JP2004123946A - Norbornene ring-opened polymer and its hydrogenated product, manufacturing process of these and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene ring-opened polymer and its hydrogenated product that have excellent mechanical properties, transparency and heat resistance and are suitable for an optical film having reduced appearance defects, a manufacturing process of these and an optical film. <P>SOLUTION: The norbornene ring opened polymer comprises a ring-opened polymer of a norbornene monomer and has a number average molecular weight of 50,000-1,000,000 measured by high speed liquid chromatography and a molecular weight distribution (weight average molecular weight/number average molecular weight) of ≤ 2.0. <P>COPYRIGHT: (C)2004,JPO

Description

【００１５】
上記一般式（１）中、Ｒ^３、Ｒ^４は、同一もしくは異なる水素、炭素数２〜２０のアルケニル基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数２〜２０のカルボキシル基、炭素数２〜２０のアルコキシ基、炭素数２〜２０のアルケニルオキシ基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアルコキシカルボニル基、炭素数２〜２０のアルキルチオ基、又は、フェロセン誘導体を表し、これらは、炭素数１〜５のアルキル基、ハロゲン原子、炭素数１〜５のアルコキシ基によって置換されたフェニルによって、必要に応じて置換されていても良い。
【００１６】
また、Ｘ^１、Ｘ^２は、同一又は異なる任意のアニオン性配位子を表し、Ｃｌ又はＢｒであることが好ましく、Ｃｌであることが更に好ましい。
【００１７】
更に、Ｌ^１、Ｌ^２は、同一又は異なる任意の中性電子供与体を表し、リン系配位子であることが好ましい。上記リン系配位子としては、一般式：ＰＲ’　Ｒ’’Ｒ’’’　で表されるホスフィン等が挙げられる。ここで、Ｒ’　、Ｒ’’及びＲ’’’　は、それぞれ独立した炭素数１〜２０のアルキル基、又は、炭素数６〜２０のアリール基を表し、好ましくはメチル基、エチル基、イソプロピル基、ｔ−ブチル基、シクロヘキシル基、フェニル基、又は、置換フェニル基の中から選ばれ、重複して選ぶこともできる。具体的には、−Ｐ（シクロヘキシル）_３、−Ｐ（フェニル）_３、−Ｐ（イソプロピル）_３等が挙げられる。
【００１８】
また、Ｌ_１、Ｌ_２としては、イミダゾリウム化合物も好適に用いられる。
具体的には、イミダゾリン−２−イリデン誘導体、４，５−ジヒドロイミダゾリン−２−イリデン誘導体が好ましく、更に具体的には、Ｎ、Ｎ′−ジメシチルイミダゾリン−２−イリデン配位子やＮ、Ｎ′−ジメシチル−４，５−ジヒドロイミダゾリン−２−イリデン配位子等がより好ましい。
更に、Ｌ１及びＬ２が同一分子となり、二座配位とすることもできる。
【００１９】
なお、Ｘ^１、Ｘ^２、Ｌ^１、Ｌ^２のうち２個又は３個は、更に一緒になって多座キレート化配位子を形成しても良い。
また、上記一般式（１）では、Ｌ^１、Ｌ^２は互いがトランス位に記述されているが、その立体嵩高さによって、また同一分子となって二座配位した場合等においてシス配位をとることもできる。
更に、Ｘ^１、Ｘ^２は互いがシス位に記述されているが、Ｌ^１、Ｌ^２の種類によってトランス配位をとることもできる。
【００２０】
上記一般式（２）中、Ｒ^５、Ｒ^６は、同一もしくは異なる水素、炭素数２〜２０のアルケニル基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数２〜２０のカルボキシル基、炭素数２〜２０のアルコキシ基、炭素数２〜２０のアルケニルオキシ基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアルコキシカルボニル基、炭素数２〜２０のアルキルチオ基、炭素数２〜２０のアルキルシリル基、炭素数２〜２０のアリールシリル基、又は、フェロセン誘導体を表し、これらは、炭素数１〜５のアルキル基、ハロゲン原子、炭素数１〜５のアルコキシ基によって置換されたフェニルによって、必要に応じて置換されていても良い。
【００２１】
ただし、Ｒ^５として、アルキルシリル基又はアリールシリル基を用いる場合には、錯体の安定性からケイ素上に重複して選ぶことができ、その際、メチル基、エチル基、イソプロピル基、ｔ−ブチル基、シクロヘキシル基、フェニル基等の中から選ばれることが好ましい。具体的には、トリメチルシリル基、トリエチルシリル基、ジフェニルメチルシリル基、ジメチルｔ−ブチルシリル基、トリイソプロピルシリル基等が挙げられる。また、この場合、錯体の安定性や活性の面から、Ｒ^６としては、ｔ−ブチル基、ｎ−ブチル基、ｎ−プロピル基、イソプロピル基、エチル基、メチル基、メトキシメチル基、フェロセニル基、トリメチルシリル基、フェニル基、トリル基、アニシル基等が好ましい。
【００２２】
また、Ｘ^３、Ｘ^４は、同一又は異なる任意のアニオン性配位子を表し、Ｃｌ又はＢｒであることが好ましく、Ｃｌであることが更に好ましい。
【００２３】
更に、Ｌ^３、Ｌ^４は、同一又は異なる任意の中性電子供与体を表し、リン系配位子であることが好ましい。上記リン系配位子としては、一般式：ＰＲ’　Ｒ’’Ｒ’’’　で表されるホスフィンが挙げられる。ここで、Ｒ’　、Ｒ’’及びＲ’’’　は、それぞれ独立した炭素数１〜２０のアルキル基、又は、炭素数６〜２０のアリール基を表し、好ましくはメチル基、エチル基、イソプロピル基、ｔ−ブチル基、シクロヘキシル基、フェニル基、又は、置換フェニル基の中から選ばれ、重複して選ぶこともできる。具体的には、−Ｐ（シクロヘキシル）_３〔ＰＣｙ_３と略記〕、−Ｐ（フェニル）_３、−Ｐ（イソプロピル）_３等が挙げられる。
【００２４】
また、Ｌ^３、Ｌ^４としては、イミダゾリウム化合物も良好に用いられる。
具体的には、イミダゾリン−２−イリデン誘導体、４，５−ジヒドロイミダゾリン−２−イリデン誘導体が好ましく、更に具体的には、Ｎ、Ｎ′−ジメシチルイミダゾリン−２−イリデン配位子やＮ、Ｎ′−ジメシチル−４，５−ジヒドロイミダゾリン−２−イリデン配位子等がより好ましい。
更に、Ｌ^３及びＬ^４が同一分子となり、二座配位とすることもできる。
【００２５】
なお、Ｘ^３、Ｘ^４、Ｌ^３、Ｌ^４のうち２個又は３個は、更に一緒になって多座キレート化配位子を形成しても良い。
【００２６】
