JP3797298B2 - Laminated body - Google Patents

Description

【００１８】
〔ただし、式中、Ｒ₁およびＲ₂は、水素、炭化水素残基またはハロゲン、エステル、ニトリル、ピリジルなどの極性基で、それぞれ同一または異なっていてもよく、また、Ｒ₁およびＲ₂は、互いに環を形成してもよい。ｎは、正の整数である。ｑは、０または正の整数である。〕
【００１９】
一般式〔Ｉ〕で表される構造単位を有するポリマーは、単量体として、例えば、ノルボルネン、並びにそのアルキルおよび／またはアルキリデン置換体、例えば、５−メチル−２−ノルボルネン、５，６−ジメチル−２−ノルボルネン、５−エチル−２−ノルボルネン、５−ブチル−２−ノルボルネン、５−エチリデン−２−ノルボルネン等；ジシクロペンタジエン、２，３−ジヒドロジシクロペンタジエン、これらのメチル、エチル、プロピル、ブチル等のアルキル置換体、およびハロゲン等の極性基置換体；ジメタノオクタヒドロナフタレン、そのアルキルおよび、またはアルキリデン置換体、およびハロゲン等の極性基置換体、例えば、６−メチル−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−エチル−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−エチリデン−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−クロロ−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−シアノ−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−ピリジル−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−メトキシカルボニル−１，４：５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン等；シクロペンタジエンの３〜４量体、例えば、４，９：５，８−ジメタノ−３ａ，４，４ａ，５，８，８ａ，９，９ａ−オクタヒドロ−１Ｈ−ベンゾンデン、４，１１：５，１０：６，９−トリメタノ−３ａ，４，４ａ，５，５ａ，６，９，９ａ，１０，１０ａ，１１，１１ａ−ドデカヒドロ−１Ｈ−シクロペンタアントラセン等を１種または２種以上使用し、公知の開環重合方法により重合して得られる開環重合体を、通常の水素添加方法により水素添加して製造される飽和ポリマーである。
【００２０】
目的とする開環重合体水素添加物（飽和ポリマー）のガラス転移温度（Ｔｇ）を１００℃以上とするには、これらのノルボルネン系モノマーの中でも４環体また５環体のものを使用するか、これらを主成分とし、２環体や３環体のモノマーと併用することが好ましい。特に、複屈折の点では、４環体の低級アルキル置換体またはアルケニル置換体を主成分とすることが好ましい。
【００２１】
また、熱可塑性飽和ノルボルネン系モノマーは、重合体〔Ｉ〕の製造過程で、分子量調節剤として、１−ブテン、１−ペンテン、１−ヘキセンなどのα−オレフィンを存在させたり、あるいはシクロプロペン、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテン、５，６−ジヒドロシクロペンタジエン等のシクロオレフィンなどの他のモノマー成分を少量成分として添加することにより、共重合したポリマーであっても構わない。
【００２２】
本発明における熱可塑性飽和ノルボルネン系ポリマーは、トルエンを溶剤とする高速液体クロマトグラフィー（ＨＬＣ）分析により測定した数平均分子量（Ｍｎ）が５０，０００〜５００，０００、好ましくは、６０，０００〜２００，０００、重量平均分子量（Ｍｗ）が１００，０００〜２，０００，０００、好ましくは１００，０００〜１，０００，０００であって、その分子量分布（Ｍｗ／Ｍｎ）が２．４以上であることが好ましい。
【００２３】
ＭｎおよびＭｗが上記範囲より小さいと、押出成形してフィルムやシート、棒などを成形した場合に、十分な強度をもつ成形品が得られない。逆に、この範囲よりも大きいと成形性が悪くなり、押出成形しようとしても粘度が高すぎるため成形が困難である。また、適当な溶剤に溶解してキャストや紡糸しようとしても溶剤に対する溶解性が不十分である。しかも、そのような高分子量ポリマーは、合成反応を制御するのが難しく、品質の安定した材料が得られないという不都合が生じる。
【００２４】
また、分子量分布（Ｍｗ／Ｍｎ）は、好ましくは２．４以上、特に好ましくは２．８以上である。
【００２５】
一般に、熱可塑性ポリマーは、分子量分布の小さい、単分散に近いポリマーほど強度と成形性のバランスに優れていて性能が良いとされている。しかしながら、本発明のように分子量の比較的大きなポリマーを押出成形して、例えば、シートやフィルムにする場合、溶融状態から冷却されて固まっていく過程において、単分散の分子がある温度において一瞬に同時に固まるよりも、いろいろな分子量の分子が分子量の大きい方から順番に段々と固まって行く場合の方が、応力が残留せず、全体に平坦で奇麗な成形品が得られる。熱可塑性飽和ノルボルネン系ポリマーでは、ポリマーが剛直であり、さらに耐熱性が高く成形温度が３００℃近くのかなりの高温になるため、この傾向が特に顕著である。このため、本発明の目的のためには、分子量分布は、好ましくは２．４以上、特に好ましくは２．８以上である。分子量分布が、この範囲より小さい場合には、押出成形がしにくく、平滑性や光学的特性などの良好な成形品が得難いという欠点がある。
【００２６】
分子量分布（Ｍｗ／Ｍｎ）が大きくなるにしたがって、成形性が改良される。一般的に、ポリカーボネートのように耐熱性が高く、剛性の高いポリマーでは、溶融状態から急激に冷却されると、内部に歪みが生じて、平坦な成形物が得られないという現象が起きやすい。熱可塑性飽和ノルボルネン系ポリマーでも同様のことがある。例えば、押出機でＴダイから押出して、シート状に引き取る場合、ロールの温度を高くしてやらないと平坦なシートが引けないという現象が起こる。Ｔｇが１４０℃程度のポリマーの場合、ロール温度を１２０〜１４０℃に上げることにより、平坦に引くことができる。しかし、通常は、ロールの加熱は、水による場合が多く、ロールの温度を最高でも９０℃位までしか上げられないことが多い。
【００２７】
分子量分布が２．４未満の場合では、ロールの温度を約１４０℃とポリマーのガラス転移温度付近まで上げても、うまく成形できないが、２．４以上では１１０〜１３０℃程度にロールの温度を上げることにより、平坦な成形物が成形可能となる。さらに、分子量分布が２．８以上に広がると、ますます成形性が改良され、９０〜１００℃位のロール温度でも平坦で、内部歪みのない成形物が可能となる。分子量分布の上限は、特にないが、あまり大きくなりすぎると、Ｍｎが大きくて、溶融粘度の高い割りには充分な強度が得られないこと、およびそのようなポリマー自体の合成が難しくなることから、概ね６．０以下が好ましい。
【００２８】
このような分子量（Ｍｎ、Ｍｗ）と分子量分布（Ｍｗ／Ｍｎ）を持った熱可塑性飽和ノルボルネン系ポリマーは、合成反応において、例えば、触媒の使用量を加減したり、重合温度を変えたり、分子量調節剤を用いる場合にはその種類や量を加減したり、さらには、モノマーをプロップで反応系に後添加したり、あるいは分子量の小さいものと大きなものを別々に合成しておいてこれらをブレンドして分子量分布を広げる等の方法により製造することができる。
【００２９】
合成したポリマーの分子鎖中に残留する不飽和結合を水素添加反応により飽和させる場合には、耐光劣化や耐候劣化性などの観点から、水素添加率を９０％以上、好ましくは９５％以上、特に好ましくは９９％以上とする。
【００３０】
本発明における熱可塑性飽和ノルボルネン系ポリマーは、耐熱性および成形性の観点から、Ｔｇが１００℃以上、好ましくは１２０〜２００℃、さらに好ましくは１３０〜１８０℃であることが望ましい。
【００３１】
（２）揮発成分の低減方法
熱可塑性飽和ノルボルネン系ポリマーは、通常の合成方法では０．５重量％以上の揮発成分を含むのが一般的である。本発明の成形材料は、熱可塑性飽和ノルボルネン系ポリマーの中に含まれる揮発成分が、０．３重量％以下、好ましくは０．２重量％以下、さらに好ましくは０．１重量％以下のものであることが望ましい。本発明においては、示差熱重量測定装置（セイコー電子工業社製ＴＧ／ＤＴＡ２００）を用いて、３０℃から３５０℃までの加熱減量を求め、その量を揮発成分の含有量とする。揮発成分の含有量が上記範囲より多いと、約２５０〜３５０℃の温度で押出成形した場合に、揮発成分が成形中に揮発し、発泡して成形品内部の欠陥になったり、強度を低下させたり、あるいは表面に条痕となって現れたりする。
【００３２】
揮発分の低減方法としては、例えば、貧溶媒によるポリマー凝固法では、凝固を繰り返し実施する方法がある。直接乾燥法では、２５０℃以上、３０Ｔｏｒｒ以下で、薄膜乾燥機や押出乾燥機を用いて乾燥することが望ましい。また、予めポリマーの溶媒溶液を数十％に濃縮した後に、直接乾燥することもできる。もちろん、これらの方法に限定されるものではない。これらの方法によって製造された熱可塑性飽和ノルボルネン系ポリマーは、実質的に非晶性であり、透明性、寸法安定性、耐熱性、吸水性に優れ、透湿性がほとんど認められない。
【００３３】
（３）酸化防止剤
本発明において、熱可塑性飽和ノルボルネン系ポリマー１００重量部に対して、低揮発性の酸化防止剤を０．０１〜５重量部の割合で配合すると、成形加工時のポリマーの分解や着色を効果的に防止することができる。
