方法である。
【００２３】
請求項８の発明は、反応が、アルカリ存在下で、かつ非プロトン性極性溶媒中および／または相間移動触媒の存在下で行われる請求項４ないし７のいずれか１項に記載の製造方法である。
【００２４】
請求項９の発明は、請求項１ないし３のいずれか１項に記載の硬化性ビニルベンジル化合物に、これと共重合可能な化合物を配合してなる硬化性樹脂組成物である。
【００２５】
請求項１０の発明は、請求項１ないし３のいずれか１項に記載の硬化性ビニルベンジル化合物自体を硬化させて得られた硬化樹脂である。
【００２６】
請求項１１の発明は、請求項９に記載の硬化性樹脂組成物を硬化させて得られた硬化樹脂である。
【００２７】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
本発明の前記一般式１で示される硬化性ビニルベンジル化合物は、前記一般式３で示されるインデン化合物の１種または２種以上とビニルベンジルハライドとを、アルカリ存在下で反応させることにより得ることができる。
また本発明の前記一般式２で示される硬化性ビニルベンジル化合物は、前記一般式３で示されるインデン化合物の１種または２種以上、ビニルベンジルハライドおよび炭素数２〜２０のジハロメチル化合物を、アルカリ存在下で反応させることにより得ることができる。なお本発明でいうジハロメチル化合物とは、分子中に−ＣＨ_２Ｘ（式中、Ｘはハロゲン原子を表す）基を２つ有する化合物である。
さらに本発明の硬化性ビニルベンジル化合物は、インデン化合物の１種または２種以上、フルオレン化合物、ビニルベンジルハライドおよび炭素数２〜２０のジハロメチル化合物を、アルカリ存在下で反応させて得られる硬化性ビニルベンジル化合物であることができる。
【００２８】
本発明におけるビニルベンジル化反応は、前記材料をアルカリ存在下、有機溶媒または水溶液中、好ましくは非プロトン性極性溶媒中および／または相間移動触媒の存在下で行うことができる。なおビニルベンジル化反応は、例えば、Ｌ．Ｊ．ＭａｔｈｉａｓらのＪ．Ｐｏｌｙｍ．Ｓｃｉ．， Ｐａｒｔ Ｂ； ３６， ２８６９ （１９９８）、Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．， Ｐａｒｔ Ａ； ３５， ５８７ （１９９７）あるいはＣ．Ｊ．ＫｅｌｌｙらのＪ．Ｃｈｅｍ．Ｒｅｓ．（Ｓ）， ４４６ （１９９７）に記載されている。
【００２９】
本発明に用いられるインデン化合物としては、インデン、またはその芳香環部分がハロゲン原子、炭素数１〜５のアルキル基、アルコキシ基、チオアルコキシ基、アリール基で置換されたインデン化合物が挙げられ、これらは単独でも２種以上を混合して用いてもよい。なお、該置換されたインデン化合物は、例えばインデンの芳香環部を臭素等によりハロゲン化し、さらにその部分に所望の基を導入することにより簡単に合成することができる。
【００３０】
本発明に用いられるフルオレン化合物としては、下記一般式４で示される化合物が好ましい。
【００３１】
【化１１】