上記一般式（３）又は（４）中、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０は、同一もしくは異なる水素、炭素数２〜２０のアルケニル基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数２〜２０のカルボキシル基、炭素数２〜２０のアルコキシ基、炭素数２〜２０のアルケニルオキシ基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアルコキシカルボニル基、炭素数２〜２０のアルキルチオ基又はフェロセン誘導体を表し、これらは、炭素数１〜５のアルキル基、ハロゲン原子、炭素数１〜５のアルコキシ基によって置換されたフェニル基によって、必要に応じて置換されていても良い。
【００２７】
また、Ｒ^７、Ｒ^９、Ｒ^１０としては、炭素数１〜２０のアルキル基、シクロへキシル基、フェニル基や、炭素数１〜５のアルキル基、炭素数１〜５のアルキルオキシ基、カルボキシル基、炭素数１〜５のアルキルシリル基、ヒドロキシル基、ニトロ基、ハロゲン、炭素数５以下のアミノ基、アセチル基、アセトキシ基で置換されたフェニル基等であることが好ましく、フェニル基、ｏ−トリル基、ｐ−トリル基、２，６−キシリル基、アニシル基、ニトロベンゼン基、クロロベンゼン基、ｏ−イソプロピルフェニル基、２，６−ジイソプロピルフェニル基、エチル基、イソプロピル基、ｔ−ブチル基、シクロへキシル基であることが更に好ましい。
【００２８】
また、Ｙ^１、Ｙ^２、Ｙ^３は、同一又は異なる硫黄、酸素、セレン元素等を表し、なかでも、硫黄、セレンであることが好ましい。
【００２９】
また、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８は、同一又は異なる任意のアニオン性配位子を表し、ＣｌまたはＢｒであることが好ましく、Ｃｌであることが更に好ましい。
【００３０】
更に、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８は、同一又は異なる任意の中性電子供与体を表し、リン系配位子であることが好ましい。上記リン系配位子としては、式：ＰＲ^’Ｒ^’’Ｒ^’’’で表されるホスフィン等が挙げられる。ここで、Ｒ^’、Ｒ^’’、Ｒ^’’’は、それぞれ独立した炭素数１〜２０のアルキル基、又は、炭素数６〜２０のアリール基等を表し、好ましくはメチル基、エチル基、イソプロピル基、ｔ−ブチル基、シクロヘキシル基、フェニル基、又は、置換フェニル基の中から選ばれ、重複して選ぶこともできる。具体的には、−Ｐ（シクロヘキシル）_３、−Ｐ（フェニル）_３、−Ｐ（イソプロピル）_３等が挙げられる。
【００３１】
また、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８としては、イミダゾリウム化合物も好適に用いられる。具体的には、イミダゾリン−２−イリデン誘導体、４，５−ジヒドロイミダゾリン−２−イリデン誘導体が好ましく、更に具体的には、Ｎ、Ｎ′−ジメシチルイミダゾリン−２−イリデン配位子やＮ、Ｎ′−ジメシチル−４，５−ジヒドロイミダゾリン−２−イリデン配位子が挙げられる。
更に、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８が同一分子となり、二座配位とすることもできる。
【００３２】
なお、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８の２個又は３個は、更に一緒になって多座キレート化配位子を形成しても良い。
【００３３】
上記一般式（１）〜（４）で表されるルテニウム系錯体は、種々の方法により製造することができるが、代表的な方法としては、一方でＬ^１〜Ｌ^８を有する配位子前駆体等の原料を公知の方法に従って合成し、他方でルテニウム錯体前駆体原料を公知の方法に従って合成し、最後に両者の原料を混合して配位子交換反応を行って製造する方法が挙げられる。
【００３４】
上記メタセシス重合反応は、不活性気体雰囲気下にて行うことが好ましいが、ルテニウム系の安定な触媒を用いた場合は、空気中で重合することができる。
一般に、メタセシス重合反応により得られる樹脂は二重結合を有し、空気中の酸素等により劣化することがある。この劣化を防止するため、重合系中に抗酸化剤を添加させることもできる。
【００３５】
上記ルテニウム系錯体を用いた重合には分子量を制御するために連鎖移動剤を用いることができる。連鎖移動剤としては２重結合を少なくとも一つ有する鎖状構造である必要がある。その中でも重合阻害を起こさず好適に用いられる連鎖移動剤としては、１−ブテン、１−ペンテン、１−ヘキセン等のα―オレフィンやアリルアセテート、ビニルアセテートなどが挙げられるが、特に限定されず、官能基や各種置換基が存在してもよい。ルテニウム系錯体は官能基によって分解されにくいため、各種官能基を有する連鎖移動剤を用いることで重合体の末端に効率よく官能基を導入することができる。
【００３６】
上記連鎖移動剤の添加量は、ノルボルネン系モノマーに対して１／１５０〜１／８０００モルの範囲が好ましく、より好ましくは１／２５０〜１／５０００モルである。
【００３７】
本発明のノルボルネン系開環重合体水素化物の合成に用いる水素添加触媒としては、例えば、ウィルキンソン錯体、酢酸コバルト／トリエチルアルミニウム、ニッケルアセチルアセテート／トリイソブチルアルミニウム、パラジウム−カーボン、ルテニウム錯体、ルテニウム−カーボン、ニッケル−けいそう土等が挙げられる。
【００３８】
また、上述の開環重合を行う際に用いる触媒が上記式（１）〜（４）の構造のものを用いる場合には、これらを水素添加用触媒として用いることもできる。
つまり重合後、そのまま水素添加を行うことにより、重合後の精製を省いて水素添加を行うことも可能である。
上記水素添加は、触媒の種類により均一系又は不均一系で、通常、０．１〜２０ＭＰａの水素圧下、０〜２５０℃で行われる。
【００３９】
本発明のノルボルネン系開環重合体の水素添加物は、光学フィルム用途に対して特に好適に使用できることができる。分子量分布を制御しながら、得られるノルボルネン系開環重合体の水素添加物の分子量を上げることで、ゲル状の不純物発生による外観の欠点がなく、かつ、力学特性にも優れたフィルムを製造することができる。上記光学フィルム用途の中でも、特に偏光板保護フィルムとして好適に用いることができる。
【００４０】
本発明のノルボルネン系開環重合体の水素添加物から光学フィルムを作製した際の欠点の数は、１平方メートルあたり１０個未満（検査面積１０平方メートルでの目視検査による１平方メートルあたりの点状欠陥の数）であることが好ましく、より好ましくは３個以下である。
【００４１】
本発明の樹脂は、上述のように、欠点の少ないフィルムを製造することができる。
【００４２】
【発明の実施の形態】以下、本発明の実施例について説明するが、本発明がこれらによって限定されるものではない。なお、各特性の測定、評価は下記の条件に従って行なった。
【００４３】
（１）高速液体クロマトグラフィーによる分子量の測定
東ソー（株）社製ＨＬＣ−８０２０とオートサンプラーＡＳ−８０２０、データ解析ＳＣ−８０２０、カラムＳｈｏｄｅｘ社製Ｋ−８０６Ｌ（２本使用）を用い、測定条件として、流量が１ｍｌ／分、オーブン温度が４０℃、屈折計温度が４０℃、試料濃度が約０．１ｗｔ％、試料注入量が３００μｌ、溶媒がクロロホルム、標準試料が標準ポリスチレンとして測定した。
【００４４】
（２）破断伸度測定
ＴＥＮＳＩＬＯＮ（ＯＲＩＥＮＴＥＣ社製）により評価した。

