JP3885850B2 - Light selective absorption resin molded product - Google Patents

Description

【０００６】
（式中、ＡおよびＢは水素原子または炭素数１〜１０の炭化水素基であり、ＸおよびＹは水素原子または一価の有機基であって、ＸおよびＹの少なくとも１つは水素原子および炭化水素基以外の極性を有する基を示し、ｍは０〜２である。）
【０００７】
前記一般式（１）において、炭化水素基以外の極性基の例としては、−（ＣＨ₂）_nＣＯＯＲ¹、−（ＣＨ₂）_nＯＣＯＲ¹、−（ＣＨ₂）_nＣＮ、−（ＣＨ₂）_nＣＯＮＲ²Ｒ³、−（ＣＨ₂）_nＣＯＯＺ、−（ＣＨ₂）_nＯＣＯＺ、−（ＣＨ₂）_nＯＺ、−（ＣＨ₂）_nＣＷ、またはＸとＹから構成された−ＣＯ−Ｏ−ＯＣ−もしくは−ＣＯ−ＮＲ⁴−ＯＣ−（Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は炭素数１〜２０の炭化水素基、Ｚはハロゲン原子で置換された炭化水素基、ＷはＳｉＲ⁵ _pＦ_3-p（Ｒ⁵は炭素数１〜１０の炭化水素基、Ｆは−ＯＣＯＲ⁶または−ＯＲ⁶（Ｒ⁶は炭素数１〜１０の炭化水素基を示す）、ｐは０〜３の整数を示す）、ｎは０〜１０の整数を示す。）などが挙げられる。
これらの中では、極性基が−（ＣＨ₂）_nＣＯＯＲ¹（ここで、Ｒ¹は炭素数１〜２０の炭化水素基、ｎは０〜１０の整数を示す）で表される基であることが、得られる重合体が高いガラス転移温度を有するものとなるので好ましい。特に、この−（ＣＨ₂）_nＣＯＯＲ¹で表される基は、一般式（１）のノルボルネン系誘導体の１分子あたりに１個含有されることが好ましい。前記一般式において、Ｒ¹は炭素数１〜２０の炭化水素基であるが、炭素数が多くなるほど得られる重合体の吸湿性が小さくなる点では好ましいが、得られる重合体のガラス転移温度とのバランスの点から、炭素数１〜４の鎖状アルキル基または炭素数５以上の（多）環状アルキル基であることが好ましく、特にメチル基、エチル基、シクロヘキシル基であることが好ましい 。
【０００８】
ｎは０〜１０であるが、ｎの値が小さいものほど、得られるノルボルネン系重合体のガラス転移温度が高くなるので好ましい。特にｎが０のものは、その合成が容易である点で、また得られる重合体がガラス転移温度の高いものとなる点で好ましい。また一般式（１）においてｍは０〜２であるが、好ましくは０〜１であり、特にｍが１であるものはガラス転移温度の高い重合体が得られる点で好ましい。
さらに、−（ＣＨ₂）_nＣＯＯＲ¹で表される基が結合した炭素原子に、同時に炭素数１〜１０の炭化水素基が置換基として結合されている一般式（１）のノルボルネン系誘導体は、吸湿性を低下させるので好ましい。特に、この置換基がメチル基またはエチル基である一般式（１）のノルボルネン系誘導体は、その合成が容易な点で好ましい。
【０００９】
一般式（１）の具体例としては、
５−メトキシカルボニルビシクロ［２，２，１］ヘプト−２−エン、５−メチル−５−メトキシカルボニルビシクロ［２，２，１，］ヘプト−２−エン、５−シアノビシクロ［２，２，１］ヘプト−２−エン、８−メトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−エトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−ｎ−プロポキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−イソプロポキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−ｎ−ブトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−（１−メチルプロピルオキシカルボニル）テトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−（２−メチルプロピルオキシカルボニル）テトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−（２，２−ジメチルエチルオキシカルボニル）テトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−シクロヘキシルオキシテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−メチル−８−エトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−メチル−８−ｎ−プロポキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−メチル−８−イソプロポキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−メチル−８−ｎ−ブトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エン、８−メチル−８−シクロヘキシルオキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−３−エンがあげられる。
これらの中では８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１^2,5１^7,10］ドデカ−８−エンが好ましい。上記の単量体は必ずしも単独で用いる必要はなく、２種以上を用いて開環共重合反応を行うこともできる。
【００１０】
本発明において、上記重合体は、上記の単量体を単独で開環重合させたものであってもよいが、当該単量体と共重合性単量体とを開環共重合させたものであってもよい。この場合に使用することのできる共重合性単量体の具体例としては、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、ビシクロ［２．２．１］ヘプト−エン、トリシクロ［５．２．１．０^2,6］−３−デセン、５−エチリデン−２−ノルボルネン、ジシクロペンタジエンなどのシクロオレフィンを挙げることができる。さらにポリブタジエン、ポリイソプレン、スチレン−ブタジエン共重合体、エチレン−非共役ジエン重合体、ポリノルボルネンなどの主鎖に炭素−炭素間二重結合を含む不飽和炭化水素系ポリマーなどの存在下に特定単量体を開環重合、水素添加させてもよい。