【００３２】
（式中、Ｒは水素原子、ハロゲン原子、炭素数１〜５の同じでも異なっていてもよいアルキル基、アルコキシ基、チオアルコキシ基、チオアリールオキシ基およびアリール基から選択される１種以上の基を示す）
【００３３】
フルオレン化合物を用いる場合、フルオレン化合物とインデン化合物の当量比は、前者：後者として０．９：０．１〜０．１：０．９となるように調整して反応に供するのがよい。フルオレン化合物の当量比を大きくすると直線状の化合物になりやすく、インデン化合物の当量比を大きくすると枝分かれの多い化合物となりやすい。
【００３４】
本発明に用いられるビニルベンジルハライドとしては、ｍ−ビニルベンジルクロライド、ｐ−ビニルベンジルクロライド、ｍ−ビニルベンジルブロマイド、ｐ−ビニルベンジルブロマイドが挙げられ、これらは単独でも２種以上を混合して用いてもよい。中でも好ましくはｍ−ビニルベンジルクロライド、ｐ−ビニルベンジルクロライドである。
【００３５】
ジハロメチル基を含む炭素数２〜２０の有機化合物としては、例えば、１，２−ジクロロエタン、１，２−ジブロモエタン、１，３−ジクロロプロパン、１，３−ジブロモプロパン、１，４−ジクロロブタン、１，４−ジブロモブタン等のアルキレンジハライド、ｏ−キシリレンジクロライド、ｏ−キシリレンジブロマイド、ｍ−キシリレンジクロライド、ｍ−キシリレンジブロマイド、ｐ−キシリレンジクロライド、ｐ−キシリレンジブロマイド、４，４’−ビス（クロロメチル）ビフェニル、４，４’−ビス（クロロメチル）ジフェニルエーテル、４，４’−ビス（クロロメチル）ジフェニルスルフィド、２，６−ビス（ブロモメチル）ナフタレン、１，８−ビス（ブロモメチル）ナフタレン、１，４−ビス（クロロメチル）ナフタレン等のジハロメチル化合物が挙げられ、これらは分子内環化反応が起こらぬ範囲でそれぞれ単独でも２種類以上を混合して用いてもよい。
【００３６】
ビニルベンジルハライドのハロメチル基と炭素数２〜２０のジハロメチル化合物のハロメチル基との当量比は、ジハロメチル化合物によるゲル化が起こらない範囲で選択できるが、前者：後者として０．９：０．１〜０．１：０．９となるように調整して反応に供するのがよい。ビニルベンジルハライドの当量比が０．１未満であると硬化性が悪くなり、耐熱性等の硬化物の諸物性が低下してしまう。
【００３７】
本発明に用いられるアルカリとしては、アルカリ金属あるいはアルカリ土類金属のアルコキサイド、水素化物、水酸化物、例えばナトリウムメトキサイド、ナトリウムエトキサイド、水素化ナトリウム、水素化カリウム、水酸化ナトリウム、水酸化カリウム等が挙げられ、反応系を非水系とするか、含水系とするかでアルカリ種を選択すればよい。
【００３８】
アルカリの使用割合は、原料のハロメチル基１当量に対して１．１〜３．０当量がよい。当量が１．１未満であると、反応速度が著しく遅くなったり、反応が完全に進行せずに原料が残ってしまい硬化物性に好ましくない影響を与える、また３当量を超えて以上用いても残存アルカリの除去に多量の洗浄水等を使用するため、経済的でない。
【００３９】
反応溶媒としてはジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、Ｎ−メチルピロリドン、ジオキサン、アセトニトリル、テトラヒドロフラン、エチレングリコールジメチルエーテル、１，３−ジメトキシプロパン、１，２−ジメトキシプロパン、テトラメチレンスルホン、ヘキサメチルホスホアミド、メチルエチルケトン、メチルイソブチルケトン、アセトン、シクロヘキサン、メチルシクロヘキサン、トルエン、キシレン等およびこれらの混合物が挙げられ、これらの中から原料種や反応条件に応じて反応系が均一になるような溶媒種を選択すればよい。中でも非プロトン性極性溶媒が好ましい。
【００４０】
本発明においては相間移動触媒を併用するのが好ましく、その例としては、各種オニウム塩、例えば、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムハイドロゲンサルフェート、ベンジルトリメチルアンモニウムクロライド、トリカプリルメチルアンモニウムクロライド等の四級アンモニウム化合物、テトラ−ｎ−ブチルホスホニウムブロマイド、ベンジルトリフェニルホスホニウムクロライド、テトラフェニルホスホニウムクロライド、テトラフェニルホスホニウムブロマイド等の四級ホスホニウム化合物、ベンジルテトラメチレンスルホニウムブロマイド等の三級スルホニウム化合物およびこれらの混合物が挙げられる。
【００４１】
これらの相間移動触媒の使用量は触媒種、あるいは反応温度により触媒効果が異なるために一概に規定できないが、一般的には原料のハロメチル基１当量に対して０．０１〜０．５当量程度使用すれば十分である。
【００４２】
反応温度および反応時間は、使用する原料化合物の種類、反応条件によって異なるために一概に規定できないが、それぞれ３０〜１００℃で０．５〜２０時間であればよい。１００℃を超える反応温度では、熱重合等の好ましくない反応を併発することがあることから好ましくない。また３０℃未満でも反応は進行するが、長時間を要することから経済的でない。
【００４３】
本発明は高重合性の不飽和ハライドであるビニルベンジルハライドを使用することから、必要に応じて反応系に重合防止剤を添加してもよく、例えば、ｔ−ブチルカテコール、２，４−ジ−ｔ−ブチルフェノール、２−ｔ−ブチルフェノール、２−ｔ−ブチル−４−ニトロフェノール、２，４−ジニトロフェノール、ハイドロキノン、メチルハイドロキノン、ハイドノキノンモノメチルエーテル、ｔ−ブチルハイドロキノン、レゾルシン、ピロガロール、フェノチアジン、銅塩等が挙げられる。これらの熱重合防止剤の使用量は、熱重合防止剤の種類によって効果が異なるため、一概に規定できないが、硬化性ビニルベンジル化合物に対して数ｐｐｍ〜２０００ｐｐｍで十分である。
【００４４】
本発明によれば、成形性の改善等を図るために、硬化性ビニルベンジル化合物に、本発明の効果を損なわない範囲においてこれと共重合可能な化合物を配合し、硬化性樹脂組成物を調製することができる。この化合物としては、ポリマー、オリゴマーおよび／またはモノマーを挙げることができ、その具体的な例としては、ビニルエステル樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、マレイミド樹脂、ポリフェノールのポリシアナート樹脂、エポキシ樹脂等のポリマー、ビニルベンジルエーテル樹脂等の重合性不飽和基を有するオリゴマー、トリアリルイソシアヌレート、トリアリルシアヌレート等のモノマーおよびプレポリマー等、さらにはフルオレンのビニルベンジル化合物等が挙げられる。さらにスチレン、ビニルトルエン、ジビニルベンゼン、ビニルベンジルエーテル化合物等の単量体や、各種公知の単官能あるいは多官能（メタ）アクリル酸誘導体化合物を用いることもできる。
【００４５】
また前記共重合可能な化合物の使用量は、共重合可能な化合物の種類、硬化性ビニルベンジル化合物との相溶性、硬化物の用途等によっても異なるため、一概に規定できないが、硬化性ビニルベンジル化合物１００重量部に対して、０〜３００重量部、好ましくは０〜２００重量部である。３００重量部を超える添加量では、硬化性ビニルベンジル化合物からの分離・滲出等が起こり易くなるために好ましくない。
【００４６】
本発明の硬化樹脂は、硬化性ビニルベンジル化合物自体、あるいは前記硬化性樹脂組成物を硬化させて得られる。硬化は、熱、光、電子線などの公知の方法を採用することができる。また硬化剤を使用して硬化反応を促進したりすることも有用である。
【００４７】
硬化剤を使用する場合は、例えば、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ｔ−ブチルクミルパーオキサイド、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルパーベンゾエート等を用途に応じて使用することができる。
【００４８】
その使用量は、硬化性ビニルベンジル化合物または硬化性樹脂組成物中の不飽和基の種類、濃度、使用する硬化剤の種類、半減期温度、必要とする安定性等によって異なるが、概ね硬化性ビニルベンジル化合物または硬化性樹脂組成物１００重量部に対して０〜１０重量部である。
【００４９】
この他、ナフテン酸マンガン、ナフテン酸鉛、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸亜鉛、ジメチルアニリン、フェニルモルフォリン等の公知の硬化促進剤を使用することもできる。
【００５０】
硬化温度は、重合性不飽和基の種類、硬化剤の種類と使用量等によって異なるため、一概に規定できないが、２０〜２５０℃、好ましくは５０〜２５０℃である。硬化温度が２０℃未満では、硬化が不十分となる場合があり、好ましくない。
【００５１】
また硬化条件の調整のために、ハイドロキノン、ベンゾキノン、銅塩等の公知の硬化遅延剤を配合してもよい。
【００５２】
その他、本発明の硬化性ビニルベンジル化合物および／または硬化性樹脂組成物は、必要に応じてニーダー、ブレンダー、ロール等を用いて着色剤、充填剤や強化繊維を配合し、成形材料や複合材料とすることもできる。充填剤としては、シリカ、アルミナ、ジルコニア、二酸化チタン、水酸化マグネシウム、水酸化アルミニウム、炭酸カルシウム等を本発明の効果が損なわれぬ範囲で添加することができる。
【００５３】
なお、前記の本発明の硬化性ビニルベンジル化合物または硬化性樹脂組成物を所望の形状に成形することにより、高周波用基板を製造することもできる。このような高周波用基板は、１００ＭＨｚ以上、特に１ＧＨｚ以上の高周波領域での使用に適する。このような高周波領域において、誘電正接は０．００２〜０．０１程度を維持することができる。
【００５４】
また、前記の硬化性ビニルベンジル化合物または硬化性樹脂組成物を繊維材料に含浸し、プリプレグを得ることができる。
このようなプリプレグの作成に用いられる繊維材料としてはガラス繊維、炭素繊維、芳香族ポリアミド繊維、炭化珪素繊維、アルミナ繊維など公知の繊維材料を用いることができるが、好ましくは低誘電性（低誘電率、低誘電正接）を有するガラス繊維からなるガラスクロスを使用することが好ましい。繊維材料の含有量は強度や成形性等の観点からプリプレグに対して３０〜７０重量％であることが好ましい。
硬化性ビニルベンジル化合物または硬化性樹脂組成物を繊維材料に含浸させる方法としては、公知の溶剤法あるいは無溶剤法のどちらの方法も用いることができる。溶剤法に用いる溶剤としては、プリプレグ中の残存溶剤をできるだけ少なくし、耐熱性の低下やクラック、ボイドの発生を回避するために比較的低沸点の溶剤、例えば、アセトン、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剤、ベンゼン、トルエン等の芳香族炭化水素系溶剤等を用いることができる。
このような方法で硬化性ビニルベンジル化合物または硬化性樹脂組成物が繊維材料に含浸したものを必要に応じて８０〜１３０℃で１０分〜１８０分乾燥および熱処理を施すことによってプリプレグを得ることができる。
【００５５】
得られたプリプレグは、これを単独で、または積層して加熱、加圧に施すことにより、高周波用基板を得ることができる。すなわち、所定の厚みのプリプレグ単独、あるいは所定の厚みとなるようにプリプレグを積層し、熱プレス等の公知の方法にて加熱加圧成形を行うことにより高周波用基板を得ることができる。成形条件は８０〜２５０℃、好ましくは１００〜２００℃、５〜１００ｋｇ／ｃｍ^２の圧力、０．５〜１０時間が例示され、必要に応じて段階的に昇温することも効果的である。
【００５６】
また、前記のプリプレグを単独で、または積層し、さらに金属箔を重ねて加熱、加圧に施すことにより、金属張り高周波用基板を製造することができる。すなわち、所定の厚みのプリプレグ単独、あるいは所定の厚みとなるようにプリプレグを積層し、その積層体の両面に金属箔を重ね、前記の加熱加圧成形を行うことにより金属張り高周波用基板を得ることができる。
金属箔としては、銅、金、銀、アルミニウム等が挙げられるが、銅が好ましい。また必要に応じて電解箔や圧延箔を使用することができる。
【００５７】
また、上述のような銅箔等の金属箔上に前記硬化性ビニルベンジル化合物または硬化性樹脂組成物あるいはその溶液をドクターブレードコート法等により塗工し、８０〜１３０℃で１０分〜１８０分乾燥および熱処理を施すことによって両者が一体化した樹脂付き金属箔を得ることも可能で、これを用いて高周波用基板としてもよい。また樹脂付き金属箔をコア材に重ねて加熱加圧成形することにより多層積層基板としてもよい。
【００５８】
また、導電層上に前記の硬化性ビニルベンジル化合物または硬化性樹脂組成物を塗工し重合・硬化させ、硬化物の上にさらに導電層を設けることにより多層積層基板を製造することができる。
このような多層積層基板は、例えば導電層として厚さ１８μｍの銅箔を用い、その上に硬化性ビニルベンジル化合物または硬化性樹脂組成物を厚さ２０〜２００μｍ好ましくは５０〜１００μｍの絶縁層として塗布し、熱硬化させ、その上にさらに導電層を形成する、いわゆるビルドアップ法により作製することができる。
【００５９】
【実施例】
以下に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。なお特記しない限り、例中の部は重量部を意味する。なお実施例で行われた測定の方法を以下に示す。
熱重量分析：ＳＩＩ社製ＴＧＡ装置を用い、窒素気流下、昇温速度１０℃／分で測定した。
誘電特性：ＨＰ社製ベクトルネットワークアナライザＨＰ８７５３Ｅを用い、１．５ｍｍ×１．５ｍｍ×７５ｍｍの角柱状試験片を用いて空洞共振器摂動法で５ＧＨｚの誘電率および誘電正接を測定した。
^１Ｈ−核磁気共鳴スペクトル（^１Ｈ−ＮＭＲ）：テトラメチルシランを内部標準物質にして、日本電子社製ＪＮＭ−ＬＡ３００を用いて測定した。
赤外線吸収スペクトル（ＩＲ）：日本電子社製フーリエ変換赤外分光光度計ＪＩＲ−ＲＦＸ３００２ＦＴ−ＩＲを用いて測定した。
高速液体クロマトグラフィー（ＨＰＬＣ）：昭和電工社製Ｓｈｏｄｅｘ Ｒ１−５１（カラムＫＦ−８０１、ＫＦ−８０２）を用い、溶出液テトラヒドロフラン、溶出速度１ｍｌ／分で測定した。
吸水率：１．５ｍｍ×４０ｍｍ×４０ｍｍの試験片を２５℃で２４時間、水に浸漬し、乾燥時の重量（Ｗ１）と吸水後の重量（Ｗ２）から、計算式［（Ｗ２−Ｗ１）／Ｗ１］×１００より算出した。
【００６０】
（実施例１）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロート、窒素吹き込み口を備えたフラスコ中を窒素置換し、そこにインデン３４．９ｇ（０．３モル）、トルエン２００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド８．７２ｇ（０．０２７モル）、フェノチアジン１．７９ｇ（０．００９モル）、５０重量％ＮａＯＨ水溶液１４４．０ｇ（ＮａＯＨ、１．８モル）を仕込み、攪拌しながら５０℃まで昇温して均一な溶液にした。濃青緑色の溶液にセイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）１５０．８ｇ（純度９１％、０．９モル）を１５分かけて滴下し、その後５０〜５２℃で１０時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の粘ちょう液体をメタノールで洗浄した後に真空乾燥することにより、本発明の硬化性ビニルベンジル化合物（主に、一般式１のＲ１、Ｒ２、Ｒ３はビニルベンジル基、Ｒ４は水素原子に相当する化合物からなる）を得た。これを化合物１とする。なお、化合物１の確認は^１Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、ＨＰＬＣから行った。化合物１は２３℃でほとんど流動性のない高粘性液体であった。図１に^１Ｈ−ＮＭＲスペクトルを、図２にＩＲスペクトルを示す。
化合物１をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で２時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
【００６１】
（実施例２）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロート、窒素吹き込み口を備えたフラスコ中を窒素置換し、そこにインデン４６．５ｇ（０．４モル）、トルエン２００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド７．７５ｇ（０．０２４モル）、フェノチアジン０．０８ｇ（０．０００４モル）、５０重量％ＮａＯＨ水溶液１２８．０ｇ（ＮａＯＨ、１．６モル）を仕込み、攪拌しながら５０℃まで昇温して均一な溶液にした。濃青緑色の溶液にセイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）１３４．１ｇ（純度９１％、０．８モル）を１５分かけて滴下し、その後５０〜５２℃で１０時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の粘ちょう液体をメタノールで洗浄した後に真空乾燥することにより、本発明の硬化性ビニルベンジル化合物（一般式１のＲ１、Ｒ２、Ｒ３はビニルベンジル基、Ｒ４は水素原子に相当する化合物と、一般式１のＲ１〜Ｒ３のうちいずれか２つがビニルベンジル基で残りが水素原子、Ｒ４は水素原子に相当する化合物と、一般式１のＲ１〜Ｒ３のうちいずれか１つがビニルベンジル基で残りが水素原子、Ｒ４は水素原子に相当する化合物との３種からなる）を得た。これを化合物２とする。なお、化合物２の確認は^１Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、ＨＰＬＣから行った。化合物２は２３℃で５０００ｐｏｉｓｅ程度の高粘性液体であった。図３に^１Ｈ−ＮＭＲスペクトルを、図４にＩＲスペクトルを示す。
化合物２をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で２時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
【００６２】
（実施例３）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロート、窒素吹き込み口を備えたフラスコ中を窒素置換し、そこにインデン４６．５ｇ（０．４モル）、トルエン２００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド３．８８ｇ（０．０１２モル）、フェノチアジン０．０４ｇ（０．０００２モル）、５０重量％ＮａＯＨ水溶液６４．０ｇ（ＮａＯＨ、０．８モル）を仕込み、攪拌しながら５０℃まで昇温して均一な溶液にした。濃青緑色の溶液にセイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）８０．４ｇ（純度９１％、０．４８モル）を１５分かけて滴下し、その後５０〜５２℃で１０時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の液体をメタノールで洗浄した後に真空乾燥することにより、本発明の硬化性ビニルベンジル化合物（主に、一般式１のＲ１〜Ｒ３のいちいずれか１つがビニルベンジル基で残りが水素原子、Ｒ４は水素原子に相当する化合物からなる）を得た。これを化合物３とする。化合物３は約１０００ｐｏｉｓｅの粘性液体であった。なお、化合物３の確認は、実施例１および２と同様に、^１Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、ＨＰＬＣから行った。
化合物３をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で２時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
【００６３】
（実施例４）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロート、窒素吹き込み口を備えたフラスコ中を窒素置換し、そこにインデン４６．５ｇ（０．４モル）、トルエン２００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド３．８８ｇ（０．０１２モル）、フェノチアジン０．０４ｇ（０．０００２モル）、５０重量％ＮａＯＨ水溶液６４．０ｇ（ＮａＯＨ、０．８モル）を仕込み、攪拌しながら５０℃まで昇温して均一な溶液にした。濃青緑色の溶液にセイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）６７．０ｇ（純度９１％、０．４０モル）を１５分かけて滴下し、その後５０〜５２℃で１０時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の液体をメタノールで洗浄した後に真空乾燥することにより、本発明の硬化性ビニルベンジル化合物（主に、一般式１のＲ１〜Ｒ３のいちいずれか１つがビニルベンジル基で残りが水素原子、Ｒ４は水素原子に相当する化合物からなる）を得た。これを化合物４とする。なお、化合物４の確認は実施例１および２と同様に、^１Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、ＨＰＬＣから行った。
化合物４をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で２時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
（実施例５）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロートを備えたフラスコにインデン１６６ｇ（１．４３モル）、トルエン１０００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド２２ｇ（０．０６９モル）、ｐ−キシリレンジクロリド２５０ｇ（１．４３モル）、セイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）２４０ｇ（純度９１％、１．４３モル）を仕込み、攪拌しながら４０℃まで昇温して均一な溶液にした。これに５０重量％ＮａＯＨ水溶液３４４ｇ（ＮａＯＨ、８．６モル）を加えて、その後７０℃で８時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の粘ちょう液体をメタノールで洗浄し、真空乾燥することにより、インデンがキシリレンでつながったオリゴマー化合物にビニルベンジル基が置換した分子量Ｍｗ３０００の固体化合物を得た（すなわち一般式２においてＲ４は水素、Ｒ５はキシリレン基、Ｒ６はビニルベンジル基、ａ〜ｃはＭｗが３０００に相当する値）。これを化合物６とする。なお、化合物６の確認は^１Ｈ−ＮＭＲから行った。本実施例で得られた化合物の^１Ｈ−ＮＭＲスペクトルを図５に、ＩＲスペクトルを図６に示す。
化合物６をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で２時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
【００６４】
（比較例１）
温度調節器、撹拌装置、冷却コンデンサー、滴下ロートを備えた四つ口フラスコに、ジシクロペンタジエン骨格フェノール樹脂ＤＰＰ−３Ｈ（日本石油化学社製特殊フェノール樹脂）４５ｇ（０．２５当量）、セイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）３８．１ｇ（純度９１％、０．２５モル）、テトラ−ｎ−ブチルアンモニウムブロマイド２．４ｇ、２，４−ジニトロフェノール０．０３８ｇ、メチルエチルケトン２００ｇを仕込み、攪拌溶解したものに７５℃で５０重量％ＮａＯＨ水溶液４０ｇ（ＮａＯＨ、０．４８モル）を２０分かけて滴下し、さらに７５℃で４時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和し、トルエン１００ｇを追加した後、有機層を蒸留水で３回洗浄した。メチルエチルケトンを減圧留去後、反応物をメタノールに沈澱させ、固形分を濾取した後、５０℃で真空乾燥し、ビニルベンジルエーテル化合物を得た。これを化合物７とする。
化合物７を実施例１と同様の方法で硬化成型して樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
【００６５】
（比較例２）
エポキシ樹脂（油化シェルエポキシ社製；エピコート８２８（エポキシ当量１８８）１００部に、２−エチル−４−メチルイミダゾール（四国化成社製）２部を配合して樹脂組成物とした。これを化合物８とする。
化合物８をガラス板の間に流し込み８０℃で２時間、１５０℃で２時間硬化して樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表１に示す。
【００６６】
【表１】