【００３４】
酸化防止剤としては、２０℃における蒸気圧が１０^-5Ｐａ以下、特に好ましくは１０^-8Ｐａ以下の酸化防止剤が望ましい。蒸気圧が１０^-5Ｐａより高い酸化防止剤は、押出成形する場合に発泡したり、また、高温にさらされたときに成形品の表面から酸化防止剤が揮散するという問題が起こる。
【００３５】
本発明で使用できる酸化防止剤としては、例えば、次のようなものを挙げることができ、これらのうちの一種または数種を組合せて用いてもよい。
【００３６】
ヒンタードフェノール系
２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔ−ブチルフェノール、４−ヒドロキシメチル−２，６−ジ−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチル−α−メトキシ−ｐ−ジメチル−フェノール、２，４−ジ−ｔ−アミルフェノール、ｔ−ブチル−ｍ−クレゾール、４−ｔ−ブチルフェノール、スチレン化フェノール、３−ｔ−ブチル−４−ヒドロキシアニソール、２，４−ジメチル−６−ｔ−ブチルフェノール、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルフォスフォネート−ジエチルエステル、４，４′−ビスフェノール、４，４′−ビス−（２，６−ジ−ｔ−ブチルフェノール）、２，２′−メチレン−ビス−（４−メチル−６−ｔ−ブチルフェノール）、２，２′−メチレン−ビス−（４−メチル−６−α−メチルシクロヘキシルフェノール）、４，４′−メチレン−ビス−（２−メチル−６−ｔ−ブチルフェノール）、４，４′−メチレン−ビス−（２，６−ジ−ｔ−ブチルフェノール）、１，１′−メチレン−ビス−（２，６−ジ−ｔ−ブチルナフトール）、４，４′−ブチリデン−ビス−（２，６−ジ−ｔ−ブチル−メタ−クレゾール）、２，２′−チオ−ビス−（４−メチル−６−ｔ−ブチルフェノール）、ジ−ｏ−クレゾールスルフィド、２，２′−チオ−ビス−（２−メチル−６−ｔ−ブチルフェノール）、４，４′−チオ−ビス（３−メチル−６−ｔ−ブチルフェノール）、４，４′−チオ−ビス−（２，３−ジ−ｓｅｃ−アミルフェノール）、１，１′−チオ−ビス−（２−ナフトール）、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルエーテル、１，６−ヘキサンジオール−ビス−〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン、２，２−チオ−ジエチレンビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、２，２−チオビス（４−メチル−６−ｔ−ブチルフェノール）、Ｎ，Ｎ′−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナマミド）、ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）カルシウム、１，３，５−トリメチル−２，４，６−トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、トリエチレングリコール−ビス〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート〕、１，３，５−トリメチル−２，４，６，−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−イソシアヌレート、ペンタエリスリチル−テトラキス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシジェニル）プロピオネート〕等。
【００３７】
アミノフェノール類
ノルマルブチル−ｐ−アミノフェノール、ノルマルブチロイル−ｐ−アミノフェノール、ノルマルペラゴノイル−ｐ−アミノフェノール、ノルマルラウロイル−ｐ−アミノフェノール、ノルマルステアロイル−ｐ−アミノフェノール、２、６−ジ−ｔ−ブチル−α−ジメチル、アミノ−ｐ−クレゾール等。
【００３８】
ハイドロキノン系
ハイドロキノン、２，５−ジ−ｔ−ブチルハイドロキノン、２，５−ジ−ｔ−アミルハイドロキノン、ハイドロキノンメチルエーテル、ハイドロキノンモノベンジルエーテル等。
【００３９】
ホスファイト系
トリホスファイト、トリス（３，４−ジ−ｔ−ブチルフェニル）ホスファイト、トリス（ノニルフェニル）フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４′−ビフェニレンフォスファナイト、２−エチルヘキシルオクチルフォスファイト等。
【００４０】
その他
２−メルカプトベンゾチアゾール亜鉛塩、ジカテコールボレート−ジ−ｏ−トリルグアニジン塩、ニッケル−ジメチルジチオカーバメイト、ニッケル−ペンタメチレンンジチオカルバネート、メルカプトベンズイミダゾール、２−メルカプトベンズイミダゾール亜鉛塩等。
【００４１】
（４）その他の成分
本発明の熱可塑性飽和ノルボルネン系ポリマーには、酸化防止剤以外の添加剤として、本発明の目的を損なわない範囲で各種の帯電防止剤、滑材、界面活性剤、紫外線吸収剤等を添加して用いてもよい。また、光学用材料以外の用途に用いる場合には、必要に応じて、ガラス繊維等のフィラー、染料、顔料等の添加剤を添加して用いてもよい。
【００４２】
（５）ペレット化および予備乾燥
プラスチック材料は、通常、直径１〜７ｍｍ程度、長さ４〜８ｍｍ程度のペレットとして供給され、これを押出成形法や射出成形法により所望の形状に成形加工される。ところで、一般に、合成後のポリマーは、凝固法や直接乾燥法により合成の際に使用した溶剤を除去し、これに前述した各種添加剤を必要量添加し、熱可塑性飽和ノルボルネン系ポリマーの場合では、概ね２３０℃以上の温度の溶融状態で所定の直径のストランド状に押出し、次いで適当なストランドカッターにより所望の長さに刻んでペレットとする。
【００４３】
通常のプラスチック材料では、このペレットをそのまま成形加工するが、例えば、ポリカーボネート樹脂、アクリル樹脂、ポリアミド樹脂等の吸湿性が高かったり、分解し易い樹脂では、ペレットの保存中に水分を吸着したり、分解物により、そのまま成形すると、激しく発泡したり、成形品の表面に大きな条痕などの欠陥が発生するため、使用する前にその樹脂のガラス転移温度以下で数時間予備乾燥してから成形するという方法が一般的になっている。
【００４４】
しかしながら、熱可塑性飽和ノルボルネン系ポリマーは吸湿性が小さく、また、保存中に分解するような成分も含まないことから、従来、この予備乾燥は不要と考えられ、予備乾燥なしに成形されていた。実際に予備乾燥を試みても、揮発成分はほとんど検出されない。ところが、驚くべきことに、熱可塑性飽和ノルボルネン系ポリマーのペレットを予備乾燥したところ、予備乾燥なしでは目視では見えない微細なボイドやクラック状の欠陥が成形品に発生しているのに対して、これらのミクロボイドのない成形品の得られることが見出された。
【００４５】
このようにして得られた成形品は、成形後においてもミクロボイドの発生がなく、さらに、例えば、７０℃以上、相対湿度８０％以上２０時間以上の高温高湿度下での耐久試験後にもミクロボイドが発生しない。また、この乾燥処理は、射出成形する場合にも有効であることも確認した。
【００４６】
予備乾燥の条件としては、温度が高く、乾燥時間の長い方が効果的であるが、温度が樹脂のガラス転移温度を超えて高すぎるとペレットどうしが熱融着して使用しにくくなることと、数時間で効果が飽和することから、好ましくは（Ｔｇ−３０）〜（Ｔｇ−５）℃、特に好ましくは（Ｔｇ−２０）〜（Ｔｇ−５）℃で、好ましくは１時間以上、特に好ましくは２時間以上処理することが望ましい。
【００４７】
乾燥は、真空乾燥でも、空気または窒素雰囲気下での常圧乾燥でも、効果がある。乾燥処理終了から成形に使用するまでの時間は、短いに越したことはないが、特に短時間である必要はなく、数日以上経過しても効果は失われない。
【００４８】
（６）成形方法
押出成形
本発明の熱可塑性飽和ノルボルネン系ポリマーは、特に押出成形に適しているが、これに限定するものではない。押出成形では、溶融押出機を用い、熱可塑性飽和ノルボルネン系ポリマーを２５０〜３００℃程度に加熱し、Ｔ型またはマニホール型のダイから押出し、各種ロールで巻き取ることにより、シートやフィルムに成形加工することができる。この場合、熱可塑性飽和ノルボルネン系ポリマーは、耐熱性が高く、剛性が高いことから、ロールで急激に冷やすとポリカーボネート同様表面が波うって平坦に成形できないため、１段目および２段目の巻き取り・冷却ロールを、前述したとおり、分子量分布（Ｍｗ／Ｍｎ）の値にしたがって、７０〜１４０℃程度の比較的高温にして、除冷するのが適当である。また、シート状の成形物を、さらに一軸または二軸方向に延伸して加工することも可能である。他に、カレンダーロールによる加工がある。
【００４９】
積層成形
熱可塑性飽和ノルボルネン系ポリマーの強度とガス透過性をさらに補うために、ポリエチレンやポリプロピレン等の他のオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ポリ塩化ビニルやポリ塩化ビニリデン等のハロゲン化炭化水素系の樹脂等と共押出加工やラミネート加工を行なうことが可能である。
【００５０】
その他の押出成形