上記の重合体は、前述の単量体あるいはこれと前記共重合性単量体を例えば特開平７―２８７１２３号公報に記載されている開環重合触媒や開環重合反応溶媒、水素添加触媒などを用いて重合、水素添加することにより得ることができる。
【００１１】
本発明において、上記水添重合体は、クロロホルム中、３０℃で測定される固有粘度（［η］_inh）が０．３〜１．５ｄｌ／ｇの範囲であることが望ましい。［η］_inhが上記範囲にあることによって、得られる樹脂の成形加工性、耐熱性、機械的特性のバランスが良好となる。
また、前記水添重合体のガラス転移温度（Ｔｇ）は１００℃〜２５０℃の範囲であることが好ましく、特に１２０〜２００℃の範囲であることが好ましい。１００℃未満では該樹脂からなる成形品の耐熱性が劣る。また、Ｔｇが２５０℃を超えるものは、成形温度が高くなり樹脂が焼けて着色するなど良質な成形品を得ることが難しくなる。
【００１２】
また、水添重合体の水素添加率は、６０ＭＨｚ、 ¹Ｈ−ＮＭＲで測定した値が５０％以上、好ましくは９０％以上、さらに好ましくは９８％以上である。水素添加率が高いほど、熱や光に対する安定性が優れる。
なお、本発明において、ノルボルナン骨格を有する熱可塑性樹脂として使用される水添重合体は、該水添重合体中に含まれるゲル含有量が５重量％以下であることが好ましく、さらに１重量％であることが好ましい。
【００１３】
上記のごとく得られる開環重合体水添物の飽和吸水率は、ＡＳＴＭ Ｄ５７０に従い２３℃で１週間浸漬して得た値が０．１〜１重量％の範囲にあることが好ましい。飽和吸水率が０．１重量％未満では成形品表面に積層される光選択吸収層との密着性に劣り、使用途中で剥離が発生する恐れがある。また、樹脂中に配合される光選択吸収剤やその他添加剤との相溶性に欠けるため、使用途中で成形品表面にブリードしたりする問題も出やすい。一方飽和吸水率が１重量％を超えると、吸水により成形品に変形が発生したりレンズの焦点が変動するなどの問題がある。
【００１４】
一般に熱可塑性ノルボルネン系樹脂は、ノルボルナン骨格における置換基がすべて水素原子あるいは炭化水素基のような非極性であると、吸水率が０．１重量％未満となり密着性や酸化防止剤の相溶性に劣るものとなる。また、上記一般式（１）においてＡ、Ｂ、ＸおよびＹのすべてが極性基であると吸水率が１重量％を超えた大きなものとなることがある。従って本発明においては、上記一般式（１）における置換基を樹脂の飽和吸水率が上記範囲内となるように選択することが好ましい。
【００１５】
本発明に用いる熱可塑性ノルボルネン系樹脂には、必要に応じて公知の酸化防止剤を添加することができる。かかる酸化防止剤としては、例えば２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，２’−ジオキシ−３，３’−ジ−ｔ−ブチル−５，５’−ジメチルフェニルメタン、テトラキス［メチレン−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］メタン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５ートリメチル−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、ステアリル−β−（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’−ジオキシ−３，３’−ジ−ｔ−ブチル−５，５’−ジエチルフェニルメタン、３，９−ビス［１，１−ジメチル−２−［β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル］、２，４，８，１０−テトラオキスピロ［５，５］ウンデカン、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、２，２−メチレンビス （４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイトなどを挙げることができる。
【００１６】
また、上記の熱可塑性ノルボルネン系樹脂には、上記のような酸化防止剤の他に、必要に応じて安定剤、帯電防止剤、難燃剤、耐衝撃性改良用エラストマーなどを添加することができる。また、成形性、加工性を向上させる目的で可塑剤、軟化剤などの添加剤を添加することもできる。
【００１７】
本発明の光選択吸収性成形品は、上記熱可塑性ノルボルネン系樹脂と光選択吸収剤が含有されてなる樹脂組成物を成形してなる成形品表面に光選択吸収層を形成して得られる。
熱可塑性ノルボルネン系樹脂に所定の光選択吸収剤を配合して得られる樹脂組成物中、光選択吸収剤の配合量は、上記熱可塑性ノルボルネン系樹脂中１００重量部に対し、好ましくは０．００１〜２０重量部、さらに好ましくは０．１〜１０重量部である。光選択吸収剤が、少なすぎると、目的とする機能が充分に発現し得ず、多すぎると光選択吸収剤と熱可塑性ノルボルネン系樹脂との相溶性が悪くなり、表面にブリードしたり色むらが起こるなど均一な成形品とすることが難しくなる。
【００１８】
このような樹脂組成物は、各種押出機、バンバリーミキサー、ニーダー、ロール、フィーダールーダーなどを用い、各成分を混練りすることにより得られる。混練り温度は、好ましくは１００〜３５０℃、さらに好ましくは１５０〜３００℃である。
また、各成分を混練りするに際しては、各成分を一括して混練りしてもよく、数回にわけて添加混練りしてもよい。混練りは、押出機を用い多段添加式で混練りしてもよく、またバンバリーミキサー、ニーダーなどで混練りし、その後、押出機でペレット化することもできる。