【００６７】
（実施例６）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロートを備えたフラスコにインデン１１６ｇ（１モル）、フルオレン１６６ｇ（１モル）、トルエン１０００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド２２ｇ（０．０６９モル）、ｐ−キシリレンジクロリド７０ｇ（０．４モル）、セイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）５５０ｇ（純度９１％、３．６モル）を仕込み、攪拌しながら４０℃まで昇温して均一な溶液にした。これに５０重量％ＮａＯＨ水溶液３５２ｇ（ＮａＯＨ、８．８モル）を加えて、その後７０℃で８時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の粘ちょう液体をメタノールで洗浄し、真空乾燥することにより、フルオレンとインデンがキシリレンでつながったオリゴマー化合物にビニルベンジル基が置換した分子量Ｍｗ７００の固体化合物を得た。これを化合物９とする。なお、化合物９の確認は^１Ｈ−ＮＭＲで行った。本実施例で得られた化合物の^１Ｈ−ＮＭＲスペクトルを図７に示す。
化合物９をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で５時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表２に示す。
【００６８】
（実施例７）
温度調節器、攪拌装置、冷却コンデンサー、滴下ロートを備えたフラスコにインデン５５ｇ（０．４８モル）、フルオレン２３７ｇ（１．４３モル）、トルエン１０００ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド２２ｇ（０．０６９モル）、ｐ−キシリレンジクロリド２５０ｇ（１．４３モル）、セイミケミカル社製ビニルベンジルクロライドＣＭＳ−ＡＭ（ｍ／ｐ異性体：５０／５０重量％混合物）２４０ｇ（純度９１％、１．４３モル）を仕込み、攪拌しながら４０℃まで昇温して均一な溶液にした。これに５０重量％ＮａＯＨ水溶液３４４ｇ（ＮａＯＨ、８．６モル）を加えて、その後７０℃で８時間反応させた。次にフラスコ内容物を２Ｎ塩酸で中和した後、蒸留水で２回洗浄し、トルエンを減圧留去後、得られたオレンジ色の粘ちょう液体をメタノールで洗浄し、真空乾燥することにより、フルオレンとインデンがキシリレンでつながったオリゴマー化合物にビニルベンジル基が置換した分子量Ｍｗ３０００の固体化合物を得た。これを化合物１０とする。なお、化合物１０の確認は^１Ｈ−ＮＭＲで行った。本実施例で得られた化合物の^１Ｈ−ＮＭＲスペクトルを図８に示す。
化合物１０をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で５時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表２に示す。
【００６９】
（参考例１）
温度調節器、撹拌装置、冷却コンデンサー、滴下ロートを備えた１リットルの四つ口フラスコに、フルオレンを４９．８ｇ（０．３モル）、トルエン２２０ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド２．９１ｇ（９×１０^−３モル）と５０重量％のＮａＯＨ水溶液９６ｇ（純度９５％、１．１４モル）を加え、６５℃に昇温した後、ｐ−キシリレンジクロライド２１ｇ（０．１２モル）を加えて２．５時間反応させた。少量の反応生成物の^１Ｈ−ＮＭＲ測定結果からｐ−キシリレンジクロライドが消費されていることを確認した後に反応系にＣＭＳ−ＡＭ５４ｇ（純度９１％、０．３６モル）を滴下し、６５℃で６．５時間反応を続けた。反応液を室温まで冷却した後、２Ｎ塩酸を加えて反応混合物を中和し、有機層に蒸留水を加えて３回洗浄した。溶剤を減圧留去した後、得られた固体をメタノール中で粉砕・ろ過し、固形分をろ取した後、真空オーブン中５０℃で乾燥してフルオレンがキシリレンでつながったオリゴマー化合物を得た。これを化合物１１とする。
この化合物１１をガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で５時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表２に示す。
【００７０】
（参考例２）
化合物６と化合物１１を等量づつ混ぜ合わせ、これをガラス板の間に流し込み、１６０℃で２時間、続いて１８０℃で５時間、２００℃で３時間硬化して１．５ｍｍ厚の樹脂板を作成し、これを用いて各測定に必要な試験片を作成した。試験結果を表２に示す。
【００７１】
【表２】