熱可塑性飽和ノルボルネン系ポリマーを適当なダイから押し出すことにより、棒状やファイバー状、チューブ状に押出成形することができる。これらの押出成形品を、ガラス転移温度以下の温度で延伸して、さらに細い棒やチューブ状に加工することもできる。
【００５１】
架橋
さらに、強度を増すために、加熱または紫外線や電子線等の放射線照射による架橋もできる。この場合、適当な架橋剤を用いることが効果的である。架橋剤は、公知のものが使用でき、例えば、ジビニルベンゼン等のビニル基を複数有するモノマー類；ジアリルフタレート、エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート等の多官能アクリレート類；トリアリルイソシアヌレート等のイソシアヌレート類；液状ポリブタジエン等の不飽和結合を複数有するポリマー類が挙げられる。
【００５２】
他の成形法
本発明の熱可塑性飽和ノルボルネン系ポリマーは、溶融押出成形以外に、次のような成形方法が可能である。熱プレスにより、シート状に成形することができる。また、熱可塑性飽和ノルボルネン系ポリマーをベンゼン、トルエン、キシレン等の芳香族炭化水素系溶剤、シクロヘキサン、メチルシクロヘキサン、デカリン等の脂環族炭化水素系溶剤、クロロホルム、モノクロルベンゼン等のハロゲン系溶剤に溶解し、これらの溶液を平板上にキャスティングしたり、ロール上にキャスティングして、成膜することが可能である。分子量の比較的大きなポリマーについては、上記溶剤溶液から糸状に紡ぐこともできる。分子量の比較的小さなポリマーは、通常の射出成形の可能であるほか、回転成形など一般的な熱可塑性樹脂の加工方法が適用可能である。
【００５３】
（７）用途
光学用材料および導電性複合材料
本発明の熱可塑性飽和ノルボルネン系ポリマー（成形用材料）は、非晶質であり、透明性に優れ、複屈折が小さいという特徴があるため、各種光学用材料として、特に、光学記録媒体の基板材料として適している。
【００５４】
本発明の熱可塑性飽和ノルボルネン系ポリマーから得られた成形品は、その表面に、真空蒸着やスパッタリング等の薄膜形成方法によって、金属、金属酸化物、金属窒化物、金属硫化物、金属ハロゲン化物等を、目的に応じ、単層または多層に成膜することができる。この際、真空中でかなりの高温にさらされることもあるが、本発明によって得られた成形品は、揮発分が少なく、アウトガスが少ないため、短時間でチェンバーを所定の真空度に引くことができ、また、表面に「フクレ」等の発生のない平坦な膜を成膜することができる。
【００５５】
透明基板上に、光学的に記録および／または読み出し可能な記録薄膜を設けて記録媒体を製造することができる。記録薄膜（記録層）を形成する記録材料としては、公知の任意の希土類−遷移金属アモルファス合金でよく、例えば、Ｔｂ−Ｆｅ系合金（特公昭５７−２０６９１号）、Ｄｙ−Ｆｅ系合金（特公昭５７−２０６９２号）、Ｃｄ−Ｔｂ−Ｆｅ系合金（特開昭５６−１２６９０７号）、Ｃｄ−Ｔｂ−Ｄｙ−Ｆｅ系合金（特開昭５７−９４９４８号）、Ｃｄ−Ｃｏ系合金（特開昭５４−１２１７１９号）、Ｔｂ−Ｆｅ−Ｃｏ系等が挙げられる。これらの希土類−遷移金属アモルファス層は、蒸着、スパッタリング、イオンプレーティング等の薄膜形成方法で形成するのが好ましい。このアモルファス層の厚さは、一般に５００〜１５００Åである。また、相変化型記録材料を記録層としてもよく、例えば、Ｇｅ−Ｔｅ系、Ｓｂ−Ｔｅ系、Ｉｎ−Ｓｂ系、Ｇｅ−Ｓｂ−Ｔｅ系、Ｉｎ−Ｓｂ−Ｔｅ系等が挙げられる。これらの相変化型の記録材料は、蒸着、スパッタリング、イオンプレーティング等の方法で形成することが好ましい。このアモルファス層の厚さは一般に５００〜２０００Åである。
【００５６】
有機色素系記録材料も使用することができ、例えば、メチン・ポリメチン系（ジアニン：インドロニン型、チアゾール型等、クロコニウム類、スクアリリウム類）（特開昭５８−１７１３６９６号）；キノン類；ナフトキノン類、アントラキノン類（特開昭５９−１９９２９１号、特開昭５８−１１２７９３号）；フタロシアニン系（金属フタロシアニン類）（特開昭６１−２３５１８８、特開昭５９−１１２９２号）；ジチオール系（ジチオール金属錯体類）（特開昭５７−１１０９０号）；その他、テトラヒドコリン類、ジオキサン類、ジチアジン類、チアピリリウム類、ポリフィリン類（特開昭５８−１９７０８８、特開昭６１−２３５１８８号、特開昭５９−７８８９１号）等を挙げることができる。この有機色素系記録材料の成膜後の膜厚は、一般に５００〜５０００Åである。
【００５７】
また、例えば、Ｔｅ−ＣＳ₂、Ｐｂ−Ｔｅ−Ｓｅ、Ｔｅ−Ｃ、ＴｅＯ₂、Ｓｂ−Ｓｅ、Ｂｌ−Ｔｅ等や、バブル形成等の形状変化を用いて追記型記録カード等にも利用できる。さらに、金、白金、アルミニウム等を反射膜として用いることができる。
【００５８】
光記録媒体には、表面に表面保護層を設けたり、記録層と本発明のポリマーからなる基板との間に、保護層、反射層、誘電層を設けてもよい。これら保護層等の層形成材料としては、例えば、ＣｄＳ、ＺｎＳｅ、ＳｉＯ₂、Ｓｉ、Ｓｉ₃Ｎ、Ｓｉ₃Ｎ₄、ＡｌＮ、ＴｉＯ₂、ＴａＯ₂、ＭｇＦ₂等の無機物、あるいは紫外線硬化樹脂等の有機物を挙げることができる。さらに、光カード等では他の材料を直接貼り合せて用いることがあり、その場合は、貼り合せ方法として、溶剤、ホットメルト、ＵＶ硬化型接着剤等通常の接着剤の他に、高周波、超音波接着方法が使用される。
【００５９】
その他の用途
本発明の熱可塑性飽和ノルボルネン系ポリマーと成形用材料は、自動車用、医療用等を含めた短距離情報伝送用のプラスチック光ファイバーおよびそのコネクター類；情報をピックアップするためのレンズ、プロジェクター用のレンズ、メガネレンズ、スポーツ用ゴーグル、自動車等のヘッドランプおよびテールランプのレンズおよびカバー等のプラスチックレンズ；表面に透明導電膜を設けたタッチ電極や液晶基板等、スクリーンや偏光フィルム、ＣＲＴ用の防眩フィルター等の情報表示用の透明板；耐湿性と絶縁性を生かして、電子デバイス等の絶縁膜、耐湿コーティング；注射器、ピペット、薬品容器、光学分析用の容器やフィルム等の医療用具；自動車用のフロントガラス、オートバイの風防、航空機用窓材、住宅用窓、透明シャッター、照明器具等の窓材および鏡；ジュース、酒、炭酸飲料等の飲料容器、食品容器；包装用フィルム、適当なフィラー、染料、顔料等を加えて溶剤に溶かして耐湿塗料などの用途に有用である。
【００６０】
また、表面に導電性膜を形成した複合材料の用途としては、透明性膜を設けて、タッチ電極や液晶基板等に使用可能である他、高周波回路基板、コンデンサー用フィルム等の電子デバイス用材料としても有用である。表面に記録薄膜を設けた光記録媒体としては、光カード、光ディスク、光テープ、その他コンピュータ用の各種メモリ等の反射型および色素系の情報記録媒体として有用である。
【００６１】
【実施例】
以下に、合成例及び参考実施例を挙げて、本発明を具体的に説明する。以下の例において、特に断りのない限り、部および％は重量基準である。
【００６２】
［合成例１］
（開環重合体の合成）
窒素雰囲気下、２００リットルの反応器中に、脱水したトルエン９０部、トリエチルアルミニウム０．５部、トリエチルアミン１．４部、および１−ヘキセン０．０８部を入れた。温度を２０℃に保ちながら、エチルテトラシクロドデセン（ＥＴＤ）３０部、および四塩化チタン０．１７部を１時間にわたって連続的に反応系に添加し、重合反応を行なった。ＥＴＤと四塩化チタンの全量を添加後、１時間反応を行なった。次いで、イソプロピルアルコール／アンモニア水（０．５部／０．５部）混合溶液を添加して反応を停止した後、反応生成物を５００部のイソプロピルアルコール中に注ぎ、凝固した。凝固した重合体を６０℃で１０時間、真空乾燥し、開環重合体２５．５部を得た。
【００６３】
（水素添加反応）
得られた開環重合体をシクロヘキサン２００部に溶解し、２００リットルオートクレーブ中にパラジウム／カーボン触媒（担持量：５％）０．６部を加え、水素圧７０ｋｇ／ｃｍ²、温度１４０℃で４時間、水素添加反応を行なった。
【００６４】
（後処理）
水素添加触媒を濾過して除去した後、反応溶液をイソプロピルアルコール６００部中に注ぎ、凝固を行なった。
【００６５】
得られた水素添加物を、６０℃で１０時間、真空乾燥した後、シクロヘキサンに再溶解して１０％の溶液とした。イソプロピルアルコール６００部中に注ぎ、再度凝固した。前記と同様にして乾燥・凝固をもう一度行なった後、各々得られた水素添加物を９０℃で４８時間、真空乾燥し、水素添加物２２．６部を得た。収率は７５％であった。
【００６６】
（ポリマーの特性）
得られた水素添加物の水素添加率は、¹Ｈ−ＮＭＲスペクトル分析によると、９９％以上であった。また、トルエンを溶剤に用いた高速液体クロマトグラフィー（ＨＬＣ）分析（東ソー社製、ＨＬＣ８０２Ｌにより、ＴＳＫｇｅｌＧ５０００Ｈ−Ｇ４０００Ｈをカラムとして、温度３８℃、流量１．０ｍｌ／分で測定）で分子量（ポリスチレン換算）を測定した結果、数平均分子量（Ｍｎ）７．０×１０⁴、重量平均分子量（Ｍｗ）１７．５×１０⁴、分子量分布（Ｍｗ／Ｍｎ）２．５であった。ＤＳＣ分析によりガラス転移温度（Ｔｇ）を測定し、揮発分量を熱重量分析（ＴＧＡ）により、窒素雰囲気下、昇温速度１０℃／分で３０℃から３５０℃までの加熱減量として測定したところ、Ｔｇは１４２℃で、揮発分は０．０８％であった。
【００６７】
（ペレット化）
得られた熱可塑性飽和ノルボルネン系ポリマー１００部に対して、酸化防止剤として、１，３，５−トリメチル−２，４，６−トリス（３，５−ターシャリーブチル−４−ヒドロキシベンジル）ベンゼン（チバガイギー社製、商標名イルガノックス１３３０、蒸気圧１．３×１０^-12Ｐａ）を０．２部加え、ヘンシェルミキサーで混合後、押出機を用いて２３０℃でペレットを作成した。