本発明の光選択吸収性成形品は上記樹脂組成物を射出成形、押出成形、圧縮成形などの公知の方法で得ることができる。ここで成形品の形状は特に限定されるものではなく、板状、円盤状、レンズ形状などであってもよい。
【００１９】
上記方法により得られた成形品表面に光選択吸収層を形成する方法としては、（ａ）光選択吸収剤を含む塗料を該成形品表面に塗布する方法、（ｂ）光選択吸収剤を上記成形品表面に真空蒸着法、イオンプレーティング法、スパッタリング法などの方法により層形成する方法、（ｃ）上記成形品を光選択吸収剤を含む溶液に含浸する方法、（ｄ）上記成形品表面に光選択吸収剤を含むフィルムを貼付する方法、またはこれらの組み合わせであってよい。
【００２０】
（ａ）の方法において、熱可塑性ノルボルネン系樹脂からなる成形品に塗布される光選択吸収剤は１種であってもよいし２種以上であってもよい。かかる光選択吸収剤は適当な溶剤またはこれに熱可塑性ノルボルネン系樹脂を溶解させてなる溶液中に溶解または分散させた後、塗布に用いられる。ここで溶剤に溶かす熱可塑性ノルボルネン系樹脂は、成形品を形成する熱可塑性ノルボルネン系樹脂と同一構造のものでもよく、また異なっていてもよいが、同一構造のものが光学特性の点からより好ましい。上記成形法において使用できる溶媒の例としては、ベンゼン、トルエン、キシレン等の芳香族化合物、酢酸ブチル、テトラヒドロフラン、ジメトキシエタン、四塩化炭素、クロロホルム、二塩化メチレンなどがあげられ、これらの混合溶媒でもよい。また上記熱可塑性ノルボルネン系樹脂を溶解する溶媒と溶解しない溶媒との混合であってもよい。さらに水や油脂を使用することもできる。
成形品に溶液を塗布する方法は特に限定されず、スプレー、ハケ、ロール、スピンコート、ディッピングなどの公知の方法を用いることができる。
【００２１】
（ｃ）の方法において、成形品を含浸する溶液は光選択吸収性の染料を水または各種溶剤に溶解または分散させてなるものである。ここで溶媒の例としては熱可塑性ノルボルネン系樹脂からなる成形品を溶解しないものが好ましく、酸、アルカリ、アルコール類を用いることができる。これらの中では分散染料を水中に分散させてなるもの、あるいはこれに付着性を高める目的で各種溶剤を加えたものが好ましい。ここで分散染料は１種であってもよく２種以上であってもよい。分散染料を水中に添加する割合は、水１００重量部に対して０．０１〜５重量部、好ましくは０．０５〜２重量部である。分散染料が０．０１重量部以下の場合には染色に時間がかかり、５重量部を超えると分散しにくくなり、濃度が増したための効果がなくなる上に均一な染色が困難となる。
【００２２】
本発明において成形品表面に光選択吸収層を積層する場合、層は単層でもよく多層であってもよい。また、本発明において成形品表面に光選択吸収層を積層する前に、必要に応じて接着層が積層されていてもよい。
本発明に用いられる光選択吸収剤としては、通常に用いられている有機または無機の染料・顔料が使用できる。これらの例としては、シアニン系、ピリリウム系、スクワリリウム系、クロコニウム系、アズレニウム系、ニトロソ系、ニトロ系、モノアゾ系、ジアゾ系、縮合アゾ系、アゾレーキ系、ジフェニルメタン系、トリフェニルメタン系、キサント系、アジン系、トリアジン系、トリアゾール系、キノリン系、インジゴ系、ナフトキノン系、アントラキノン系、インドフェノール系、フタロシアニン系、ジアリリド系、ベンズイミダゾロン系、キナクリド系、ペリレン系などの染顔料、酸化インジウム、酸化スズ、チッ化チタン、チッ化ジルコニウム、チッ化ハフニウム、チタン、鉄、クロム、ＳＵＳ鋼、銀、アルミニウム、スズ、ニッケル、コバルト、プラセオジム、ネオジム、サマリウム、ユーロピウム、ジスプロシウム、ホルミウム、ツリウム等の無機物または無機化合物などが挙げられる。これらは各波長帯域における光線透過率を調節するために適宜選択され、１種または２種以上を組み合わせてもよい。
【００２３】
また、光学フィルターとして、光選択吸収剤のほかにさらに紫外線領域の遮光性能を高めるため紫外線吸収剤を適宜併用してもよい。これらの具体例としては、例えば２―（５―メチルー２―ヒドロキシフェニル）ベンゾトリアゾール、２［２―ヒドロキシ−３，５―ビス（α、α―ジメチルベンジル）フェニル］−２Ｈ―ベンゾトリアゾール、２―（３，５―ジーｔ―ブチルー２―ヒドロキシフェニル）ベンゾトリアゾール、２−（３―ｔ―ブチルー５―メチルー２―ヒドロキシフェニル）５―クロロベンゾトリアゾール、２−（３，５―ジーｔ―ブチルー２―ヒドロキシフェニル）５―クロロベンゾトリアゾール、２―（３，５―ジーｔ―アミルー２―ヒドロキシフェニル）ベンゾトリアゾール、２―（２'―ヒドロキシー５'―ｔ―オクチルフェニル）ベンゾトリアゾール、メチルー３―［３―ｔ―ブチルー５―（２Ｈ―ベンゾトリアゾールー２―イル）―４―ヒドロキシフェニル］プロピオネート・ポリエチレングリコール縮合物、ヒドロキシフェニルベンゾトリアゾール誘導体などのベンゾトリアゾール系；２―ヒドロキシー４―メチルオキシベンゾフェノンー５―スルホキシド、２―ヒドロキシー４―ｎ−オクトキシベンゾフェノン、２―ヒドロキシー４−ｎ−ドデシロキシベンゾフェノン、２―ヒドロキシー４―ベンジロキシベンゾフェノンなどのベンゾフェノン系紫外線吸収剤が挙げられる。これらは光選択吸収剤とともに、目的とする吸収波長帯になるように適宜選択して使用することができる。
【００２４】
本発明の光選択吸収性樹脂成形品において、選択透過させる光の波長領域は特に限定されなず、目的に応じて選択することができる。例えば、可視光領域（４００ｎｍ〜７５０ｎｍ）のみを選択透過させたい場合は、紫外領域（２００ｎｍ〜４００ｎｍ）の光を吸収する光選択吸収剤と、近赤外・赤外領域（７５０ｎｍ〜１０００μｍ）の光を吸収する光選択吸収剤のうちの一方を本発明で使用する熱可塑性ノルボルネン系樹脂に配合させて得られる樹脂組成物を所望の成形品とした後、もう一方の光選択吸収剤を用いて該成形品表面に前述の方法で層形成すればよい。また、近赤外領域（７５０ｎｍ〜２０００ｎｍ）の光のみを選択透過させる場合は紫外・可視光領域（２００ｎｍ〜７５０ｎｍ）の光を吸収する光選択吸収剤と赤外領域（２０００ｎｍ〜１０００μｍ）の光を吸収する光選択吸収剤の一方を樹脂に配合させ、一方を成形品表面に層形成させるようにすればよい。その他、光選択吸収剤の組み合わせによってさまざまな特定波長領域の光を選択透過することが可能である。