【００４５】
（３）外観
得られたフィルムを透過式にて欠点の数を目視検査（検査面積１０ｍ^２）により評価した。
【００４６】
［触媒の合成例１］
５．５７ｇ（９．１ｍｍｏｌ）のＲｕ（ｐ−ｃｙｍｅｎｅ）Ｃ^１２に対して、１８．２ｍｍｏｌのＰＣｙ_３及び９．１ｍｍｏｌのｔ−ブチルアセチレンを１５０ｍｌのトルエンとともに３００ｍｌのフラスコ中で窒素気流下、７時間反応させた。反応終了後、トルエンを減圧除去し、ＴＨＦ／エタノール系にて再結晶を行うことにより、下式（５）のルテニウム錯体化合物を合成した。
【００４７】
【化２】

【００４８】
［触媒の合成例２］
米国特許第５，８３１，１０８号明細書に記載の方法に従って、下式（６）のルテニウム錯体化合物を合成した。
【００４９】
【化３】

【００５０】
［触媒の合成例３］
ＷＯ９９／００３９６号明細書に記載の方法に従って、下式（７）のルテニウム錯体化合物を合成した。
【００５１】
【化４】

【００５２】
（実施例１）
アリルアセテート０．０１モルと式（５）のルテニウム錯体０．００２モルをシクロヘキサン１０ｍＬに溶解させ、テトラシクロドデセン１０モルを４Ｌのシクロヘキサンに溶解させた溶液に加えた。反応溶液を窒素気流下、シクロヘキサンの還流温度にて２４時間反応させた。その後室温まで降温させ、０．０２モルのエチルビニルエーテルを加えた。得られた反応溶液をメタノール１０Ｌを用いて再沈精製し、減圧乾燥させ開環重合体を得た。重合結果を表１に示した。
【００５３】
得られた開環重合体４５０ｇを９０００ｍｌのテトラヒドロフランに溶解し、パラジウム濃度が５重合％のパラジウム−アルミナ触媒４５ｇを加え、水素ガスを圧力が９．８ＭＰａとなるよう仕込んで、１５０℃で５時間水素添加反応させた。水素添加反応後、触媒を濾別し、濾液を塩酸酸性の大過剰量のメタノール中に注いで、開環重合体の水素添加物を得た。水素添加物の水素添加率は実質上１００％であった。結果を表１に示した。
得られた開環重合体の水素添加物を２軸溶融押出機を用いて２８０℃で溶融混合し、Ｔダイスにより厚み４０μｍのフィルムを製造した。得られたフィルムの物性評価結果を表１に示した。
【００５４】
（実施例２）
アリルアセテート０．００５モルとルテニウム錯体（６）０．００２モルをシクロヘキサン１０ｍＬに溶解させ、下式（８）で表される８−メチル−８−カルボキシメチルテトラシクロ〔４．４．０．１^２，５．１^７，１０〕−３−ドデセン１０モルを４Ｌのシクロヘキサンに溶解させた溶液に加えた。反応溶液を窒素気流下、シクロヘキサンの還流温度にて２４時間反応させた。その後室温まで降温させ、０．０２モルのエチルビニルエーテルを加えた。得られた反応溶液をメタノール１０Ｌを用いて再沈精製し、減圧乾燥させ開環重合体を得た。重合結果を表１に示した。
【００５５】
上記開環重合体の水素添加物を実施例１と同様の方法で得た後、この水素添加物を２軸溶融押出機を用いて２８０℃で溶融混合し、Ｔダイスにより厚み４０μｍのフィルムを製造した。得られたフィルムの物性評価結果を表１に示した。
【００５６】
【化５】