【００６８】
（成形）
サーモプラスチック社製３０ｍｍφの押出機を使用し、樹脂温度を２８０℃に昇温加熱して溶融し、Ｔ型ダイから押出成形して、幅２０ｃｍ、厚さ１００μｍのフィルムを得た。この際、引き取りロールの温度は、１段目１３０℃、２段目１２１℃であった。
【００６９】
目視により観察したところ、フィルムの表面に条痕はなく、内部の発泡もみられず、透明で欠陥のないフィルムが得られた。引張り強さを測定したところ９００ｋｇ／ｃｍ²の強度であった。また、このフィルムを、偏光軸を互いに直行させた２枚の偏光板の間に挟んで回転させて観察したところ、明るく見える部分はなく、複屈折はなかった。さらに、このフィルムをエアーオーブン中で１１０℃で４８時間加熱したが、着色はなかった。
【００７０】
［参考実施例１］
予備乾燥の効果を見るために、次のような実験を行なった。
合成例１で得られたペレットをそのまま合成例１と同様の条件で押出成形し、厚さ５００μｍのシート状成形品を得た。シートの引張強度は、９００ｋｇ／ｃｍ²であった。この成形品を目視で観察したところ、透明で目だった大きな欠陥はなかったが、さらに４００倍の光学顕微鏡で１０視野観察し、ミクロボイドを数えたところ、大きさ５μｍ程度のミクロボイドが観察された。また、このシートを８０℃、相対湿度９０％の恒温恒湿ボックス中に１０００時間保持した後に取り出して目視観察したところ、全体に白濁し小さなクラック状欠陥が多数観察された。
【００７１】
同様に合成例１のペレットに対して、温風乾燥機で各種乾燥条件を変えて予備乾燥を行なった後に成形加工したシートに対する試験結果を上記の結果と合わせて表１に示す。
【００７２】
【表１】

【００７３】
（注）顕微鏡観察の評価基準は以下のとおりである。
Ａ：ミクロボイドなし、
Ｂ：ミクロボイドの個数２以下、
Ｃ：ミクロボイドの個数４以下、
Ｄ：ミクロボイドの個数５以上。
【００７４】
前記ペレット及びシートは、合成例１と同様の条件で押出成形し、そして、ポリエチレンやポリプロピレン等の他のオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ポリ塩化ビニルやポリ塩化ビニリデン等のハロゲン化炭化水素系の樹脂等と共押出加工やラミネート加工を行なうことが可能である。
【００７５】
【発明の効果】
本発明によれば、耐熱性、耐水性、強度等に優れた熱可塑性飽和ノルボルネン系ポリマーと他の樹脂とを共押出加工などを行うことにより、熱可塑性飽和ノルボルネン系ポリマーの強度やガス透過性などを更に補うことができる積層体が提供される。また、本発明によれば、耐熱性、耐水性、強度等に優れるとともに、ミクロボイドや発泡、条痕等による欠陥のない成形品を与えることができる熱可塑性飽和ノルボルネン系ポリマーと他の樹脂とからなる積層体が提供される。本発明の積層体は、前記した各種用途、例えば、包装用フィルムや容器などとして好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a co-extrusion process, a lamination process, etc., with a thermoplastic saturated norbornene polymer comprising a norbornene monomer ring-opening polymer hydrogenated product and other olefin resin, polyester resin, halogenated hydrocarbon resin, etc. The present invention relates to a laminate obtained. The laminate of the present invention is one in which the strength and gas permeability of the thermoplastic saturated norbornene polymer are supplemented by coextrusion or lamination with other resins.
[0002]
[Prior art]
In general, polyolefin-based polymers are composed of only carbon and hydrogen and do not have unsaturated bonds, so they have a low affinity for water, do not absorb or permeate moisture, and are free of acid, alkali, other chemicals, It is characterized by high resistance to various solvents. Typical examples are polyethylene and polypropylene, which are formed into a sheet, film, cylinder or rod by melt extrusion and used for a wide range of applications. However, these conventional materials are not sufficient in heat resistance, and are heat-deformed at a relatively low temperature of 70 to 80 ° C. or less, and cannot be used at higher temperatures. In addition, these materials have poor transparency and cannot be used for optical applications.
[0003]
On the other hand, for example, polycarbonate (PC) and polymethyl methacrylate (PMMA) have been mainly used as transparent plastic molding materials for optics such as optical disk substrates and plastic lenses. However, PC has a large birefringence, and PMMA has a large water absorption property and insufficient heat resistance, making it difficult to meet the demands for higher sophistication.
[0004]
Recently, thermoplastic saturated norbornene polymers such as hydrogenated products of ring-opening polymers of norbornene monomers and addition polymers of norbornene monomers and ethylene have attracted attention as optical plastic molding materials such as optical disk substrates. (JP-A-60-26024, JP-A-64-24826, JP-A-60-168708, JP-A-61-115912, JP-A-61-120816, etc.).
[0005]
These thermoplastic saturated norbornene polymers are a kind of polyolefin polymer, exhibit excellent water resistance, chemical resistance and solvent resistance like other polyolefins, and have high heat resistance with a glass transition temperature of 100 ° C. or higher. It is a highly transparent material that can be synthesized and has a total light transmittance of 90% or more.
[0006]
From the above, the thermoplastic saturated norbornene-based polymer not only can be used for various applications as a heat-resistant polyolefin material, but also has small birefringence and excellent transparency, water resistance and heat resistance. As a transparent material, it can be used for optical applications.