【００２５】
本発明の光選択吸収性成形品は、板状の場合は光学フィルターとして、レンズ形状の場合は光選択吸収性レンズとして、光通信機器やセンサー類などの光ファイバーモジュール用フィルターおよびレンズ；テレビ受像器、ＶＴＲ、その他のＡＶ機器、エアコン等の家庭内使用機器類のリモコン用受光部の窓材；一眼レフカメラ、コンパクトカメラ、カメラ一体型ＶＴＲなどのオートフォーカス用窓材；自動ドアやセキュリティ関係の感知機用窓材など広範な用途に使用可能である。
【００２６】
【実施例】
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例中、部および％は、特に断らない限り重量基準である。
参考例１
特定単量体として、下記化（２）で表される８―メチルー８―メトキシカルボニルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン２５０部と１−ヘキセン４１部とトルエン７５０部を、窒素置換した反応容器に仕込み、６０℃に加熱した。
【００２７】
【化２】

【００２８】
これに、トリエチルアルミニウム（１．５モル／ｌ）のトルエン溶液０．６２部、ｔＢｕＯＨ／ＭｅＯＨで変性（ｔＢｕＯＨ／ＭｅＯＨ／Ｗ=０．３５／０．３／１；モル比）したＷＣｌ₆溶液（濃度０．０５モル／ｌ）３．７部を加え、８０℃で３時間加熱攪拌して、開環重合体溶液（ａ）を得た。
この重合反応における重合転化率は９７％であり、重合体の固有粘度（η_inh）は０．４５であった。
この重合体溶液（ａ）４０００部をオートクレーブに入れ、これにＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃０．４８部を加え、水素ガス圧を１００ｋｇ／ｃｍ²、反応温度１６５℃の条件で３時間加熱攪拌した。
得られた反応溶液を冷却した後、水素ガス圧を放圧し、水素添加重合体溶液（ｂ）を得た。こうして得られた水素添加重合体を大量のメタノールに注いで、重合体を凝固させた。こうして得られた水素添加重合体Ａ−１の水素化率は実質上１００％であった。
【００２９】
参考例２
特定単量体として８−エチリデンテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン２００部を用いたこと以外は参考例１と同様にして開環重合反応、水素添加反応させ、水素添加重合体Ａ−２を得た。
【００３０】
実施例１
参考例１で得られた水素添加重合体Ａ−１を１００部、緑色着色剤ソルベントグリーン２８を０．５部添加し、温度２８０℃で４０ｍ／ｍ押出機を用いて混合してペレット状の熱可塑性樹脂組成物を製造した。
この熱可塑性樹脂組成物を用いて樹脂温度３２０℃、金型温度１３０℃で射出成形し、厚み１ｍｍの平板を得た。この平板表面に酸化インジウムスズ（ＩＴＯ）を用いスパッタリング法により３００ｎｍの膜を形成し、光学フィルターを作成した。この光学フィルターについて、近赤外光透過性、光遮断性、熱変形性および耐湿性を評価した。評価結果を表１に示す。なお、各測定は以下のように行った。
【００３１】
近赤外光透過性（％）
分光光度計を用い、厚み１ｍｍの光学フィルターについて波長９５０ｎｍの近赤外領域光の透過率を測定した。
光遮断性（％）
分光光度計を用い、厚み１ｍｍの光学フィルターについて波長４００〜７００ｎｍの可視領域光及び２０００ｎｍ以上の赤外領域光の透過率を測定した。
熱変形性
１２０℃のエアーオーブンに２４時間入れた後の成形品の外観変化を目視で観察し、以下の評価基準に従って熱変形性を評価した。
○：ソリなどの変形が全く見られないもの
×：ソリなどの変形が顕著であるもの
耐久性
８０℃、９０％相対湿度の条件で１０００時間保持した後の成形品の外観により、以下の評価基準に従って耐久性を評価した。
○：光選択吸収剤の成形品からの層剥離もしくはブリードアウト、または成形品の変形がなく発光が均一であるもの
×：光選択吸収剤の成形品からの層剥離もしくはブリードアウト、または成形品の変形が顕著であり使用に耐えないもの
【００３２】
実施例２
水素添加重合体Ａ−１を１００部、赤色着色剤ソルベントレッド５２を０．１部をジクロロメタン／ジクロロエタン混合溶液に溶解してなる濃度１０重量％の樹脂溶液を得た。
一方、参考例１で得られた水素添加重合体Ａ―１を１００部と緑色着色剤ソルベントグリーン２８を０．５部添加し、実施例１と同様に製造された熱可塑性樹脂組成物を用いて市販の射出成形機にて樹脂温度３２０℃、金型温度１３０℃で射出成形し、厚み１ｍｍの平板を得た。この平板の表面に、上記樹脂溶液をスピンコートにより塗布・乾燥して厚さ３００ｎｍの着色層を形成して光学フィルターを得た。この光学フィルターについて、実施例１と同様の評価を行った。評価結果を表１に示す。
【００３３】
比較例１
水素添加重合体Ａ−１のかわりに水素添加重合体Ａ−２を用いた他は実施例１と同様にして熱可塑性樹脂組成物を製造し、実施例１と同様に光学フィルターを成形して評価を行った。評価結果を表１に示す。
比較例２
熱可塑性ノルボルネン系樹脂Ａ−１のかわりにポリメチルメタクリレート樹脂（ＰＭＭＡ）（商品名「アクリペットＶＨ」、三菱レイヨン（株）製）を用い、樹脂温度２３０℃、金型温度１００℃とした他は実施例１と同様にして熱可塑性樹脂組成物を製造し、実施例１と同様に平板を成形して評価を行った。評価結果を表１に示す。
【００３４】
【表１】

【００３５】
表１から明らかなように、本発明の光選択吸収性成形品は光選択吸収性に優れ、しかも耐熱性や耐湿性に優れている。
これらに対し、比較例１は高温高湿下で使用するうちに成形品からの光選択吸収剤のブリードアウトや剥離が発生するため、実使用において問題が発生しやすい。また透明基材樹脂にＰＭＭＡを用いたもの（比較例２）は、熱や湿度による変形が大きく用途範囲や使用条件が限られるものである。