【００５７】
（実施例３）
ルテニウム錯体（６）の代わりに、ルテニウム錯体（７）を用いたこと以外は、実施例２と同様の操作を行ってフィルムを得、フィルムの物性評価結果を表１に示した。
【００５８】
（比較例１）
テトラシクロドデセン１０モルを４Ｌのシクロヘキサンに溶解させ、０．０２モルのトリエチルアルミニウムを溶解させたシクロヘキサン溶液５０ｍＬ、連鎖移動剤として１−ヘキセン０．００５モル、及びトリエチルアミン０．０８モルを添加した。この溶液を３０℃に保ちながらテトラシクロドデセン１０モル、０．０２モルの四塩化チタンを溶解させたシクロヘキサン溶液５０ｍＬに１時間にわたって連続的に添加して重合を行った。
テトラシクロドデセンと四塩化チタンの全量を添加し、３０分後、０．００５モルの六塩化タングステンを溶解させたシクロヘキサン溶液２０ｍＬを添加し、さらに３０分間攪拌した。その後、反応溶液をメタノールにて再沈精製し、減圧乾燥して開環重合体を得た。結果を表１に示した。
【００５９】
得られた開環重合体４５０ｇを９０００ｍｌのシクロヘキサンに溶解し、パラジウム濃度が５重合％のパラジウム−アルミナ触媒４５ｇを加え、水素ガスを圧力が９．８ＭＰａとなるよう仕込んで、１５０℃で５時間水素添加反応させた。水素添加反応後触媒を濾別し、濾液を塩酸酸性の大過剰量のメタノール中に注いで、開環重合体の水素添加物を得た。重合体の水素添加率は実質上１００％であった。結果を表１に示した。
得られた開環重合体の水素添加物を２軸溶融押出機を用いて２８０℃で溶融混合し、Ｔダイスにより厚み４０μｍのフィルムを製造した。得られたフィルムの物性評価結果を表１に示した。
【００６０】
（比較例２）
窒素ガスで置換した反応容器内に、上記式（８）で示される８−メチル−８−カルボキシメチルテトラシクロ〔４．４．０．１^２，５．１^７，１０〕−３−ドデセン３モルと、１，２−ジクロロエタン２００ｍｌと、連鎖移動剤である１−ヘキセン０．０１モルと、触媒として、六塩化タングステンの濃度０．０７Ｍ／リットルのクロロベンゼン溶液９０ｍｌと、パラアルデヒドの濃度０．１５Ｍ／リットルの１，２−ジクロロエタン溶液７０ｍｌと、トリイソブチルアルミニウムの濃度０．７Ｍ／リットルのトルエン溶液３７ｍｌとを加え、６０℃で８時間反応させることにより開環重合体４４０ｇを得た。
【００６１】
この開環重合体を９０００ｍｌのテトラヒドロフランに溶解し、パラジウム濃度が５重合％のパラジウム−アルミナ触媒４５ｇを加え、水素ガスを圧力が１００ｋｇ／ｃｍ２　となるよう仕込んで、１４０℃で５時間水素添加反応させた。
水素添加反応後触媒を濾別し、濾液を塩酸酸性の大過剰量のメタノール中に注いで、開環重合体の水素添加物を得た。この重合体の水素添加率は実質上１００％であった。
得られた開環重合体の水素添加物を２軸溶融押出機を用いて２８０℃で溶融混合し、Ｔダイスにより厚み４０μｍのフィルムを製造した。得られたフィルムの物性評価結果を表１に示した。
【００６２】
【表１】