[0007]
However, these thermoplastic saturated norbornene-based polymers are more brittle than polyethylene, polypropylene, and PMMA, and when extruded into a sheet, film, or rod shape, they do not have a sufficient strength that is easily broken or broken. In addition, there are often problems that foam-like defects are generated in the extrusion-molded product, appearing as large streaks on the surface, and the strength is further reduced. Even if there are no visible large streaks, fine voids and crack-like defects (hereinafter referred to as “microvoids”) that cannot be seen with the eyes can be found inside by using an optical microscope. In the past, in the extrusion molding of a thermoplastic saturated norbornene polymer, a molded product having no microvoids has not been obtained.
[0008]
As another method for obtaining a sheet-like or film-like molded article, there is a casting method in which a polymer is cast as a solution of an appropriate solvent and the solvent is evaporated. According to this method, a molded article having almost no microvoids can be obtained. However, even if the molded product is as thin as several μm, the solvent does not completely evaporate and remains about several percent, so that sufficient strength cannot be obtained or There is a problem that the residual solvent evaporates to change the characteristics of the molded product, or the evaporated solvent adversely affects other components incorporated around the molded product. The film-like or sheet-like molded product has a tensile strength of 800 kg / cm from the viewpoint of durability.²Or more, preferably 900 kg / cm²Although the above is required, the casting method has not been obtained with such a sufficient strength.
[0009]
Therefore, conventionally, it is a sheet-like or film-like molded article made of a thermoplastic saturated norbornene-based polymer, which has no generation of fine voids or crack-like defects, and has a tensile strength of 800 kg / cm.²There is no provision of sufficient strength.
[0010]
[Problems to be solved by the invention]
The object of the present invention is to perform the strength and gas permeability of the thermoplastic saturated norbornene polymer by co-extrusion processing of the thermoplastic saturated norbornene polymer excellent in heat resistance, water resistance, strength and the like with another resin. It is providing the laminated body which can supplement further.
[0011]
Another object of the present invention is composed of a thermoplastic norbornene polymer and other resins that are excellent in heat resistance, water resistance, strength, etc., and that can give a molded article free from defects due to microvoids, foaming, streaks, etc. The object is to provide a laminate.
[0012]
As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic saturated norbornene polymer comprising a hydrogenated norbornene monomer ring-opening polymer having a volatile component content of 0.3% by weight or less, and The inventors have come up with a laminate comprising at least one resin selected from the group consisting of other olefin resins, polyester resins, and halogenated hydrocarbon resins. Such a laminate can be obtained by coextrusion processing, lamination processing, or the like. The present invention has been completed based on these findings.
[0013]
[Means for Solving the Problems]
  According to the present invention, (A)The number average molecular weight (Mn) measured by high performance liquid chromatography analysis using toluene as a solvent is 50,000 to 500,000, the weight average molecular weight (Mw) is 100,000 to 2,000,000, and the molecular weight distribution ( Mw / Mn) is 2.4 to 6.0,It consists of a hydrogenated norbornene-based monomer ring-opening polymer having a volatile component content of 0.3% by weight or less, and a vapor pressure at 20 ° C. of 10^-5A co-polymer comprising a thermoplastic saturated norbornene polymer blended with an antioxidant of Pa or less and at least one resin selected from the group consisting of (B) other olefin resins, polyester resins, and halogenated hydrocarbon resins. A laminate obtained by extrusion or laminating is provided.
[0014]
  According to the present invention, (A)The number average molecular weight (Mn) measured by high performance liquid chromatography analysis using toluene as a solvent is 50,000 to 500,000, the weight average molecular weight (Mw) is 100,000 to 2,000,000, and the molecular weight distribution ( Mw / Mn) is 2.4 to 6.0,It consists of a hydrogenated norbornene-based monomer ring-opening polymer having a volatile component content of 0.3% by weight or less, and reserves for at least 1 hour at a temperature of its glass transition temperature (Tg) -30 ° C. to (Tg-5 ° C.). Co-extrusion processing or laminating processing comprising a thermoplastic saturated norbornene-based polymer subjected to a drying treatment and (B) at least one resin selected from the group consisting of other olefin-based resins, polyester resins, and halogenated hydrocarbon-based resins Thus obtained laminate is provided.
[0015]
  Furthermore, according to the present invention, the following aspects are provided.
1. The laminate described above, which is obtained by coextrusion during extrusion molding of a thermoplastic saturated norbornene-based polymer into a sheet or film.
2. The laminate described above, which is obtained by coextrusion during extrusion when a thermoplastic saturated norbornene-based polymer is extruded into a sheet-like molded product and further stretched in a uniaxial or biaxial direction. .
3. The laminate as described above, which is a packaging film or container.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
(1) Thermoplastic saturated norbornene polymer
The molding material targeted by the present invention is a thermoplastic saturated norbornene-based polymer, and specific examples thereof include a polymer having a structural unit represented by the following general formula [I].
Formula [I]
[0017]
[Chemical 1]

[0018]
[However, in the formula, R₁And R₂Are polar groups such as hydrogen, hydrocarbon residues or halogens, esters, nitriles, pyridyls, which may be the same or different, and R₁And R₂May form a ring with each other. n is a positive integer. q is 0 or a positive integer. ]
[0019]
The polymer having the structural unit represented by the general formula [I] includes, for example, norbornene and alkyl and / or alkylidene substituted products thereof such as 5-methyl-2-norbornene, 5,6-dimethyl as monomers. -2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, etc .; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, their methyl, ethyl, propyl , Alkyl substituents such as butyl, and polar group substituents such as halogen; dimethanooctahydronaphthalene, its alkyl and / or alkylidene substituents, and polar group substituents such as halogen, for example, 6-methyl-1,4 : 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydrona Talen, 6-ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8-dimethano- 1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a- Octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4: 5,8- Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8 , 8a-octahydronaphthalene, etc .; 3-4 tetramers of cyclopentadiene, such as 4,9: , 8-Dimethano-3a, 4,4a, 5,8,8,9,9a-octahydro-1H-benzondene, 4,11: 5, 10: 6,9-trimethano-3a, 4,4a, 5,5a , 6,9,9a, 10,10a, 11,11a-dodecahydro-1H-cyclopentanthanthene and the like, and a ring-opening polymer obtained by polymerization by a known ring-opening polymerization method is used. , A saturated polymer produced by hydrogenation by an ordinary hydrogenation method.
[0020]
In order to increase the glass transition temperature (Tg) of the target ring-opening polymer hydrogenated product (saturated polymer) to 100 ° C. or higher, is it necessary to use a tetracyclic or pentacyclic monomer among these norbornene monomers? These are the main components and are preferably used in combination with a bicyclic or tricyclic monomer. In particular, in terms of birefringence, it is preferable to use a tetracyclic lower alkyl-substituted product or alkenyl-substituted product as a main component.
[0021]
In addition, the thermoplastic saturated norbornene-based monomer is used in the production process of the polymer [I], in the presence of an α-olefin such as 1-butene, 1-pentene, 1-hexene as a molecular weight regulator, or cyclopropene, A polymer copolymerized by adding other monomer components such as cycloolefin such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and 5,6-dihydrocyclopentadiene as a minor component may be used.
[0022]
  The thermoplastic saturated norbornene polymer in the present invention has a number average molecular weight (Mn) of 50,000 to 500,000, preferably 60,000 to 200, as measured by high performance liquid chromatography (HLC) analysis using toluene as a solvent. And a weight average molecular weight (Mw) of 100,000 to 2,000,000, preferably 100,000 to 1,000,000, and its molecular weight distribution (Mw / Mn) is2.4The above is preferable.
[0023]
When Mn and Mw are smaller than the above ranges, a molded product having sufficient strength cannot be obtained when a film, sheet, rod or the like is formed by extrusion molding. On the other hand, if it is larger than this range, the moldability is deteriorated, and even if it is attempted to be extruded, the viscosity is too high, making it difficult to mold. Further, even if an attempt is made to dissolve or cast in an appropriate solvent, the solubility in the solvent is insufficient. Moreover, such a high molecular weight polymer has a disadvantage that it is difficult to control the synthesis reaction and a material with stable quality cannot be obtained.
[0024]
  The molecular weight distribution (Mw / Mn) isGoodIt is preferably 2.4 or more, particularly preferably 2.8 or more.