【００７２】
【発明の効果】
本発明によれば、電子機器材料に求められる低誘電率、低誘電正接、高耐熱性、および低吸水性に優れた硬化物となり得る硬化性ビニルベンジル化合物、その製造方法、該化合物を含む硬化性樹脂組成物、およびその硬化樹脂が提供される。
【図面の簡単な説明】
【図１】実施例１で得られた化合物の^１Ｈ−ＮＭＲスペクトルである。
【図２】実施例１で得られた化合物のＩＲスペクトルである。
【図３】実施例２で得られた化合物の^１Ｈ−ＮＭＲスペクトルである。
【図４】実施例２で得られた化合物のＩＲスペクトルである。
【図５】実施例５で得られた化合物の^１Ｈ−ＮＭＲスペクトルである。
【図６】実施例５で得られた化合物のＩＲスペクトルである。
【図７】実施例６で得られた化合物の^１Ｈ−ＮＭＲスペクトルである。
【図８】実施例７で得られた化合物の^１Ｈ−ＮＭＲスペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curable vinylbenzyl compound and a method for producing the same, and more specifically, can be a cured product excellent in low dielectric constant, low dielectric loss tangent, high heat resistance, and low water absorption required for electronic device materials. The present invention relates to a curable vinylbenzyl compound, a production method thereof, a curable resin composition containing the compound, and a cured resin thereof.
[0002]
[Prior art]
With the advancement of the advanced information society in recent years, higher speed and higher functionality are required in the fields of information processing and information communication. Along with this, higher performance has been required for the material of parts used in computers and mobile communication devices.
In order to cope with the increase in the amount of information, the calculation speed must be improved. For this purpose, it is necessary to increase the signal propagation speed, that is, to shorten the signal propagation delay time. Here, the delay of signal propagation is closely related to the dielectric constant of the material, and the lower the dielectric constant, the more advantageous is the reduction of the delay time.
In the field of information communication, as the number of channels of mobile communication devices increases, the frequency used is shifting to a higher frequency. Since high frequency has the property of being converted to heat and being lost, a material with low transmission loss is required to efficiently transmit an electric signal. Transmission loss is closely related to dielectric constant and dielectric loss tangent, and the lower these are, the smaller transmission loss is.
[0003]
From such a background, materials excellent in low dielectric constant and low dielectric loss tangent are strongly demanded in the fields of information processing and information communication. In addition, these materials are also required to have high heat resistance, low water absorption, and high adhesion to other equipment.
Various materials are being actively developed to meet these requirements. For example, polybenzocyclobutene (RA Kirchoff et al., Macromol. Symp. 54/55, 531 (1992)), fluorinated polybiphenylene ether (Japanese Patent Laid-Open No. 10-74751), heterocyclic side chain Polyphenylene compound (Japanese Patent Laid-Open No. 9-278879), polyfumaric acid ester (Japanese Patent Laid-Open No. 9-208697), polynorbornene (Japanese Patent Laid-Open No. 5-214079), polyquinoxaline (Japanese Patent No. 2705799), fluorination Polyquinoline (Japanese Unexamined Patent Publication No. 6-500971), side chain allyl group-substituted polyphenylene ether (Japanese Patent Laid-Open No. 64-69628, Japanese Patent Laid-Open No. 4-183707, No. 6-207096), allyl group or propargyl group End-capped polyphenylene ether -Tel (Japanese Patent Publication No. 7-51625).
However, these materials proposed in the prior art require a special solvent for shaping, which requires a low cross-linking density, a large coefficient of linear expansion, poor chemical resistance, poor toughness, complicated and multi-step production. As a matter of fact, there are various problems such as these, and the actual situation is that they have not been fully put into practical use at present.
[0004]
The present inventors also proposed a vinyl benzyl ether compound exhibiting a low dielectric constant, a low dielectric loss tangent, and a low water absorption in a wide range of temperatures and frequencies as a compound that can solve the above-mentioned problems (Japanese Patent Laid-Open No. 9-31006). ). This compound is one of the few materials that meets the stringent demands of current electronic materials. However, demands for various characteristics of electronic materials are becoming stricter. For example, in future next generation communication devices and the like, even more excellent dielectric characteristics are required.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a curable vinylbenzyl compound that can be a cured product excellent in low dielectric constant, low dielectric loss tangent, high heat resistance, and low water absorption, a method for producing the same, a curable resin composition containing the compound, And providing a cured resin thereof.
[0006]
[Means for Solving the Problems]
The invention of claim 1 is a curable vinylbenzyl compound represented by the following general formula.
(General formula 1)
[0007]
[Chemical 6]