【００６３】
【発明の効果】本発明のノルボルネン系開環重合体及びその水素添加物は、上述の構成であり、その水素添加物から得られるフィルムは、耐熱性、透明性、伸度や弾性率等の力学的特性に優れ、外観欠点が少なく、光学用部品、電気・電子関係の絶縁材料として好適に用いられる。[0001]
[Industrial applications]
The present invention relates to a norbornene-based ring-opened polymer and a hydrogenated product thereof, a production method thereof, and an optical film.
[0002]
[Prior art]
Norbornene resins have excellent properties such as heat resistance, optical properties, transparency, and electrical properties, and are being considered for applications as films to automotive parts, electrical and electronic parts, optical parts, and building materials, etc. I have.
Norbornene-based resins are disclosed in Patent Documents 1 to 4 and the like, and films are manufactured by an extrusion molding method, a solution casting method, or the like.
[0003]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 4-170425 [Patent Document 2]
JP-A-6-51117 [Patent Document 3]
JP-A-4-361230 [Patent Document 4]
JP-A-3-223328
Patent Document 5 discloses a norbornene-based resin having a number-average molecular weight of 20,000 to 50,000. However, if the molecular weight exceeds 50,000, the moldability deteriorates and it cannot be used. Although high mechanical strength can be expected by using a high molecular weight material as a molding material, it cannot be used for high-performance optical material applications because gel-like impurities are generated due to the wide molecular weight distribution and appearance defects are caused. Was.
[0005]
[Patent Document 5]
JP-A-4-170425
[Problems to be solved by the present invention]
The present invention has been made in view of the above-described problems, and has excellent mechanical properties, transparency, heat resistance, and a norbornene-based ring-opening polymer and a norbornene-based ring-opening polymer that are suitable for an optical film having few appearance defects. An object is to provide a hydrogenated product, a method for producing the same, and an optical film.
[0007]
[Means for Solving the Problems]
The norbornene-based ring-opened polymer of the present invention is a ring-opened polymer of a norbornene-based monomer, and has a number average molecular weight of 50,000 to 1,000,000 as measured by high performance liquid chromatography, and a molecular weight distribution (weight average). (Molecular weight / number average molecular weight) of 2.0 or less.
[0008]
Hereinafter, the present invention will be described in detail.
As the norbornene-based monomer of the present invention, a tetracyclododecene derivative is preferable in that a polymer having a high glass transition point can be obtained, but the structure of the monomer can be freely selected depending on the application.
[0009]
Preferred compounds of the norbornene-based monomer include, for example, 8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^1,10 ] -3-dodecene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . Compounds having a functional group such as [ ^17,10 ] -3-dodecene, 5-carboxymethyl-bicyclo [2.2.1] -2-heptene, and cyclic olefin compounds such as cyclopentene, cyclooctene, 1,5- Cycloolefins such as cyclooctadiene and 1,5,9-cyclododecatriene; bicyclo [2.2.1] -2-heptene, tricyclo [5.2.1.0 ^2,6 ] -8-decene; Tricyclo [5.2.1.0 ^2,6 ] -3-decene, tricyclo [6.2.1.0 ^1,8 ] -9-undecene, tricyclo [6.2.1.0 ^1,8 ]- 4-undecene, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [6.6.1.13,6. 02,7. 09,14] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ^09,13 ] -11-pentadecene, dicyclopentadiene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] - pentadeca-4,11 may be mentioned poly cycloalkene such a diene.
[0010]
Further, these norbornene monomers have a carbon-carbon double bond in the main chain of a polymer such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer. Ring-opening polymerization can also be carried out in the presence of the unsaturated hydrocarbon-based polymer contained. A ring-opening polymerization method and a hydrogenation method of a norbornene-based monomer and a copolymerizable monomer copolymerizable with the norbornene-based monomer include the methods described in JP-A-1-132626. The hydrogenation rate of the hydrogenated norbornene ring-opening polymer obtained is usually preferably 50% or more, more preferably 70% or more, and further preferably 90% or more.
A polymer having a hydrogenation ratio of less than 50% has a low hydrogenation ratio, so that the resulting film has reduced light resistance and heat resistance deterioration.
[0011]
The number average molecular weight of the norbornene-based ring-opened polymer of the present invention and its hydrogenated product measured by high performance liquid chromatography is in the range of 50,000 to 1,000,000.
If the number average molecular weight is less than 50,000, the mechanical properties of the molding material obtained from the norbornene-based ring-opened polymer and its hydrogenated product are insufficient, which is not preferable. Further, when the number average molecular weight exceeds 1,000,000, the viscosity becomes extremely high when dissolved in a solvent, and it becomes difficult to cast, and the melt viscosity at the time of melting is too high, so that it can be uniformly formed at the time of melt molding. Cannot be used because of difficulty.
[0012]
The molecular weight distribution (weight average molecular weight / number average molecular weight) of the norbornene-based ring-opened polymer and its hydrogenated product of the present invention is 2.0 or less. If the molecular weight distribution is more than 2.0, gel-like impurities are generated, resulting in defects in the appearance of the molded product, and cannot be used.
A more preferable range of the molecular weight distribution is 1.8 or less, and still more preferably 1.6 or less.
[0013]
The norbornene-based ring-opening polymer of the present invention can be polymerized using a known polymerization catalyst, but when a functional group having a high polarity is present, a ruthenium-based or osmium-based polymerization catalyst is stable, It is preferable in terms of the polymerization rate.
As the ruthenium-based catalyst, a highly active ruthenium complex catalyst which can be used in the air and is not so unstable to water is preferable. As such a ruthenium complex catalyst, for example, a ruthenium (or osmium) alkylidene complex catalyst described in US Pat. No. 5,831,108, and further excellent in heat resistance, oxygen resistance and reaction controllability, The ruthenium complex catalysts represented by the general formulas (1) to (4) are particularly preferred.
[0014]
Embedded image