[0025]
  In general, it is said that a thermoplastic polymer having a smaller molecular weight distribution and closer to monodispersion has better balance between strength and formability and better performance. However, when a polymer having a relatively large molecular weight is extruded as in the present invention to form a sheet or film, for example, in the process of cooling and solidifying from a molten state, a monodisperse molecule is instantaneously at a certain temperature. Rather than solidifying at the same time, when the molecules of various molecular weights are gradually solidified in order from the larger molecular weight, no stress remains, and a flat and beautiful molded product can be obtained as a whole. In the thermoplastic saturated norbornene-based polymer, this tendency is particularly noticeable because the polymer is rigid, has high heat resistance, and has a molding temperature close to 300 ° C. Thus, for the purposes of the present invention, the molecular weight distribution isGoodIt is preferably 2.4 or more, particularly preferably 2.8 or more. When the molecular weight distribution is smaller than this range, there is a drawback that extrusion molding is difficult and it is difficult to obtain a molded product having good smoothness and optical characteristics.
[0026]
As the molecular weight distribution (Mw / Mn) increases, the moldability improves. In general, a polymer having high heat resistance and high rigidity such as polycarbonate tends to cause a phenomenon in which a flat molded product cannot be obtained due to internal distortion when rapidly cooled from a molten state. The same applies to thermoplastic saturated norbornene polymers. For example, when extruding from a T die with an extruder and pulling it into a sheet shape, a phenomenon occurs in which a flat sheet cannot be pulled unless the temperature of the roll is increased. In the case of a polymer having a Tg of about 140 ° C., it can be drawn flat by raising the roll temperature to 120 to 140 ° C. However, usually, the roll is heated by water in many cases, and the temperature of the roll can be raised only to about 90 ° C. at most.
[0027]
  Molecular weight distribution2.4If the temperature is less than 1, even if the roll temperature is increased to about 140 ° C. and near the glass transition temperature of the polymer, molding cannot be performed successfully.2.4In the above, a flat molded product can be formed by raising the temperature of the roll to about 110 to 130 ° C. Further, when the molecular weight distribution is expanded to 2.8 or more, the moldability is further improved, and a molded product which is flat even at a roll temperature of about 90 to 100 ° C. and has no internal strain becomes possible. The upper limit of the molecular weight distribution is not particularly limited, but if it is too large, Mn is large, and sufficient strength cannot be obtained for a high melt viscosity, and synthesis of such a polymer itself becomes difficult. In general, it is preferably 6.0 or less.
[0028]
A thermoplastic saturated norbornene polymer having such molecular weight (Mn, Mw) and molecular weight distribution (Mw / Mn) can be used in a synthesis reaction, for example, by adjusting the amount of catalyst used, changing the polymerization temperature, When using a regulator, the type and amount are adjusted, and the monomer is added to the reaction system with a prop, or a low molecular weight and a large one are synthesized separately and blended together. Thus, it can be produced by a method such as broadening the molecular weight distribution.
[0029]
When the unsaturated bond remaining in the molecular chain of the synthesized polymer is saturated by a hydrogenation reaction, the hydrogenation rate is 90% or more, preferably 95% or more, particularly from the viewpoint of light resistance deterioration, weather resistance deterioration, etc. Preferably it is 99% or more.
[0030]
The thermoplastic saturated norbornene-based polymer in the present invention desirably has a Tg of 100 ° C. or higher, preferably 120 to 200 ° C., more preferably 130 to 180 ° C. from the viewpoints of heat resistance and moldability.
[0031]
(2) Volatile component reduction method
The thermoplastic saturated norbornene-based polymer generally contains 0.5% by weight or more of volatile components in a normal synthesis method. The molding material of the present invention has a volatile component contained in the thermoplastic saturated norbornene-based polymer of 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. It is desirable to be. In the present invention, a heat loss from 30 ° C. to 350 ° C. is determined using a differential thermogravimetric measuring device (TG / DTA200 manufactured by Seiko Denshi Kogyo Co., Ltd.), and the amount is defined as the content of volatile components. If the content of the volatile component is larger than the above range, when extrusion molding is performed at a temperature of about 250 to 350 ° C., the volatile component volatilizes during molding, foams and becomes a defect inside the molded product, or decreases the strength. Or appear as streaks on the surface.
[0032]
As a method for reducing the volatile matter, for example, in a polymer coagulation method using a poor solvent, there is a method of repeatedly coagulating. In the direct drying method, it is desirable to dry using a thin film dryer or an extrusion dryer at 250 ° C. or higher and 30 Torr or lower. Alternatively, the polymer solvent solution may be concentrated to several tens of percent in advance and then directly dried. Of course, it is not limited to these methods. The thermoplastic saturated norbornene-based polymer produced by these methods is substantially amorphous, excellent in transparency, dimensional stability, heat resistance and water absorption, and hardly has moisture permeability.
[0033]
(3) Antioxidant
In the present invention, when a low-volatile antioxidant is blended at a ratio of 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic saturated norbornene-based polymer, the polymer is effectively decomposed and colored during the molding process. Can be prevented.
[0034]
As an antioxidant, the vapor pressure at 20 ° C. is 10^-FivePa or less, particularly preferably 10^-8An antioxidant of Pa or less is desirable. Vapor pressure is 10^-FiveWhen the antioxidant is higher than Pa, there is a problem that foaming occurs when extrusion molding is performed, and that the antioxidant is volatilized from the surface of the molded product when exposed to a high temperature.
[0035]
Examples of the antioxidant that can be used in the present invention include the following, and one or a combination of these may be used.
[0036]
Hintard phenol
2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-butyl- α-methoxy-p-dimethyl-phenol, 2,4-di-t-amylphenol, t-butyl-m-cresol, 4-t-butylphenol, styrenated phenol, 3-t-butyl-4-hydroxyanisole, 2,4-dimethyl-6-tert-butylphenol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate Nate-diethyl ester, 4,4'-bisphenol, 4,4'-bis- (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-methyl-6-α-methylcyclohexylphenol), 4,4′-methylene-bis- (2-methyl-6) -T-butylphenol), 4,4'-methylene-bis- (2,6-di-t-butylphenol), 1,1'-methylene-bis- (2,6-di-t-butylnaphthol), 4 , 4'-butylidene-bis- (2,6-di-t-butyl-meta-cresol), 2,2'-thio-bis- (4-methyl-6-t-butylphenol), di-o-cresol Sulfide, 2,2'-thio-bis- (2-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 4,4'-thio- Bis- (2,3-di-sec-amylf Nol), 1,1'-thio-bis- (2-naphthol), 3,5-di-t-butyl-4-hydroxybenzyl ether, 1,6-hexanediol-bis- [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5 -Triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium , , 3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-tert-butyl-5- Methyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6, -tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5 -Di-t-butyl-4-hydroxybenzyl) -isocyanurate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxygenyl) propionate] and the like.
[0037]
Aminophenols
Normal butyl-p-aminophenol, normal butyroyl-p-aminophenol, normal peragonoyl-p-aminophenol, normal lauroyl-p-aminophenol, normal stearoyl-p-aminophenol, 2,6-di-t -Butyl-α-dimethyl, amino-p-cresol and the like.
[0038]
Hydroquinone
Hydroquinone, 2,5-di-t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone, hydroquinone methyl ether, hydroquinone monobenzyl ether, and the like.
[0039]
Phosphite series
Triphosphite, tris (3,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphinite 2-ethylhexyl octyl phosphite, etc.
[0040]
Other
2-mercaptobenzothiazole zinc salt, dicatechol borate-di-o-tolylguanidine salt, nickel-dimethyldithiocarbamate, nickel-pentamethylene dithiocarbanate, mercaptobenzimidazole, 2-mercaptobenzimidazole zinc salt and the like.
[0041]
(4) Other ingredients
In the thermoplastic saturated norbornene-based polymer of the present invention, various antistatic agents, lubricants, surfactants, ultraviolet absorbers and the like are added as additives other than the antioxidant as long as the object of the present invention is not impaired. May be used. Moreover, when using for uses other than optical materials, you may add and use additives, such as fillers, such as glass fiber, dye, and a pigment, as needed.
[0042]
(5) Pelletization and preliminary drying
The plastic material is usually supplied as pellets having a diameter of about 1 to 7 mm and a length of about 4 to 8 mm, and this is molded into a desired shape by an extrusion molding method or an injection molding method. By the way, in general, in the case of a thermoplastic saturated norbornene-based polymer, a polymer used after synthesis is prepared by removing the solvent used in the synthesis by a coagulation method or a direct drying method, and adding necessary amounts of the above-mentioned various additives. Extruded into a strand having a predetermined diameter in a molten state at a temperature of approximately 230 ° C. or higher, and then cut into a desired length by a suitable strand cutter to form pellets.
[0043]
In a normal plastic material, the pellet is molded as it is.For example, a polycarbonate resin, an acrylic resin, a polyamide resin or the like has a high hygroscopic property, or a resin that easily decomposes adsorbs moisture during storage of the pellet, If it is molded as it is due to the decomposed product, it will foam violently or defects such as large streaks will occur on the surface of the molded product, so it is molded after pre-drying for several hours below the glass transition temperature of the resin before use This method has become common.