【００３６】
実施例３
参考例１で得られた水素添加重合体１００部と緑色着色剤ソルベントグリーン２８を０．５重量部添加し、実施例１と同様に製造された熱可塑性樹脂組成物を用いて実施例１の市販の射出成形機にて樹脂温度３２０℃、金型温度１３０℃で射出成形し、外径７．４ｍｍφ、レンズ面厚み２．７ｍｍ、周辺部厚み３．０ｍｍのレンズを得た。このレンズの表面に酸化インジウムスズ（ＩＴＯ）を用いスパッタリング法により３００ｎｍの膜を形成した。
このレンズについて分光光度計を用い、各波長における光透過性を測定したところ、波長９５０ｎｍの近赤外領域において９０％、波長４００〜７００ｎｍの可視領域光、および波長２０００ｎｍの赤外領域光においてそれぞれ透過率１％、２％と極めて良好な光選択吸収性を示した。
【００３７】
【発明の効果】
本発明の熱可塑性樹脂組成物は、高温高湿下での耐久性に優れ、しかも光選択吸収性に優れた成形品を与えるので、光選択吸収・透過を目的とする広範な用途に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a light selective absorption resin molded article that selectively absorbs light of a specific wavelength, and an optical filter and lens comprising the same, and a light selective absorption resin excellent in durability that does not deteriorate performance even in long-term use. It relates to molded products.
[0002]
[Prior art]
Conventionally, molded products that selectively absorb light of a specific wavelength have been widely used in the fields of electrical and electronic equipment and optical communication. Such a filter is obtained by appropriately coating a substance on the surface of a transparent plate made of glass or plastic, and a material comprising a composition having desired optical properties obtained by appropriately blending a substance with the transparent substance itself. In the case of a filter that selectively transmits only a specific wavelength and blocks the others, a composition comprising a transparent resin and a light selective absorbent is molded. A technique is generally used in which the surface of an optical molded article is subjected to a treatment such as coating, vapor deposition, and sputtering of an appropriate material having photoselectivity.
Transparent materials such as glass and acrylic are used as transparent materials for such compositions, but filters made of glass are fragile and heavy, and they can be processed such as forming, cutting, and polishing during filter production. There is a problem that it is difficult. As transparent resins, acrylic thermosetting resins and acrylic thermoplastic resins are known because they require low birefringence. However, thermosetting resins take a long time to mold and are inferior in productivity. The thermoplastic acrylic resin has a low heat deformation temperature of about 80 ° C. and a relatively large water absorption rate, so there is a risk of deformation depending on the heat applied when forming the light selective absorption layer on the molded product and the use environment of the product. There is a problem that the forming method and the application range are limited.