[0008]
(In the formula, R1, R2 and R3 represent a group selected from a vinylbenzyl group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group and an aryl group. And at least one is a vinylbenzyl group, and R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. Represents one or more selected groups)
[0009]
The invention of claim 2 is a curable vinylbenzyl compound represented by the following general formula.
(General formula 2)
[0010]
[Chemical 7]

[0011]
(In the formula, R5 represents a divalent organic group having 2 to 20 carbon atoms, R6 represents a vinylbenzyl group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group. A group selected from a group and an aryl group, at least one of which is a vinylbenzyl group, a, b and c each represent an integer of 0 to 20, R4 represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 5; One or more groups selected from alkyl groups, alkoxy groups, thioalkoxy groups, thioaryloxy groups and aryl groups, which may be the same or different from each other)
[0012]
The invention of claim 3 is obtained by reacting one or more of the indene compounds represented by the following general formula 3, a fluorene compound, vinylbenzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. It is a curable vinylbenzyl compound.
(General formula 3)
[0013]
[Chemical 8]

[0014]
(In the formula, R 4 is one or more selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. Group)
[0015]
The invention according to claim 4 is characterized in that one or more of the indene compounds represented by the following general formula 3 are reacted with vinylbenzyl halide in the presence of an alkali. A method for producing a compound.
(General formula 3)
[0016]
[Chemical 9]

[0017]
(In the formula, the definition of R4 is the same as above.)
[0018]
The invention according to claim 5 is characterized in that one or more of the indene compounds represented by the following general formula 3 are reacted with vinylbenzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. Item 3. A method for producing the curable vinylbenzyl compound according to Item 2.
(General formula 3)
[0019]
[Chemical Formula 10]

[0020]
(In the formula, the definition of R4 is the same as above.)
[0021]
Invention of Claim 6 is a manufacturing method of Claim 4 or 5 whose vinyl benzyl halide is m-vinyl benzyl chloride and / or p-vinyl benzyl chloride.
[0022]
In the invention of claim 7, the equivalent ratio of the halomethyl group of vinylbenzyl halide to the halomethyl group of the dihalomethyl compound having 2 to 20 carbon atoms is defined as 0.9: 0.1 to 0.1: 0.9 as the former: the latter. It is a manufacturing method of Claim 5 or 6 which adjusts so that it may become and it uses for reaction.
[0023]
The invention according to claim 8 is the production method according to any one of claims 4 to 7, wherein the reaction is performed in the presence of an alkali and in an aprotic polar solvent and / or in the presence of a phase transfer catalyst. is there.
[0024]
The invention of claim 9 is a curable resin composition comprising the curable vinyl benzyl compound according to any one of claims 1 to 3 and a compound copolymerizable therewith.
[0025]
A tenth aspect of the present invention is a cured resin obtained by curing the curable vinylbenzyl compound according to any one of the first to third aspects.
[0026]
The invention of claim 11 is a cured resin obtained by curing the curable resin composition of claim 9.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The curable vinylbenzyl compound represented by the general formula 1 of the present invention is obtained by reacting one or more of the indene compounds represented by the general formula 3 with vinylbenzyl halide in the presence of an alkali. Can do.
Further, the curable vinylbenzyl compound represented by the general formula 2 of the present invention is obtained by converting one or more of the indene compounds represented by the general formula 3, a vinylbenzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms into an alkali. It can be obtained by reacting in the presence. The dihalomethyl compound referred to in the present invention means —CH in the molecule. ₂ A compound having two groups of X (wherein X represents a halogen atom).
Furthermore, the curable vinyl benzyl compound of the present invention is a curable vinyl obtained by reacting one or more of the indene compounds, a fluorene compound, a vinyl benzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. It can be a benzyl compound.
[0028]
The vinyl benzylation reaction in the present invention can be performed in the presence of an alkali in an organic solvent or an aqueous solution, preferably in an aprotic polar solvent and / or in the presence of a phase transfer catalyst. The vinyl benzylation reaction is described in, for example, L. J. et al. Mathias et al. Polym. Sci. , Part B; 36 , 2869 (1998), J. Am. Polym. Sci. , Part A; 35 , 587 (1997) or C.I. J. et al. Kelly et al. Chem. Res. (S), 446 (1997).
[0029]
Examples of the indene compounds used in the present invention include indene or indene compounds in which the aromatic ring portion is substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a thioalkoxy group, or an aryl group. May be used alone or in admixture of two or more. The substituted indene compound can be easily synthesized, for example, by halogenating the aromatic ring part of indene with bromine or the like and introducing a desired group into the part.
[0030]
The fluorene compound used in the present invention is preferably a compound represented by the following general formula 4.
[0031]
Embedded image