[0015]
In the general formula (1), R ³ and R ⁴ are the same or different, hydrogen, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 carbon atoms. -20 carboxyl group, 2-20 carbon atom alkoxy group, 2-20 carbon atom alkenyloxy group, 6-20 carbon atom aryloxy group, 2-20 carbon atom alkoxycarbonyl group, 2-20 carbon atom Represents an alkylthio group or a ferrocene derivative, which may be optionally substituted by phenyl substituted by an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms. good.
[0016]
X ¹ and X ² represent the same or different arbitrary anionic ligands, and are preferably Cl or Br, and more preferably Cl.
[0017]
Further, L ¹ and L ² represent the same or different neutral electron donors, and are preferably phosphorus-based ligands. Examples of the phosphorus ligand include phosphine represented by the general formula: PR′R ″ R ′ ″. Here, R ′, R ″ and R ′ ″ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, preferably a methyl group, an ethyl group, and an isopropyl group. Group, a t-butyl group, a cyclohexyl group, a phenyl group, or a substituted phenyl group. Specifically, -P (cyclohexyl) ₃ , -P (phenyl) ₃ , -P (isopropyl) _{3 and the} like can be mentioned.
[0018]
Further, as L ₁ and L ₂ , imidazolium compounds are also suitably used.
Specifically, imidazoline-2-ylidene derivatives and 4,5-dihydroimidazoline-2-ylidene derivatives are preferred, and more specifically, N, N'-dimesitylimimidazoline-2-ylidene ligands and N And N'-dimesityl-4,5-dihydroimidazoline-2-ylidene ligand and the like are more preferred.
Furthermore, L1 and L2 may be the same molecule and may be in a bidentate configuration.
[0019]
Note that two or three of X ¹ , X ² , L ¹ , and L ² may further form a polydentate chelating ligand.
Further, in the above general formula (1), L ¹ and L ² are described as being trans to each other. However, due to their steric bulkiness, and in the case of bidentate coordination with the same molecule, etc., cis coordination occurs. Can also be taken.
Further, X ¹ and X ² are described in the cis position with respect to each other, but may be in a trans configuration depending on the type of L ¹ and L ² .
[0020]
In the general formula (2), R ⁵ and R ⁶ are the same or different hydrogen, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 carbon atoms. -20 carboxyl group, 2-20 carbon atom alkoxy group, 2-20 carbon atom alkenyloxy group, 6-20 carbon atom aryloxy group, 2-20 carbon atom alkoxycarbonyl group, 2-20 carbon atom Represents an alkylthio group, an alkylsilyl group having 2 to 20 carbon atoms, an arylsilyl group having 2 to 20 carbon atoms, or a ferrocene derivative, and these are an alkyl group having 1 to 5 carbon atoms, a halogen atom, It may be optionally substituted by phenyl substituted by an alkoxy group of 5.
[0021]
However, when an alkylsilyl group or an arylsilyl group is used as R ⁵ , it can be selected on silicon from the viewpoint of the stability of the complex. In this case, a methyl group, an ethyl group, an isopropyl group, a t-butyl group is used. It is preferably selected from a group, a cyclohexyl group, a phenyl group and the like. Specific examples include a trimethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a dimethyl t-butylsilyl group, and a triisopropylsilyl group. In this case, in view of the stability and activity of the complex, R ⁶ is t-butyl, n-butyl, n-propyl, isopropyl, ethyl, methyl, methoxymethyl, or ferrocenyl. , A trimethylsilyl group, a phenyl group, a tolyl group, an anisyl group and the like.
[0022]
X ³ and X ⁴ represent the same or different arbitrary anionic ligands, and are preferably Cl or Br, and more preferably Cl.
[0023]
Further, L ³ and L ⁴ represent the same or different neutral electron donors, and are preferably phosphorus-based ligands. Examples of the phosphorus ligand include a phosphine represented by a general formula: PR′R ″ R ′ ″. Here, R ′, R ″ and R ′ ″ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, preferably a methyl group, an ethyl group, and an isopropyl group. Group, a t-butyl group, a cyclohexyl group, a phenyl group, or a substituted phenyl group. Specifically, -P _{(cyclohexyl) 3} [PCy ₃ abbreviated], -P _(phenyl) 3, -P _{(isopropyl) 3.}
[0024]
Further, as L ³ and L ⁴ , imidazolium compounds are also preferably used.
Specifically, imidazoline-2-ylidene derivatives and 4,5-dihydroimidazoline-2-ylidene derivatives are preferred, and more specifically, N, N'-dimesitylimimidazoline-2-ylidene ligands and N And N'-dimesityl-4,5-dihydroimidazoline-2-ylidene ligand and the like are more preferred.
Furthermore, L ³ and L ⁴ may be the same molecule and may be bidentate.
[0025]
In addition, two or three of X ³ , X ⁴ , L ³ , and L ⁴ may be further combined to form a polydentate chelating ligand.
[0026]
In the general formula (3) or (4), R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are the same or different hydrogen, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and a carbon number. 6-20 aryl groups, C2-C20 carboxyl group, C2-C20 alkoxy group, C2-C20 alkenyloxy group, C6-C20 aryloxy group, C2-C20 An alkoxycarbonyl group, an alkylthio group having 2 to 20 carbon atoms or a ferrocene derivative, which is an alkyl group having 1 to 5 carbon atoms, a halogen atom, a phenyl group substituted by an alkoxy group having 1 to 5 carbon atoms, It may be substituted as needed.
[0027]
Further, as R ⁷ , R ⁹ , and R ¹⁰ , an alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, a phenyl group, an alkyl group having 1 to 5 carbon atoms, an alkyloxy group having 1 to 5 carbon atoms, It is preferably a phenyl group substituted with a carboxyl group, an alkylsilyl group having 1 to 5 carbon atoms, a hydroxyl group, a nitro group, a halogen, an amino group having 5 or less carbon atoms, an acetyl group, an acetoxy group, and the like. o-tolyl group, p-tolyl group, 2,6-xylyl group, anisyl group, nitrobenzene group, chlorobenzene group, o-isopropylphenyl group, 2,6-diisopropylphenyl group, ethyl group, isopropyl group, t-butyl group And a cyclohexyl group.