For the purpose of improving these heat resistance and moisture resistance, a technique using a light selective absorption composition comprising a thermoplastic norbornene resin is disclosed in JP-A-6-200113 and JP-A-6-256564.
[0003]
[Problems to be solved by the invention]
However, some of these thermoplastic norbornene-based resins have poor compatibility and dispersibility with the photoselective absorber, and it is difficult to obtain a good molded product, and the light formed on the surface of the molded product is difficult. There was also a problem that the adhesion with the selective absorption layer was poor and these layers were peeled off from the molded product during use.
The present invention has been made against the background of the above-described prior art, and is excellent in moldability, workability, heat resistance, moisture resistance, and does not deteriorate in performance due to long-term use. The purpose is to provide goods.
[0004]
[Means to solve the problem]
The light-selective absorbent resin molded article of the present invention is a monomer comprising at least one norbornene derivative represented by the following general formula (1) or a copolymerizable monomer copolymerizable with this monomer. Photoselective absorbent resin in which a photoselective absorption layer is further formed on the surface of a molded article formed from a composition comprising a hydrogenated polymer obtained by ring polymerization and a photoselective absorber It is a molded product.
[0005]
[Chemical 1]

[0006]
(In the formula, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom or a monovalent organic group, and at least one of X and Y is a hydrogen atom and A group having polarity other than a hydrocarbon group is shown, and m is 0 to 2.)
[0007]
In the general formula (1), examples of polar groups other than hydrocarbon groups include — (CH₂)_nCOOR¹,-(CH₂)_nOCOR¹,-(CH₂)_nCN,-(CH₂)_nCONR²R^Three,-(CH₂)_nCOOZ,-(CH₂)_nOCOS,-(CH₂)_nOZ,-(CH₂)_nCW, or —CO—O—OC— or —CO—NR composed of X and Y^Four-OC- (R¹, R², R^Three, R^FourIs a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group substituted with a halogen atom, W is SiR^Five _pF_3-p(R^FiveIs a hydrocarbon group having 1 to 10 carbon atoms, F is -OCOR⁶Or -OR⁶(R⁶Represents a hydrocarbon group having 1 to 10 carbon atoms), p represents an integer of 0 to 3), and n represents an integer of 0 to 10. ) And the like.
Among these, the polar group is — (CH₂)_nCOOR¹(Where R¹Is a group represented by a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 10), since the resulting polymer has a high glass transition temperature. In particular, this-(CH₂)_nCOOR¹Is preferably contained per molecule of the norbornene derivative of the general formula (1). In the above general formula, R¹Is a hydrocarbon group having 1 to 20 carbon atoms, which is preferable in terms of decreasing the hygroscopicity of the polymer obtained as the number of carbon atoms increases, but from the point of balance with the glass transition temperature of the polymer obtained, carbon A chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is particularly preferable.
[0008]
Although n is 0-10, since the glass transition temperature of the norbornene-type polymer obtained becomes high so that the value of n is small, it is preferable. In particular, n = 0 is preferable in that the synthesis is easy and the polymer obtained has a high glass transition temperature. In the general formula (1), m is 0 to 2, preferably 0 to 1, and particularly preferably m is 1 in that a polymer having a high glass transition temperature is obtained.
Furthermore,-(CH₂)_nCOOR¹The norbornene derivative of the general formula (1) in which a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the group represented by formula (I) is bonded is preferable because it reduces hygroscopicity. In particular, the norbornene derivative of the general formula (1) in which the substituent is a methyl group or an ethyl group is preferable from the viewpoint of easy synthesis.
[0009]
As a specific example of the general formula (1),
5-methoxycarbonylbicyclo [2,2,1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2,2,1,] hept-2-ene, 5-cyanobicyclo [2,2, 1] hept-2-ene, 8-methoxycarbonyltetracyclo [4.4.0.1^2,51^7,10] Dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8- (1-methylpropyloxycarbonyl) tetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8- (2-methylpropyloxycarbonyl) tetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8- (2,2-dimethylethyloxycarbonyl) tetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-cyclohexyloxytetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo [4.4.0.1]^2,51^7,10] Dodec-3-ene.
Among these, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1^2,51^7,10] Dodec-8-ene is preferred. The above-mentioned monomers do not necessarily need to be used alone, and the ring-opening copolymerization reaction can be performed using two or more kinds.
[0010]
In the present invention, the polymer may be obtained by ring-opening polymerization of the above monomer alone, but is obtained by ring-opening copolymerization of the monomer and a copolymerizable monomer. It may be. Specific examples of the copolymerizable monomer that can be used in this case include cyclobutene, cyclopentene, cycloheptene, cyclooctene, bicyclo [2.2.1] hept-ene, and tricyclo [5.2.1.0].^2,6And cycloolefin such as 3-decene, 5-ethylidene-2-norbornene, and dicyclopentadiene. In addition, specific units in the presence of unsaturated hydrocarbon polymers containing a carbon-carbon double bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene polymer, and polynorbornene. The monomer may be ring-opening polymerized or hydrogenated.
The above-mentioned polymer may be prepared by combining the above-mentioned monomer or the copolymerizable monomer with the above-described monomer, for example, a ring-opening polymerization catalyst, a ring-opening polymerization reaction solvent, a hydrogenation catalyst described in JP-A-7-287123. Can be obtained by polymerization and hydrogenation.