[0032]
(In the formula, R is one or more selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. Group)
[0033]
When a fluorene compound is used, the equivalent ratio of the fluorene compound and the indene compound is preferably adjusted to be 0.9: 0.1 to 0.1: 0.9 as the former: the latter and used for the reaction. Increasing the equivalent ratio of the fluorene compound tends to be a linear compound, and increasing the equivalent ratio of the indene compound tends to result in a compound with many branches.
[0034]
Examples of the vinyl benzyl halide used in the present invention include m-vinyl benzyl chloride, p-vinyl benzyl chloride, m-vinyl benzyl bromide, and p-vinyl benzyl bromide. These may be used alone or in combination of two or more. May be. Of these, m-vinylbenzyl chloride and p-vinylbenzyl chloride are preferred.
[0035]
Examples of the organic compound having 2 to 20 carbon atoms containing a dihalomethyl group include 1,2-dichloroethane, 1,2-dibromoethane, 1,3-dichloropropane, 1,3-dibromopropane, and 1,4-dichlorobutane. , Alkylene dihalides such as 1,4-dibromobutane, o-xylylene dichloride, o-xylylene dibromide, m-xylylene dichloride, m-xylylene dibromide, p-xylylene dichloride, p-xylylene dibromide, 4 , 4′-bis (chloromethyl) biphenyl, 4,4′-bis (chloromethyl) diphenyl ether, 4,4′-bis (chloromethyl) diphenyl sulfide, 2,6-bis (bromomethyl) naphthalene, 1,8- Such as bis (bromomethyl) naphthalene, 1,4-bis (chloromethyl) naphthalene, etc. Halomethyl compounds can be mentioned, which may be used as a mixture of two or more at singly within a range which is not occur intramolecular cyclization reaction.
[0036]
The equivalent ratio of the halomethyl group of vinylbenzyl halide to the halomethyl group of the dihalomethyl compound having 2 to 20 carbon atoms can be selected within a range in which gelation by the dihalomethyl compound does not occur. It is good to adjust to 0.1: 0.9 and to use for reaction. If the equivalent ratio of vinylbenzyl halide is less than 0.1, the curability is deteriorated, and various physical properties of the cured product such as heat resistance are lowered.
[0037]
Examples of the alkali used in the present invention include alkali metal or alkaline earth metal alkoxide, hydride, hydroxide, such as sodium methoxide, sodium ethoxide, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide. The alkali species may be selected depending on whether the reaction system is a non-aqueous system or a hydrous system.
[0038]
The use ratio of the alkali is preferably 1.1 to 3.0 equivalents relative to 1 equivalent of the halomethyl group of the raw material. If the equivalent is less than 1.1, the reaction rate is remarkably slow, or the reaction does not proceed completely, leaving the raw material unfavorably affecting the cured material properties. Since a large amount of washing water is used to remove residual alkali, it is not economical.
[0039]
Reaction solvents include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, tetramethylene sulfone, hexamethylphosphoamide , Methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexane, methylcyclohexane, toluene, xylene, etc., and mixtures thereof. From these, select the solvent type that makes the reaction system uniform according to the raw material type and reaction conditions do it. Of these, aprotic polar solvents are preferred.
[0040]
In the present invention, a phase transfer catalyst is preferably used in combination, and examples thereof include various onium salts such as tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride, tricaprylmethyl. Quaternary ammonium compounds such as ammonium chloride, tetra-n-butylphosphonium bromide, benzyltriphenylphosphonium chloride, quaternary phosphonium compounds such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tertiary sulfonium compounds such as benzyltetramethylenesulfonium bromide And mixtures thereof.
[0041]
The amount of use of these phase transfer catalysts cannot be defined unconditionally because the catalytic effect varies depending on the catalyst type or reaction temperature, but is generally about 0.01 to 0.5 equivalents relative to 1 equivalent of the halomethyl group of the raw material. It is enough to use it.
[0042]
The reaction temperature and reaction time cannot be defined unconditionally because they vary depending on the type of raw material compound used and the reaction conditions, but may be 0.5 to 20 hours at 30 to 100 ° C., respectively. A reaction temperature exceeding 100 ° C. is not preferable because it may cause undesirable reactions such as thermal polymerization. The reaction proceeds even below 30 ° C., but it is not economical because it takes a long time.
[0043]
Since the present invention uses vinylbenzyl halide, which is a highly polymerizable unsaturated halide, a polymerization inhibitor may be added to the reaction system as necessary, for example, t-butylcatechol, 2,4-di- -T-butylphenol, 2-t-butylphenol, 2-t-butyl-4-nitrophenol, 2,4-dinitrophenol, hydroquinone, methylhydroquinone, hydronoquinone monomethyl ether, t-butylhydroquinone, resorcin, pyrogallol, phenothiazine And copper salts. The amount of these thermal polymerization inhibitors used varies depending on the kind of the thermal polymerization inhibitor, and thus cannot be defined unconditionally. However, several ppm to 2000 ppm is sufficient for the curable vinylbenzyl compound.
[0044]
According to the present invention, in order to improve moldability and the like, a curable vinyl benzyl compound is blended with a compound copolymerizable with the compound within a range not impairing the effects of the present invention to prepare a curable resin composition. can do. Examples of this compound include polymers, oligomers and / or monomers, and specific examples thereof include vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, maleimide resins, polyphenol polycyanate resins, epoxy resins, and the like. Polymers, oligomers having a polymerizable unsaturated group such as vinylbenzyl ether resin, monomers and prepolymers such as triallyl isocyanurate and triallyl cyanurate, and vinylbenzyl compounds of fluorene. Furthermore, monomers such as styrene, vinyl toluene, divinyl benzene, and vinyl benzyl ether compounds, and various known monofunctional or polyfunctional (meth) acrylic acid derivative compounds can also be used.
[0045]
Further, the amount of the copolymerizable compound varies depending on the type of the copolymerizable compound, compatibility with the curable vinylbenzyl compound, use of the cured product, etc. It is 0-300 weight part with respect to 100 weight part of compounds, Preferably it is 0-200 weight part. An addition amount exceeding 300 parts by weight is not preferable because separation / exudation from the curable vinylbenzyl compound easily occurs.
[0046]
The curable resin of the present invention is obtained by curing the curable vinyl benzyl compound itself or the curable resin composition. Curing can employ known methods such as heat, light, and electron beam. It is also useful to accelerate the curing reaction using a curing agent.
[0047]
When a curing agent is used, for example, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylcumyl peroxide, methyl ethyl ketone peroxide Oxide, dicumyl peroxide, t-butyl perbenzoate and the like can be used depending on the application.
[0048]
The amount used varies depending on the type and concentration of the unsaturated group in the curable vinylbenzyl compound or curable resin composition, the type of curing agent used, the half-life temperature, the required stability, etc., but is generally curable. The amount is 0 to 10 parts by weight based on 100 parts by weight of the vinylbenzyl compound or the curable resin composition.
[0049]
In addition, known curing accelerators such as manganese naphthenate, lead naphthenate, zinc naphthenate, cobalt naphthenate, zinc octylate, dimethylaniline, and phenylmorpholine can also be used.
[0050]
The curing temperature varies depending on the type of polymerizable unsaturated group, the type and amount of curing agent, and the like, and thus cannot be defined unconditionally, but is 20 to 250 ° C, preferably 50 to 250 ° C. When the curing temperature is less than 20 ° C., curing may be insufficient, which is not preferable.
[0051]
Moreover, you may mix | blend well-known hardening retarders, such as hydroquinone, a benzoquinone, and a copper salt, in order to adjust hardening conditions.
[0052]
In addition, the curable vinyl benzyl compound and / or the curable resin composition of the present invention may be blended with a colorant, a filler, or a reinforcing fiber using a kneader, a blender, a roll, or the like, if necessary, to form a molding material or a composite material. It can also be. As the filler, silica, alumina, zirconia, titanium dioxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, and the like can be added within a range that does not impair the effects of the present invention.
[0053]
In addition, the high frequency board | substrate can also be manufactured by shape | molding the said curable vinyl benzyl compound or curable resin composition of this invention in a desired shape. Such a high frequency substrate is suitable for use in a high frequency region of 100 MHz or higher, particularly 1 GHz or higher. In such a high frequency region, the dielectric loss tangent can be maintained at about 0.002 to 0.01.
[0054]
Moreover, a prepreg can be obtained by impregnating a fiber material with the curable vinylbenzyl compound or the curable resin composition.
As the fiber material used for producing such a prepreg, known fiber materials such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, and alumina fiber can be used. It is preferable to use a glass cloth made of glass fibers having a high rate and low dielectric loss tangent. The content of the fiber material is preferably 30 to 70% by weight with respect to the prepreg from the viewpoint of strength, moldability, and the like.
As a method for impregnating the fiber material with the curable vinyl benzyl compound or the curable resin composition, either a known solvent method or a solventless method can be used. Solvents used in the solvent method include as little residual solvent as possible in the prepreg, and relatively low boiling point solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., in order to avoid deterioration of heat resistance, cracks and voids. Ketone solvents, aromatic hydrocarbon solvents such as benzene and toluene can be used.
A prepreg can be obtained by drying and heat-treating a fiber material impregnated with a curable vinylbenzyl compound or a curable resin composition at 80 to 130 ° C. for 10 to 180 minutes as necessary. it can.
[0055]
The obtained prepreg can be subjected to heating and pressurization alone or laminated to obtain a high frequency substrate. That is, a high-frequency substrate can be obtained by laminating a prepreg having a predetermined thickness alone or by stacking prepregs so as to have a predetermined thickness and performing heat-pressure molding by a known method such as hot pressing. The molding conditions are 80 to 250 ° C., preferably 100 to 200 ° C., 5 to 100 kg / cm. ² The pressure is 0.5 to 10 hours, and it is also effective to raise the temperature stepwise as necessary.
[0056]
Further, a metal-clad high-frequency substrate can be manufactured by laminating the above prepregs alone or by laminating them, and further applying metal foils to heat and pressure. That is, a prepreg having a predetermined thickness alone or a prepreg is laminated so as to have a predetermined thickness, metal foils are stacked on both surfaces of the laminate, and the above-mentioned heat-pressure molding is performed to obtain a metal-clad high-frequency substrate. be able to.
Examples of the metal foil include copper, gold, silver, and aluminum, but copper is preferable. Moreover, electrolytic foil and rolled foil can be used as needed.
[0057]
Further, the curable vinyl benzyl compound or the curable resin composition or a solution thereof is coated on a metal foil such as the copper foil as described above by a doctor blade coating method or the like, and is performed at 80 to 130 ° C. for 10 minutes to 180 minutes. It is also possible to obtain a metal foil with a resin in which both are integrated by drying and heat treatment, and this may be used as a high frequency substrate. Moreover, it is good also as a multilayer laminated substrate by laminating | stacking resin-coated metal foil on a core material, and heat-press-molding.
[0058]
Moreover, a multilayer laminated substrate can be manufactured by coating the above-mentioned curable vinyl benzyl compound or curable resin composition on a conductive layer, polymerizing and curing, and further providing a conductive layer on the cured product.
Such a multilayer laminated substrate uses, for example, a copper foil having a thickness of 18 μm as a conductive layer, and a curable vinylbenzyl compound or a curable resin composition is formed thereon as an insulating layer having a thickness of 20 to 200 μm, preferably 50 to 100 μm. It can be produced by a so-called build-up method in which it is applied, thermally cured, and a conductive layer is further formed thereon.
[0059]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Unless otherwise specified, parts in the examples mean parts by weight. In addition, the method of the measurement performed in the Example is shown below.
Thermogravimetric analysis: Measured using a TII apparatus manufactured by SII under a nitrogen stream at a heating rate of 10 ° C./min.
Dielectric characteristics: Using a vector network analyzer HP8753E manufactured by HP, a dielectric constant and a dielectric loss tangent of 5 GHz were measured by a cavity resonator perturbation method using a prismatic test piece of 1.5 mm × 1.5 mm × 75 mm.
¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR): Measured using JNM-LA300 manufactured by JEOL Ltd. using tetramethylsilane as an internal standard substance.
Infrared absorption spectrum (IR): Measured using a Fourier transform infrared spectrophotometer JIR-RFX3002FT-IR manufactured by JEOL Ltd.
High performance liquid chromatography (HPLC): Measured using Shodex R1-51 (column KF-801, KF-802) manufactured by Showa Denko KK at eluent tetrahydrofuran and elution rate of 1 ml / min.
Water absorption: A test piece of 1.5 mm × 40 mm × 40 mm is immersed in water at 25 ° C. for 24 hours, and calculated from the weight (W1) at the time of drying and the weight (W2) after water absorption [(W2-W1) / W1] × 100.
[0060]
Example 1
A flask equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel and a nitrogen blowing port was purged with nitrogen, and 34.9 g (0.3 mol) of indene, 200 g of toluene, tetra-n-butylammonium bromide 8 .72 g (0.027 mol), 1.79 g (0.009 mol) of phenothiazine, and 144.0 g (NaOH, 1.8 mol) of a 50 wt% NaOH aqueous solution were added, and the temperature was raised to 50 ° C. with stirring to be uniform. Solution. 150.8 g (purity 91%, 0.9 mol) of vinylbenzyl chloride CMS-AM (m / p isomer: 50/50% by weight mixture) manufactured by Seimi Chemical Co., Ltd. was dropped into the dark blue-green solution over 15 minutes. Then, the reaction was carried out at 50 to 52 ° C. for 10 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange viscous liquid was washed with methanol, followed by vacuum drying. The curable vinyl benzyl compound of the present invention (mainly R1, R2, and R3 in the general formula 1 are composed of a compound corresponding to a vinylbenzyl group and R4 is a hydrogen atom) was obtained. This is referred to as Compound 1. The confirmation of Compound 1 is ¹ Performed from 1 H-NMR spectrum, IR spectrum, HPLC. Compound 1 was a highly viscous liquid having almost no fluidity at 23 ° C. Figure 1 ¹ The H-NMR spectrum is shown in FIG. 2 and the IR spectrum is shown.
Compound 1 is poured between glass plates and cured at 160 ° C. for 2 hours, then at 180 ° C. for 2 hours, and at 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 1.
[0061]
(Example 2)
A flask equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel and a nitrogen blowing port was purged with nitrogen, and 46.5 g (0.4 mol) of indene, 200 g of toluene, tetra-n-butylammonium bromide 7 .75 g (0.024 mol), phenothiazine 0.08 g (0.0004 mol), and 50 wt% NaOH aqueous solution 128.0 g (NaOH, 1.6 mol) were charged, and the temperature was raised to 50 ° C. with stirring to be uniform. Solution. To the dark blue-green solution, 134.1 g (purity 91%, 0.8 mol) of vinylbenzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., Ltd. was dropped over 15 minutes. Then, the reaction was carried out at 50 to 52 ° C. for 10 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange viscous liquid was washed with methanol, followed by vacuum drying. The curable vinylbenzyl compound of the present invention (R1, R2, and R3 in general formula 1 are vinylbenzyl groups, R4 is a compound corresponding to a hydrogen atom, and any two of R1 to R3 in general formula 1 are vinylbenzyl groups. The remaining is a hydrogen atom, R4 is a compound corresponding to a hydrogen atom, and any one of R1 to R3 in the general formula 1 is a vinylbenzyl group, the remaining is a hydrogen atom, and R4 is a compound corresponding to a hydrogen atom. Obtained). This is designated Compound 2. The confirmation of compound 2 is ¹ Performed from 1 H-NMR spectrum, IR spectrum, HPLC. Compound 2 was a highly viscous liquid of about 5000 poise at 23 ° C. In FIG. ¹ The H-NMR spectrum is shown in FIG. 4 and the IR spectrum is shown.
Compound 2 is poured between glass plates and cured at 160 ° C. for 2 hours, then at 180 ° C. for 2 hours, and at 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 1.
[0062]
(Example 3)
A flask equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel and a nitrogen blowing port was purged with nitrogen, and 46.5 g (0.4 mol) of indene, 200 g of toluene, tetra-n-butylammonium bromide 3 .88 g (0.012 mol), 0.04 g (0.0002 mol) of phenothiazine, and 64.0 g (NaOH, 0.8 mol) of a 50 wt% NaOH aqueous solution were added, and the temperature was raised to 50 ° C. with stirring to be uniform. Solution. 80.4 g (purity 91%, 0.48 mol) of vinylbenzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., Ltd. was dropped into the dark blue-green solution over 15 minutes. Then, the reaction was carried out at 50 to 52 ° C. for 10 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange liquid was washed with methanol and then vacuum-dried. The curable vinylbenzyl compound (mainly, any one of R1 to R3 in the general formula 1 is a vinylbenzyl group, the remainder is a hydrogen atom, and R4 is a compound corresponding to a hydrogen atom). This is referred to as Compound 3. Compound 3 was a viscous liquid of about 1000 poise. In addition, the confirmation of the compound 3 is the same as in Examples 1 and 2, ¹ Performed from 1 H-NMR spectrum, IR spectrum, HPLC.
Compound 3 is poured between glass plates and cured at 160 ° C. for 2 hours, then at 180 ° C. for 2 hours and at 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 1.
[0063]
Example 4
A flask equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel and a nitrogen blowing port was purged with nitrogen, and 46.5 g (0.4 mol) of indene, 200 g of toluene, tetra-n-butylammonium bromide 3 .88 g (0.012 mol), 0.04 g (0.0002 mol) of phenothiazine, and 64.0 g (NaOH, 0.8 mol) of a 50 wt% NaOH aqueous solution were added, and the temperature was raised to 50 ° C. with stirring to be uniform. Solution. 67.0 g (purity 91%, 0.40 mol) of vinylbenzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., Ltd. was dropped into the dark blue-green solution over 15 minutes. Then, the reaction was carried out at 50 to 52 ° C. for 10 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange liquid was washed with methanol and then vacuum-dried. The curable vinylbenzyl compound (mainly, any one of R1 to R3 in the general formula 1 is a vinylbenzyl group, the remainder is a hydrogen atom, and R4 is a compound corresponding to a hydrogen atom). This is designated Compound 4. The confirmation of compound 4 was the same as in Examples 1 and 2, ¹ Performed from 1 H-NMR spectrum, IR spectrum, HPLC.
Compound 4 is poured between glass plates and cured at 160 ° C. for 2 hours, then at 180 ° C. for 2 hours and at 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 1.
(Example 5)
In a flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel, 166 g (1.43 mol) of indene, 1000 g of toluene, 22 g (0.069 mol) of tetra-n-butylammonium bromide, 250 g of p-xylylene dichloride (1.43 mol), 240 g (purity 91%, 1.43 mol) of vinyl benzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., Ltd., and stirred at 40 ° C. The temperature was raised to a homogeneous solution. To this was added 344 g (NaOH, 8.6 mol) of a 50 wt% NaOH aqueous solution, and then reacted at 70 ° C. for 8 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange viscous liquid was washed with methanol, followed by vacuum drying. A solid compound having a molecular weight of Mw 3000 in which an oligomer compound in which indene is connected by xylylene was substituted with a vinylbenzyl group was obtained. A value corresponding to 3000). This is designated Compound 6. The confirmation of compound 6 is ¹ Performed from 1 H-NMR. Of the compound obtained in this example. ¹ The H-NMR spectrum is shown in FIG. 5, and the IR spectrum is shown in FIG.
Compound 6 is poured between glass plates and cured at 160 ° C. for 2 hours, then at 180 ° C. for 2 hours and at 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 1.
[0064]
(Comparative Example 1)
In a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel, 45 g (0.25 equivalent) of dicyclopentadiene skeleton phenol resin DPP-3H (Nippon Petrochemical Co., Ltd. special phenol resin), Seimi Chemical Vinyl benzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) 38.1 g (purity 91%, 0.25 mol), tetra-n-butylammonium bromide 2.4 g, 2, 4 -0.038 g of dinitrophenol and 200 g of methyl ethyl ketone were charged, and 40 g of 50 wt% NaOH aqueous solution (NaOH, 0.48 mol) was added dropwise at 75 ° C. over 20 minutes to the mixture that was stirred and dissolved, and further reacted at 75 ° C. for 4 hours. It was. Next, the flask contents were neutralized with 2N hydrochloric acid, and after adding 100 g of toluene, the organic layer was washed with distilled water three times. After the methyl ethyl ketone was distilled off under reduced pressure, the reaction product was precipitated in methanol, and the solid content was collected by filtration and then vacuum dried at 50 ° C. to obtain a vinylbenzyl ether compound. This is designated as Compound 7.
Compound 7 was cured and molded in the same manner as in Example 1 to prepare a resin plate, and using this, test pieces necessary for each measurement were prepared. The test results are shown in Table 1.
[0065]
(Comparative Example 2)
2 parts of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.) was blended with 100 parts of epoxy resin (manufactured by Yuka Shell Epoxy; Epicoat 828 (epoxy equivalent 188)) to obtain a resin composition. Eight.
Compound 8 was poured between glass plates and cured at 80 ° C. for 2 hours and at 150 ° C. for 2 hours to prepare a resin plate. Using this, a test piece necessary for each measurement was prepared. The test results are shown in Table 1.
[0066]
[Table 1]