[0028]
Y ¹ , Y ² , and Y ³ represent the same or different elements of sulfur, oxygen, and selenium, and among them, sulfur and selenium are preferable.
[0029]
X ⁵ , X ⁶ , X ⁷ , and X ⁸ represent the same or different arbitrary anionic ligands, and are preferably Cl or Br, and more preferably Cl.
[0030]
Further, L ⁵ , L ⁶ , L ⁷ , and L ⁸ represent the same or different neutral electron donors, and are preferably phosphorus-based ligands. As the phosphorus-based ligands of the formula: PR ^{'R' 'phosphine} represented by R'^'', and the like. Here, R ^′ , R ^″ , and R ^{″ ″} each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably a methyl group, an ethyl group, It is selected from an isopropyl group, a t-butyl group, a cyclohexyl group, a phenyl group, or a substituted phenyl group, and can be selected repeatedly. Specifically, -P (cyclohexyl) ₃ , -P (phenyl) ₃ , -P (isopropyl) _{3 and the} like can be mentioned.
[0031]
As L ⁵ , L ⁶ , L ⁷ , and L ⁸ , imidazolium compounds are also suitably used. Specifically, imidazoline-2-ylidene derivatives and 4,5-dihydroimidazoline-2-ylidene derivatives are preferred, and more specifically, N, N'-dimesitylimimidazoline-2-ylidene ligands and N , N'-dimesityl-4,5-dihydroimidazoline-2-ylidene ligands.
Further, L ⁵ , L ⁶ , L ⁷ , and L ⁸ may be the same molecule and have a bidentate coordination.
[0032]
Note that two or three of X ⁵ , X ⁶ , X ⁷ , X ⁸ , L ⁵ , L ⁶ , L ⁷ , and L ⁸ may be further combined to form a polydentate chelating ligand. good.
[0033]
The ruthenium-based complexes represented by the general formulas (1) to (4) can be produced by various methods. As a typical method, on the other hand, a ligand precursor having L ^{1 to} L ⁸ is used. A raw material such as a compound is synthesized according to a known method, while a ruthenium complex precursor raw material is synthesized according to a known method, and finally, both raw materials are mixed and a ligand exchange reaction is performed to produce the compound. .
[0034]
The metathesis polymerization reaction is preferably performed in an inert gas atmosphere, but when a ruthenium-based stable catalyst is used, the polymerization can be performed in air.
Generally, a resin obtained by a metathesis polymerization reaction has a double bond and may be deteriorated by oxygen in the air or the like. In order to prevent this deterioration, an antioxidant can be added to the polymerization system.
[0035]
In the polymerization using the ruthenium-based complex, a chain transfer agent can be used to control the molecular weight. The chain transfer agent must have a chain structure having at least one double bond. Among them, chain transfer agents preferably used without causing polymerization inhibition include 1-butene, 1-pentene, α-olefins such as 1-hexene and allyl acetate, vinyl acetate, but are not particularly limited, Functional groups and various substituents may be present. Since the ruthenium-based complex is not easily decomposed by the functional group, the functional group can be efficiently introduced into the terminal of the polymer by using a chain transfer agent having various functional groups.
[0036]
The amount of the chain transfer agent to be added is preferably in the range of 1/150 to 1/8000 mol, more preferably 1/250 to 1/5000 mol, based on the norbornene-based monomer.
[0037]
Examples of the hydrogenation catalyst used for synthesizing the norbornene ring-opening polymer hydride of the present invention include Wilkinson complex, cobalt acetate / triethylaluminum, nickel acetylacetate / triisobutylaluminum, palladium-carbon, ruthenium complex, ruthenium-carbon , Nickel-diatomaceous earth and the like.
[0038]
When the catalyst used in the ring-opening polymerization described above has a structure of the above formulas (1) to (4), these can be used as a hydrogenation catalyst.
In other words, hydrogenation can be performed without performing purification after polymerization by directly performing hydrogenation after polymerization.
The above-mentioned hydrogenation is carried out at 0 to 250 ° C under a hydrogen pressure of 0.1 to 20 MPa in a homogeneous or heterogeneous system depending on the type of the catalyst.
[0039]
The hydrogenated product of the norbornene ring-opening polymer of the present invention can be particularly suitably used for optical film applications. By increasing the molecular weight of the hydrogenated product of the resulting norbornene-based ring-opening polymer while controlling the molecular weight distribution, it is possible to produce a film with no appearance defects due to generation of gel-like impurities and excellent mechanical properties. be able to. Among the above optical film applications, it can be particularly suitably used as a polarizing plate protective film.
[0040]
When an optical film was prepared from a hydrogenated product of the norbornene ring-opening polymer of the present invention, the number of defects was less than 10 per square meter (point defects per square meter by visual inspection at an inspection area of 10 square meters). Number), more preferably 3 or less.
[0041]
The resin of the present invention can produce a film having few defects as described above.
[0042]
DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited by these embodiments. In addition, the measurement and evaluation of each characteristic were performed according to the following conditions.
[0043]
(1) Measurement of Molecular Weight by High-Performance Liquid Chromatography Measurement conditions using HLC-8020 manufactured by Tosoh Corporation, AS-8020 autosampler, SC-8020 data analysis, K-806L manufactured by Column Shodex (using two tubes). The flow rate was 1 ml / min, the oven temperature was 40 ° C., the refractometer temperature was 40 ° C., the sample concentration was about 0.1 wt%, the sample injection amount was 300 μl, the solvent was chloroform, and the standard sample was standard polystyrene.
[0044]
(2) Measurement of Elongation at Break Evaluated by TENSILON (manufactured by ORIENTEC).