[0044]
However, since the thermoplastic saturated norbornene-based polymer has low hygroscopicity and does not contain any component that decomposes during storage, it has been conventionally considered that this predrying is unnecessary and has been molded without predrying. Even if preliminary drying is actually attempted, volatile components are hardly detected. Surprisingly, however, when the thermoplastic saturated norbornene polymer pellets were pre-dried, fine voids and crack-like defects that were not visible to the naked eye without pre-drying occurred in the molded product, It has been found that moldings without these microvoids can be obtained.
[0045]
The molded article thus obtained does not generate microvoids even after molding, and further, for example, microvoids are also present after a durability test under a high temperature and high humidity of 70 ° C. or higher and a relative humidity of 80% or higher and 20 hours or longer. Does not occur. It was also confirmed that this drying process is effective in the case of injection molding.
[0046]
As pre-drying conditions, the higher the temperature and the longer the drying time is, the more effective, but if the temperature exceeds the glass transition temperature of the resin and is too high, the pellets are heat-fused and difficult to use. Since the effect is saturated in several hours, preferably (Tg-30) to (Tg-5) ° C., particularly preferably (Tg-20) to (Tg-5) ° C., preferably 1 hour or more, particularly The treatment is preferably performed for 2 hours or more.
[0047]
Drying is effective in both vacuum drying and atmospheric pressure drying in an air or nitrogen atmosphere. Although the time from the end of the drying process to the time of use for molding does not exceed a short time, it does not need to be particularly short, and the effect is not lost even after several days or more.
[0048]
(6) Molding method
Extrusion molding
The thermoplastic saturated norbornene-based polymer of the present invention is particularly suitable for extrusion molding, but is not limited thereto. In extrusion molding, using a melt extruder, a thermoplastic saturated norbornene-based polymer is heated to about 250 to 300 ° C, extruded from a T-type or manifold-type die, and wound up with various rolls to form a sheet or film. can do. In this case, since the thermoplastic saturated norbornene-based polymer has high heat resistance and high rigidity, if it is cooled rapidly with a roll, the surface undulates like a polycarbonate and cannot be formed flatly. As described above, it is appropriate to remove the cooling roll at a relatively high temperature of about 70 to 140 ° C. according to the value of the molecular weight distribution (Mw / Mn). Further, the sheet-like molded product can be further stretched in a uniaxial or biaxial direction. In addition, there is processing with a calendar roll.
[0049]
Laminate molding
To further supplement the strength and gas permeability of thermoplastic saturated norbornene polymers, other olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, and halogenated hydrocarbons such as polyvinyl chloride and polyvinylidene chloride. It is possible to perform co-extrusion processing or laminating processing with these resins.
[0050]
Other extrusion molding
By extruding a thermoplastic saturated norbornene polymer from an appropriate die, it can be extruded into a rod shape, a fiber shape, or a tube shape. These extruded products can be stretched at a temperature not higher than the glass transition temperature and further processed into a thin rod or tube.
[0051]
Cross-linking
Furthermore, in order to increase the strength, crosslinking by heating or irradiation with radiation such as ultraviolet rays or electron beams can also be performed. In this case, it is effective to use an appropriate crosslinking agent. Known crosslinking agents can be used, for example, monomers having a plurality of vinyl groups such as divinylbenzene; polyfunctional acrylates such as diallyl phthalate, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate; triallyl isocyanurate Isocyanurates, such as polymers having a plurality of unsaturated bonds such as liquid polybutadiene.
[0052]
Other molding methods
In addition to melt extrusion molding, the thermoplastic saturated norbornene-based polymer of the present invention can be molded as follows. It can be formed into a sheet by hot pressing. In addition, thermoplastic saturated norbornene polymers are dissolved in aromatic hydrocarbon solvents such as benzene, toluene and xylene, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decalin, and halogen solvents such as chloroform and monochlorobenzene. These films can be cast on a flat plate or cast on a roll to form a film. A polymer having a relatively large molecular weight can also be spun into a thread form from the solvent solution. A polymer having a relatively small molecular weight can be subjected to ordinary injection molding, and a general thermoplastic resin processing method such as rotational molding can be applied.
[0053]
(7) Application
Optical materials and conductive composite materials
The thermoplastic saturated norbornene-based polymer (molding material) of the present invention is amorphous, excellent in transparency, and low in birefringence. Therefore, as an optical material, in particular, a substrate of an optical recording medium. Suitable as material.
[0054]
The molded product obtained from the thermoplastic saturated norbornene-based polymer of the present invention has a metal, metal oxide, metal nitride, metal sulfide, metal halide, etc. on its surface by a thin film forming method such as vacuum deposition or sputtering. Can be formed into a single layer or a multilayer according to the purpose. At this time, although it may be exposed to a considerably high temperature in a vacuum, the molded product obtained by the present invention has a low volatile content and a low outgas, so that the chamber can be pulled to a predetermined degree of vacuum in a short time. In addition, it is possible to form a flat film with no occurrence of “bulge” or the like on the surface.
[0055]
A recording medium can be manufactured by providing a recording thin film capable of optical recording and / or reading on a transparent substrate. The recording material for forming the recording thin film (recording layer) may be any known rare earth-transition metal amorphous alloy, such as a Tb-Fe alloy (Japanese Patent Publication No. 57-20691), a Dy-Fe alloy (special No. 57-20692), Cd—Tb—Fe alloys (Japanese Patent Laid-Open No. 56-126907), Cd—Tb—Dy—Fe based alloys (Japanese Patent Laid-Open No. 57-94948), Cd—Co based alloys (special No. 54-121719), Tb—Fe—Co, and the like. These rare earth-transition metal amorphous layers are preferably formed by a thin film forming method such as vapor deposition, sputtering, or ion plating. The thickness of this amorphous layer is generally 500-1500 mm. In addition, a phase change recording material may be used as the recording layer, and examples thereof include Ge—Te, Sb—Te, In—Sb, Ge—Sb—Te, and In—Sb—Te. These phase change recording materials are preferably formed by a method such as vapor deposition, sputtering, or ion plating. The thickness of this amorphous layer is generally 500 to 2000 mm.
[0056]
Organic dye-based recording materials can also be used. For example, methine / polymethine (dianin: indolonin type, thiazole type, croconiums, squaryliums) (Japanese Patent Laid-Open No. 58-1713696); quinones; naphthoquinones, Anthraquinones (JP 59-199291, JP 58-112793); Phthalocyanines (metal phthalocyanines) (JP 61-235188, JP 59-11292); Dithiols (dithiol metal complexes) In addition, tetrahydrocholines, dioxanes, dithiazines, thiapyryliums, porphyrins (Japanese Patent Laid-Open Nos. 58-197088, 61-235188, 59) -78891). The film thickness of the organic dye-based recording material after film formation is generally 500 to 5000 mm.
[0057]
For example, Te-CS₂, Pb-Te-Se, Te-C, TeO₂, Sb-Se, Bl-Te, etc., and can also be used for write-once type recording cards using shape changes such as bubble formation. Furthermore, gold, platinum, aluminum, or the like can be used as the reflective film.
[0058]
In the optical recording medium, a surface protective layer may be provided on the surface, or a protective layer, a reflective layer, and a dielectric layer may be provided between the recording layer and the substrate made of the polymer of the present invention. Examples of layer forming materials such as these protective layers include CdS, ZnSe, and SiO.₂, Si, Si_ThreeN, Si_ThreeN_Four, AlN, TiO₂, TaO₂, MgF₂Inorganic substances such as UV or organic substances such as ultraviolet curable resins can be used. Furthermore, optical cards and the like may be used by directly bonding other materials. In that case, as a bonding method, in addition to normal adhesives such as solvents, hot melts, UV curable adhesives, A sonic bonding method is used.
[0059]
Other uses
The thermoplastic saturated norbornene-based polymer and molding material of the present invention include plastic optical fibers and connectors for short-range information transmission including those for automobiles and medical use; lenses for picking up information, lenses for projectors, Glasses lenses, sports goggles, plastic lenses such as head lamps and tail lamp lenses for automobiles and covers; touch electrodes and liquid crystal substrates with a transparent conductive film on the surface, screens, polarizing films, anti-glare filters for CRT, etc. Transparent plate for displaying information; insulating film for electronic devices, moisture-resistant coating, taking advantage of moisture resistance and insulation; medical devices such as syringes, pipettes, chemical containers, optical analysis containers and films; front for automobiles Glass, motorcycle windshield, aircraft window material, residential window, transparent shutter -Window materials and mirrors for lighting equipment, etc .; beverage containers such as juice, liquor, carbonated drinks, food containers; packaging films, suitable fillers, dyes, pigments, etc. are added to dissolve in solvents and used for moisture resistant paints, etc. Useful.