[0067]
(Example 6)
Indene 116 g (1 mol), fluorene 166 g (1 mol), toluene 1000 g, tetra-n-butylammonium bromide 22 g (0.069 mol), p in a flask equipped with a temperature controller, stirrer, cooling condenser and dropping funnel -70 g (0.4 mol) of xylylene dichloride, 550 g (purity 91%, 3.6 mol) of vinyl benzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., While stirring, the temperature was raised to 40 ° C. to obtain a uniform solution. To this, 352 g (NaOH, 8.8 mol) of a 50 wt% NaOH aqueous solution was added, and then reacted at 70 ° C. for 8 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange viscous liquid was washed with methanol, followed by vacuum drying. A solid compound having a molecular weight of Mw 700 was obtained in which a vinylbenzyl group was substituted for an oligomer compound in which fluorene and indene were connected by xylylene. This is designated Compound 9. The confirmation of compound 9 is ¹ Performed by 1 H-NMR. Of the compound obtained in this example. ¹ The H-NMR spectrum is shown in FIG.
Compound 9 is poured between glass plates and cured at 160 ° C. for 2 hours, followed by curing at 180 ° C. for 5 hours and 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 2.
[0068]
(Example 7)
In a flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel, 55 g (0.48 mol) indene, 237 g (1.43 mol) fluorene, 1000 g toluene, 22 g tetra-n-butylammonium bromide (0.069) Mol), 250 g (1.43 mol) of p-xylylene dichloride, 240 g (purity 91%, 1.43 mol) of vinyl benzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., Ltd. And heated to 40 ° C. with stirring to make a uniform solution. To this was added 344 g (NaOH, 8.6 mol) of a 50 wt% NaOH aqueous solution, and then reacted at 70 ° C. for 8 hours. Next, the flask contents were neutralized with 2N hydrochloric acid, then washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange viscous liquid was washed with methanol, followed by vacuum drying. A solid compound having a molecular weight Mw of 3000 was obtained in which a vinylbenzyl group was substituted for an oligomer compound in which fluorene and indene were connected by xylylene. This is designated Compound 10. The confirmation of compound 10 is ¹ Performed by 1 H-NMR. Of the compound obtained in this example. ¹ The H-NMR spectrum is shown in FIG.
Compound 10 is poured between glass plates and cured at 160 ° C. for 2 hours, followed by curing at 180 ° C. for 5 hours and 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is used for each measurement. A test piece was prepared. The test results are shown in Table 2.
[0069]
(Reference Example 1)
In a 1 liter four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel, 49.8 g (0.3 mol) of fluorene, 220 g of toluene, 2.91 g of tetra-n-butylammonium bromide ( 9x10 ^-3 Mol) and 96 g of 50% by weight NaOH aqueous solution (purity 95%, 1.14 mol), the temperature was raised to 65 ° C., and 21 g (0.12 mol) of p-xylylene dichloride was added for 2.5 hours. Reacted. Small amount of reaction product ¹ After confirming that p-xylylene dichloride is consumed from the H-NMR measurement results, 54 g (purity 91%, 0.36 mol) of CMS-AM was added dropwise to the reaction system, and the reaction was carried out at 65 ° C. for 6.5 hours. Continued. After cooling the reaction solution to room temperature, 2N hydrochloric acid was added to neutralize the reaction mixture, and distilled water was added to the organic layer and washed three times. After the solvent was distilled off under reduced pressure, the obtained solid was pulverized and filtered in methanol, and the solid content was collected by filtration and then dried at 50 ° C. in a vacuum oven to obtain an oligomer compound in which fluorene was connected with xylylene. This is designated Compound 11.
This compound 11 is poured between glass plates and cured at 160 ° C. for 2 hours, then at 180 ° C. for 5 hours, and at 200 ° C. for 3 hours to prepare a 1.5 mm thick resin plate, which is necessary for each measurement. Specimens were made. The test results are shown in Table 2.
[0070]
(Reference Example 2)
Compound 6 and Compound 11 are mixed in equal amounts, poured between glass plates, and cured at 160 ° C. for 2 hours, then at 180 ° C. for 5 hours, and at 200 ° C. for 3 hours to produce a 1.5 mm thick resin plate Then, using this, a test piece necessary for each measurement was prepared. The test results are shown in Table 2.
[0071]
[Table 2]