[0045]
(3) Appearance The obtained film was evaluated by visual inspection (inspection area 10 m ² ) for the number of defects by a transmission system.
[0046]
[Synthesis example 1 of catalyst]
Relative Ru ^{(p-cymene) C 12} of 5.57 g (9.1 mmol), under a nitrogen stream in a flask of 300ml of PCy ₃ and 9.1 mmol of t- butyl acetylene 18.2mmol with toluene 150 ml, The reaction was performed for 7 hours. After completion of the reaction, toluene was removed under reduced pressure, and recrystallization was performed in a THF / ethanol system to synthesize a ruthenium complex compound represented by the following formula (5).
[0047]
Embedded image

[0048]
[Synthesis example 2 of catalyst]
According to the method described in US Pat. No. 5,831,108, a ruthenium complex compound represented by the following formula (6) was synthesized.
[0049]
Embedded image

[0050]
[Synthesis example 3 of catalyst]
According to the method described in WO 99/00396, a ruthenium complex compound of the following formula (7) was synthesized.
[0051]
Embedded image

[0052]
(Example 1)
0.01 mol of allyl acetate and 0.002 mol of the ruthenium complex of the formula (5) were dissolved in 10 mL of cyclohexane, and added to a solution of 10 mol of tetracyclododecene dissolved in 4 L of cyclohexane. The reaction solution was reacted at a reflux temperature of cyclohexane for 24 hours under a nitrogen stream. Thereafter, the temperature was lowered to room temperature, and 0.02 mol of ethyl vinyl ether was added. The obtained reaction solution was purified by reprecipitation using 10 L of methanol, and dried under reduced pressure to obtain a ring-opened polymer. The polymerization results are shown in Table 1.
[0053]
450 g of the obtained ring-opening polymer was dissolved in 9000 ml of tetrahydrofuran, 45 g of a palladium-alumina catalyst having a palladium concentration of 5% by mass was added, and hydrogen gas was charged so that the pressure became 9.8 MPa, and the mixture was heated at 150 ° C. for 5 hours. A hydrogenation reaction was performed. After the hydrogenation reaction, the catalyst was separated by filtration, and the filtrate was poured into a large excess of methanol acidic with hydrochloric acid to obtain a hydrogenated product of a ring-opened polymer. The hydrogenation rate of the hydrogenated product was substantially 100%. The results are shown in Table 1.
The obtained hydrogenated product of the ring-opened polymer was melt-mixed at 280 ° C. using a twin-screw extruder, and a film having a thickness of 40 μm was produced with a T-die. Table 1 shows the evaluation results of the physical properties of the obtained film.
[0054]
(Example 2)
0.005 mol of allyl acetate and 0.002 mol of ruthenium complex (6) are dissolved in 10 mL of cyclohexane, and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 represented by the following formula (8) is dissolved. ^2,5 . 10 mol of [ ^17,10 ] -3-dodecene was added to a solution of 4 L of cyclohexane. The reaction solution was reacted at a reflux temperature of cyclohexane for 24 hours under a nitrogen stream. Thereafter, the temperature was lowered to room temperature, and 0.02 mol of ethyl vinyl ether was added. The obtained reaction solution was purified by reprecipitation using 10 L of methanol, and dried under reduced pressure to obtain a ring-opened polymer. The polymerization results are shown in Table 1.
[0055]
After obtaining the hydrogenated product of the ring-opened polymer in the same manner as in Example 1, the hydrogenated product was melt-mixed at 280 ° C. using a twin screw extruder, and a 40 μm thick film was formed with a T-die. Manufactured. Table 1 shows the evaluation results of the physical properties of the obtained film.
[0056]
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[0057]
(Example 3)
A film was obtained by performing the same operation as in Example 2 except that the ruthenium complex (7) was used instead of the ruthenium complex (6), and the physical property evaluation results of the film are shown in Table 1.
[0058]
(Comparative Example 1)
10 mol of tetracyclododecene was dissolved in 4 L of cyclohexane, 50 mL of a cyclohexane solution in which 0.02 mol of triethylaluminum was dissolved, 0.005 mol of 1-hexene as a chain transfer agent, and 0.08 mol of triethylamine were added. . While maintaining this solution at 30 ° C., polymerization was carried out by continuously adding over 1 hour to 50 mL of a cyclohexane solution in which 10 mol of tetracyclododecene and 0.02 mol of titanium tetrachloride were dissolved.
The total amount of tetracyclododecene and titanium tetrachloride was added, and 30 minutes later, 20 mL of a cyclohexane solution in which 0.005 mol of tungsten hexachloride was dissolved was added, and the mixture was further stirred for 30 minutes. Thereafter, the reaction solution was purified by reprecipitation with methanol, and dried under reduced pressure to obtain a ring-opened polymer. The results are shown in Table 1.
[0059]
450 g of the obtained ring-opening polymer was dissolved in 9000 ml of cyclohexane, 45 g of a palladium-alumina catalyst having a palladium concentration of 5% by mass was added, and hydrogen gas was charged so that the pressure became 9.8 MPa, and the mixture was heated at 150 ° C. for 5 hours. A hydrogenation reaction was performed. After the hydrogenation reaction, the catalyst was separated by filtration, and the filtrate was poured into a large excess of methanol acidic with hydrochloric acid to obtain a hydrogenated product of a ring-opening polymer. The hydrogenation rate of the polymer was substantially 100%. The results are shown in Table 1.
The obtained hydrogenated product of the ring-opened polymer was melt-mixed at 280 ° C. using a twin-screw extruder, and a film having a thickness of 40 μm was produced with a T-die. Table 1 shows the evaluation results of the physical properties of the obtained film.
[0060]
(Comparative Example 2)
In a reaction vessel purged with nitrogen gas, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 3 ^7,10 ] -3-dodecene, 200 ml of 1,2-dichloroethane, 0.01 mol of 1-hexene as a chain transfer agent, and chlorobenzene having a concentration of tungsten hexachloride of 0.07 M / liter as a catalyst. By adding 90 ml of the solution, 70 ml of a 1,2-dichloroethane solution having a concentration of 0.15 M / liter of paraaldehyde, and 37 ml of a toluene solution having a concentration of 0.7 M / liter of triisobutylaluminum, and reacting at 60 ° C. for 8 hours. 440 g of a ring-opened polymer was obtained.
[0061]
This ring-opened polymer was dissolved in 9000 ml of tetrahydrofuran, 45 g of a palladium-alumina catalyst having a palladium concentration of 5% by weight was added, hydrogen gas was charged to a pressure of 100 kg / cm 2, and hydrogenation reaction was performed at 140 ° C. for 5 hours. I let it.
After the hydrogenation reaction, the catalyst was filtered off, and the filtrate was poured into a large excess of methanol acidic with hydrochloric acid to obtain a hydrogenated product of a ring-opened polymer. The hydrogenation rate of this polymer was substantially 100%.
The hydrogenated product of the obtained ring-opened polymer was melt-mixed at 280 ° C. using a twin-screw extruder, and a film having a thickness of 40 μm was produced with a T-die. Table 1 shows the evaluation results of the physical properties of the obtained film.
[0062]
[Table 1]

[0063]
The norbornene-based ring-opened polymer and the hydrogenated product thereof according to the present invention have the above-mentioned constitution, and the film obtained from the hydrogenated product has heat resistance, transparency, elongation, elastic modulus and the like. It is excellent in mechanical properties, has few appearance defects, and is suitably used as an optical component and an electrical / electronic insulating material.

Claims (6)

A ring-opened polymer of a norbornene-based monomer, having a number average molecular weight of 50,000 to 1,000,000 as measured by high performance liquid chromatography and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.0 or less. Norbornene ring-opening polymer. A hydrogenated product of a ring-opened polymer of a norbornene-based monomer, having a number average molecular weight of 50,000 to 1,000,000 and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.0 or less, as measured by high performance liquid chromatography. A hydrogenated product of a norbornene-based ring-opening polymer, characterized in that: The method for producing a norbornene-based ring-opened polymer according to claim 1, wherein the polymerization is carried out using a ruthenium-based catalyst and a chain transfer agent in an amount of 1/150 to 1/8000 mol with respect to the norbornene-based monomer. The hydrogenated product of the norbornene-based ring-opening polymer according to claim 2, wherein the polymerization is performed using a ruthenium-based catalyst and a chain transfer agent in an amount of 1/150 to 1/8000 mol with respect to the norbornene-based monomer. Production method. An optical film comprising a hydrogenated product of the norbornene ring-opening polymer according to claim 2. The optical film of claim 7, wherein the number of the drawbacks of per 1 m ² is less than 10.