[0011]
In the present invention, the hydrogenated polymer has an intrinsic viscosity ([η]) measured at 30 ° C. in chloroform._inh) Is preferably in the range of 0.3 to 1.5 dl / g. [Η]_inhIs in the above range, the balance of molding processability, heat resistance, and mechanical properties of the resulting resin is improved.
The glass transition temperature (Tg) of the hydrogenated polymer is preferably in the range of 100 ° C. to 250 ° C., particularly preferably in the range of 120 to 200 ° C. If it is less than 100 degreeC, the heat resistance of the molded article which consists of this resin is inferior. In addition, when the Tg exceeds 250 ° C., it becomes difficult to obtain a high-quality molded product such that the molding temperature becomes high and the resin is burnt and colored.
[0012]
The hydrogenation rate of the hydrogenated polymer is 60 MHz,¹The value measured by H-NMR is 50% or more, preferably 90% or more, more preferably 98% or more. The higher the hydrogenation rate, the better the stability to heat and light.
In the present invention, the hydrogenated polymer used as the thermoplastic resin having a norbornane skeleton preferably has a gel content contained in the hydrogenated polymer of 5% by weight or less, and more preferably 1% by weight. It is preferable that
[0013]
The saturated water absorption rate of the ring-opened polymer hydrogenated product obtained as described above is preferably in the range of 0.1 to 1% by weight obtained by immersion for 1 week at 23 ° C. according to ASTM D570. When the saturated water absorption is less than 0.1% by weight, the adhesiveness with the light selective absorption layer laminated on the surface of the molded product is inferior, and peeling may occur during use. Moreover, since the compatibility with the light selective absorbent and other additives blended in the resin is lacking, there is a tendency to bleed on the surface of the molded product during use. On the other hand, when the saturated water absorption exceeds 1% by weight, there are problems such as deformation of the molded product due to water absorption and fluctuation of the focal point of the lens.
[0014]
In general, a thermoplastic norbornene-based resin has a water absorption of less than 0.1% by weight when the substituents in the norbornane skeleton are all non-polar, such as a hydrogen atom or a hydrocarbon group, thereby improving adhesion and compatibility of antioxidants. It will be inferior. Further, in the above general formula (1), if all of A, B, X and Y are polar groups, the water absorption rate may be as large as more than 1% by weight. Therefore, in the present invention, the substituent in the general formula (1) is preferably selected so that the saturated water absorption rate of the resin falls within the above range.
[0015]
A known antioxidant can be added to the thermoplastic norbornene resin used in the present invention, if necessary. Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethylphenylmethane, Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl-benzene, stearyl-β- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- [β- ( 3-t-butyl-4- Droxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxospiro [5,5] undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neo Pentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2-methylenebis And (4,6-di-t-butylphenyl) octyl phosphite.
[0016]
In addition to the above antioxidants, stabilizers, antistatic agents, flame retardants, impact resistance improving elastomers, and the like can be added to the thermoplastic norbornene-based resins as necessary. . In addition, additives such as a plasticizer and a softener can be added for the purpose of improving moldability and processability.
[0017]
The light selective absorption molded article of the present invention is obtained by forming a light selective absorption layer on the surface of a molded article formed by molding the resin composition containing the thermoplastic norbornene resin and the light selective absorbent.
In the resin composition obtained by blending a predetermined photoselective absorber with a thermoplastic norbornene resin, the blending amount of the photoselective absorber is preferably 0.001 with respect to 100 parts by weight in the thermoplastic norbornene resin. -20 parts by weight, more preferably 0.1-10 parts by weight. If the photoselective absorber is too small, the target function cannot be sufficiently exhibited. If the photoselective absorber is too much, the compatibility between the photoselective absorber and the thermoplastic norbornene resin is deteriorated, causing bleeding or uneven color on the surface. It becomes difficult to make a uniform molded product such as.
[0018]
Such a resin composition is obtained by kneading each component using various extruders, Banbury mixers, kneaders, rolls, feeder ruders, and the like. The kneading temperature is preferably 100 to 350 ° C, more preferably 150 to 300 ° C.
Moreover, when kneading each component, each component may be kneaded in a lump or may be added and kneaded in several times. The kneading may be performed by a multistage addition method using an extruder, or may be kneaded by a Banbury mixer, a kneader or the like, and then pelletized by an extruder.
The light selective absorption molded article of the present invention can be obtained by a known method such as injection molding, extrusion molding or compression molding of the resin composition. Here, the shape of the molded product is not particularly limited, and may be a plate shape, a disk shape, a lens shape, or the like.
[0019]
As a method of forming the light selective absorption layer on the surface of the molded product obtained by the above method, (a) a method of applying a paint containing a light selective absorbent to the surface of the molded product, and (b) the light selective absorber described above. A method of forming a layer on the surface of the molded article by a method such as vacuum deposition, ion plating, or sputtering; (c) a method of impregnating the molded article in a solution containing a light selective absorbent; and (d) a surface of the molded article. It may be a method of attaching a film containing a light selective absorber to the above, or a combination thereof.