[0072]
【The invention's effect】
According to the present invention, a curable vinylbenzyl compound that can be a cured product excellent in low dielectric constant, low dielectric loss tangent, high heat resistance, and low water absorption required for electronic device materials, a method for producing the same, and curing including the compound Resin composition and cured resin thereof are provided.
[Brief description of the drawings]
FIG. 1 shows the compound obtained in Example 1. ¹ It is a 1 H-NMR spectrum.
2 is an IR spectrum of the compound obtained in Example 1. FIG.
FIG. 3 shows the compound obtained in Example 2. ¹ It is a 1 H-NMR spectrum.
4 is an IR spectrum of the compound obtained in Example 2. FIG.
FIG. 5 shows the result of the compound obtained in Example 5. ¹ It is a 1 H-NMR spectrum.
6 is an IR spectrum of the compound obtained in Example 5. FIG.
FIG. 7 shows the result of the compound obtained in Example 6. ¹ It is a 1 H-NMR spectrum.
FIG. 8 shows the compound obtained in Example 7. ¹ It is a 1 H-NMR spectrum.

Claims (11)

A curable vinylbenzyl compound represented by the following general formula.
(General formula 1)

(In the formula, R1, R2 and R3 represent a group selected from a vinylbenzyl group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group and an aryl group. At least one is a vinylbenzyl group, R4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. Represents one or more selected groups) A curable vinylbenzyl compound represented by the following general formula.
(General formula 2)

(In the formula, R5 represents a divalent organic group having 2 to 20 carbon atoms, R6 represents a vinylbenzyl group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group. A group selected from a group and an aryl group, at least one of which is a vinylbenzyl group, a, b and c are each an integer of 0 to 20, and R4 is a hydrogen atom, a halogen atom or a carbon number of 1 to 5; One or more groups selected from alkyl groups, alkoxy groups, thioalkoxy groups, thioaryloxy groups and aryl groups, which may be the same or different from each other) A curable vinylbenzyl compound obtained by reacting one or more of the indene compounds represented by the following general formula 3, a fluorene compound, a vinylbenzyl halide, and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali.
(General formula 3)

(In the formula, R 4 is one or more selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. Group) The method for producing a curable vinylbenzyl compound according to claim 1, wherein one or more indene compounds represented by the following general formula 3 are reacted with vinylbenzyl halide in the presence of an alkali.
(General formula 3)

(In the formula, the definition of R4 is the same as above.) 3. The curable vinyl according to claim 2, wherein one or more of the indene compounds represented by the following general formula 3 are reacted with vinylbenzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. A method for producing a benzyl compound.
(General formula 3)

(In the formula, the definition of R4 is the same as above.) 6. The production method according to claim 4, wherein the vinyl benzyl halide is m-vinyl benzyl chloride and / or p-vinyl benzyl chloride. The equivalent ratio of the halomethyl group of vinylbenzyl halide and the halomethyl group of the dihalomethyl compound having 2 to 20 carbon atoms is adjusted to 0.9: 0.1 to 0.1: 0.9 as the former: the latter. The manufacturing method of Claim 5 or 6 with which it uses for reaction. The production method according to any one of claims 4 to 7, wherein the reaction is carried out in the presence of an alkali and in an aprotic polar solvent and / or in the presence of a phase transfer catalyst. A curable resin composition comprising the curable vinylbenzyl compound according to any one of claims 1 to 3 and a compound copolymerizable therewith. A cured resin obtained by curing the curable vinylbenzyl compound itself according to any one of claims 1 to 3. A cured resin obtained by curing the curable resin composition according to claim 9.

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