[0060]
In addition, composite materials with a conductive film on the surface can be used for touch electrodes, liquid crystal substrates, etc. by providing a transparent film, and materials for electronic devices such as high-frequency circuit boards and capacitor films. It is also useful. As an optical recording medium having a recording thin film on its surface, it is useful as a reflection type and dye-based information recording medium such as an optical card, an optical disk, an optical tape, and other various memories for computers.
[0061]
【Example】
The present invention will be specifically described below with reference to synthesis examples and reference examples. In the following examples, parts and% are based on weight unless otherwise specified.
[0062]
[Synthesis Example 1]
(Synthesis of ring-opening polymer)
Under a nitrogen atmosphere, 90 parts of dehydrated toluene, 0.5 parts of triethylaluminum, 1.4 parts of triethylamine, and 0.08 part of 1-hexene were placed in a 200-liter reactor. While maintaining the temperature at 20 ° C., 30 parts of ethyltetracyclododecene (ETD) and 0.17 part of titanium tetrachloride were continuously added to the reaction system over 1 hour to carry out a polymerization reaction. The reaction was carried out for 1 hour after the total amount of ETD and titanium tetrachloride was added. Subsequently, after adding isopropyl alcohol / ammonia water (0.5 part / 0.5 part) mixed solution to stop the reaction, the reaction product was poured into 500 parts of isopropyl alcohol and solidified. The solidified polymer was vacuum-dried at 60 ° C. for 10 hours to obtain 25.5 parts of a ring-opened polymer.
[0063]
(Hydrogenation reaction)
The obtained ring-opening polymer was dissolved in 200 parts of cyclohexane, 0.6 parts of a palladium / carbon catalyst (supported amount: 5%) was added to a 200 liter autoclave, and the hydrogen pressure was 70 kg / cm.²The hydrogenation reaction was carried out at 140 ° C. for 4 hours.
[0064]
(Post-processing)
After removing the hydrogenation catalyst by filtration, the reaction solution was poured into 600 parts of isopropyl alcohol and coagulated.
[0065]
The obtained hydrogenated product was vacuum-dried at 60 ° C. for 10 hours and then redissolved in cyclohexane to obtain a 10% solution. It was poured into 600 parts of isopropyl alcohol and solidified again. After drying and coagulation once again in the same manner as described above, each obtained hydrogenated product was vacuum-dried at 90 ° C. for 48 hours to obtain 22.6 parts of hydrogenated product. The yield was 75%.
[0066]
(Polymer characteristics)
The hydrogenation rate of the obtained hydrogenated product is¹According to 1 H-NMR spectrum analysis, it was 99% or more. Also, molecular weight (polystyrene conversion) by high performance liquid chromatography (HLC) analysis using toluene as a solvent (measured at 38 ° C. and a flow rate of 1.0 ml / min using TSKgel G5000H-G4000H as a column by HLC802L manufactured by Tosoh Corporation) As a result of measurement, number average molecular weight (Mn) 7.0 × 10^Four, Weight average molecular weight (Mw) 17.5 × 10^FourThe molecular weight distribution (Mw / Mn) was 2.5. The glass transition temperature (Tg) was measured by DSC analysis, and the volatile content was measured by thermogravimetric analysis (TGA) as a heating loss from 30 ° C. to 350 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere. The Tg was 142 ° C. and the volatile content was 0.08%.
[0067]
(Pelletized)
As an antioxidant, 1,3,5-trimethyl-2,4,6-tris (3,5-tertiarybutyl-4-hydroxybenzyl) benzene was used as an antioxidant with respect to 100 parts of the obtained thermoplastic saturated norbornene polymer. (Trade name: Irganox 1330, vapor pressure 1.3 × 10, manufactured by Ciba Geigy Corp.^-120.2 parts of Pa) was added, mixed with a Henschel mixer, and pellets were prepared at 230 ° C. using an extruder.
[0068]
(Molding)
Using a 30 mmφ extruder manufactured by Thermo Plastic Co., Ltd., the resin temperature was raised to 280 ° C. and melted, and extrusion was performed from a T-type die to obtain a film having a width of 20 cm and a thickness of 100 μm. At this time, the temperature of the take-up roll was 130 ° C. at the first stage and 121 ° C. at the second stage.
[0069]
As a result of visual observation, there was no streak on the surface of the film, no internal foaming was observed, and a transparent and defect-free film was obtained. Measurement of tensile strength is 900kg / cm²Strength. Further, when this film was observed by being sandwiched and rotated between two polarizing plates whose polarization axes were perpendicular to each other, there was no portion that looked bright and there was no birefringence. Furthermore, this film was heated in an air oven at 110 ° C. for 48 hours, but it was not colored.
[0070]
[Reference Example 1]
In order to see the effect of preliminary drying, the following experiment was conducted.
The pellets obtained in Synthesis Example 1 were extruded as they were under the same conditions as in Synthesis Example 1 to obtain a sheet-like molded product having a thickness of 500 μm. The tensile strength of the sheet is 900 kg / cm²Met. When this molded product was visually observed, there were no transparent and conspicuous large defects, but further 10 microscopic observations were made with a 400 × optical microscope, and microvoids having a size of about 5 μm were observed. Further, when this sheet was kept in a constant temperature and humidity box at 80 ° C. and 90% relative humidity for 1000 hours and then taken out and visually observed, a large number of small crack-like defects were observed.
[0071]
Similarly, Table 1 shows the test results for the sheet formed after the pellets of Synthesis Example 1 were pre-dried by changing various drying conditions with a hot air dryer together with the above results.
[0072]
[Table 1]

[0073]
(Note) Evaluation criteria for microscopic observation are as follows.
A: No microvoid
B: The number of microvoids is 2 or less,
C: The number of microvoids is 4 or less,
D: Number of microvoids is 5 or more.
[0074]
The pellets and sheets are extruded under the same conditions as in Synthesis Example 1, and other olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, and halogenated carbonization such as polyvinyl chloride and polyvinylidene chloride. It is possible to perform coextrusion processing or laminating processing with a hydrogen-based resin or the like.
[0075]
【The invention's effect】
According to the present invention, the thermoplastic saturated norbornene polymer having excellent heat resistance, water resistance, strength, and the like is coextruded with other resins, and the strength and gas permeability of the thermoplastic saturated norbornene polymer are thus obtained. The laminated body which can supplement further etc. is provided. In addition, according to the present invention, the thermoplastic saturated norbornene-based polymer and other resins that are excellent in heat resistance, water resistance, strength, etc. and can give a molded product free from defects due to microvoids, foaming, streaks, etc. A laminate is provided. The laminate of the present invention is suitable for various applications as described above, for example, packaging films and containers.

Claims (6)

(A) The number average molecular weight (Mn) measured by high performance liquid chromatography analysis using toluene as a solvent is 50,000 to 500,000, the weight average molecular weight (Mw) is 100,000 to 2,000,000, and It consists of a norbornene-based monomer ring-opening polymer hydrogenated product having a molecular weight distribution (Mw / Mn) of 2.4 to 6.0 and a volatile component content of 0.3% by weight or less, and a vapor pressure at 20 ° C. of 10 ^From a thermoplastic saturated norbornene polymer blended with an antioxidant of ⁻⁵ Pa or less, and (B) at least one resin selected from the group consisting of other olefin resins, polyester resins, and halogenated hydrocarbon resins. A laminate obtained by coextrusion or lamination. (A) The number average molecular weight (Mn) measured by high performance liquid chromatography analysis using toluene as a solvent is 50,000 to 500,000, the weight average molecular weight (Mw) is 100,000 to 2,000,000, and It consists of hydrogenated norbornene-based monomer ring-opening polymer having a molecular weight distribution (Mw / Mn) of 2.4 to 6.0 and a volatile component content of 0.3% by weight or less, and its glass transition temperature (Tg) A thermoplastic saturated norbornene polymer preliminarily dried at a temperature of −30 ° C. to (Tg−5 ° C.) for 1 hour or more and (B) other olefin resin, polyester resin, and halogenated hydrocarbon resin. A laminate obtained by coextrusion processing or laminating processing comprising at least one resin selected from the group.   The laminate according to claim 1 or 2, wherein the thermoplastic saturated norbornene polymer comprises a hydrogenated norbornene monomer ring-opening polymer having a volatile component content of 0.1 wt% or less.   The laminate according to any one of claims 1 to 3, wherein the laminate is obtained by coextrusion during extrusion molding of a thermoplastic saturated norbornene-based polymer into a sheet or film.   The thermoplastic saturated norbornene-based polymer is obtained by co-extrusion at the time of extrusion when extruding into a sheet-like molded product and further stretching in a uniaxial or biaxial direction. 4. The laminate according to any one of 3 above.   It is a film for packaging or a container, The laminated body of any one of Claims 1 thru | or 5.