[0020]
In the method (a), the photoselective absorbent applied to the molded article made of the thermoplastic norbornene resin may be one type or two or more types. Such a light selective absorber is used for coating after being dissolved or dispersed in a suitable solvent or a solution obtained by dissolving a thermoplastic norbornene resin in this solvent. Here, the thermoplastic norbornene-based resin dissolved in the solvent may have the same structure as or different from the thermoplastic norbornene-based resin forming the molded article, but the same structure is more preferable from the viewpoint of optical characteristics. . Examples of solvents that can be used in the above molding method include aromatic compounds such as benzene, toluene, xylene, butyl acetate, tetrahydrofuran, dimethoxyethane, carbon tetrachloride, chloroform, methylene dichloride, and the like. Good. Moreover, the mixture of the solvent which melt | dissolves the said thermoplastic norbornene-type resin and the solvent which does not melt | dissolve may be sufficient. Furthermore, water and fats and oils can also be used.
The method for applying the solution to the molded article is not particularly limited, and a known method such as spraying, brushing, roll, spin coating, dipping or the like can be used.
[0021]
In the method (c), the solution for impregnating the molded article is obtained by dissolving or dispersing a light selective absorbing dye in water or various solvents. Here, as an example of the solvent, a solvent that does not dissolve a molded article made of a thermoplastic norbornene resin is preferable, and acids, alkalis, and alcohols can be used. Among these, those obtained by dispersing a disperse dye in water or those added with various solvents for the purpose of improving adhesion are preferred. Here, the disperse dye may be one kind or two or more kinds. The proportion of the disperse dye added to water is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of water. When the amount of the disperse dye is 0.01 parts by weight or less, it takes time for dyeing. When the amount exceeds 5 parts by weight, it becomes difficult to disperse, and the effect of increasing the concentration is lost and uniform dyeing becomes difficult.
[0022]
In the present invention, when the light selective absorption layer is laminated on the surface of the molded product, the layer may be a single layer or a multilayer. Moreover, before laminating | stacking a light selective absorption layer on the molded article surface in this invention, the contact bonding layer may be laminated | stacked as needed.
As the light selective absorbent used in the present invention, organic or inorganic dyes / pigments which are usually used can be used. Examples of these include cyanine, pyrylium, squarylium, croconium, azurenium, nitroso, nitro, monoazo, diazo, condensed azo, azo lake, diphenylmethane, triphenylmethane, xanthate , Azine, triazine, triazole, quinoline, indigo, naphthoquinone, anthraquinone, indophenol, phthalocyanine, diarylide, benzimidazolone, quinaclide, perylene, and other pigments, indium oxide, Tin oxide, titanium nitride, zirconium nitride, hafnium nitride, titanium, iron, chromium, SUS steel, silver, aluminum, tin, nickel, cobalt, praseodymium, neodymium, samarium, europium, dysprosium, holmium, thulium Such mineral or inorganic compound and the like. These are appropriately selected for adjusting the light transmittance in each wavelength band, and may be used alone or in combination of two or more.
[0023]
Further, as the optical filter, in addition to the light selective absorbent, an ultraviolet absorbent may be used in combination as appropriate in order to further improve the light shielding performance in the ultraviolet region. Specific examples thereof include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) 5-chlorobenzotriazole, 2- (3,5-di-t- Butyl-2-hydroxyphenyl) 5-chlorobenzotriazole, 2- (3,5-di-t-amylu-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, methyl- 3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxy Enyl] propionate-polyethylene glycol condensate, benzotriazole type such as hydroxyphenylbenzotriazole derivative; 2-hydroxy-4-methyloxybenzophenone-5-sulfoxide, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n -A benzophenone ultraviolet absorber, such as dodecyloxybenzophenone and 2-hydroxy-4-benzyloxybenzophenone. These can be selected and used together with the light selective absorber so as to obtain the intended absorption wavelength band.
[0024]
In the light selective absorption resin molded product of the present invention, the wavelength region of light to be selectively transmitted is not particularly limited and can be selected according to the purpose. For example, when it is desired to selectively transmit only the visible light region (400 nm to 750 nm), a light selective absorber that absorbs light in the ultraviolet region (200 nm to 400 nm) and a near infrared / infrared region (750 nm to 1000 μm). A resin composition obtained by blending one of the light selective absorbers that absorbs light with the thermoplastic norbornene resin used in the present invention is used as a desired molded article, and then the other light selective absorber is used. Then, the layer may be formed on the surface of the molded product by the method described above. In the case of selectively transmitting only light in the near infrared region (750 nm to 2000 nm), a light selective absorber that absorbs light in the ultraviolet / visible light region (200 nm to 750 nm) and light in the infrared region (2000 nm to 1000 μm). One of the light selective absorbents that absorbs water may be blended with the resin, and the other may be layered on the surface of the molded product. In addition, it is possible to selectively transmit light in various specific wavelength regions by combining light selective absorbers.
[0025]
The light selective absorptive molded article of the present invention is an optical filter in the case of a plate, a light selective absorptive lens in the case of a lens, a filter and a lens for optical fiber modules such as optical communication equipment and sensors; a television receiver. , VTR, other AV equipment, window material for remote control light receiving parts of home-use equipment such as air conditioners; autofocus window materials such as single-lens reflex cameras, compact cameras, camera-integrated VTRs; automatic doors and security-related It can be used for a wide range of applications such as sensor window materials.
[0026]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example. In the examples, parts and% are based on weight unless otherwise specified.
Reference example 1
As the specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 represented by the following chemical formula (2):^2,5. 1^7,10] 250 parts of 3-dodecene, 41 parts of 1-hexene and 750 parts of toluene were charged into a nitrogen-substituted reaction vessel and heated to 60 ° C.
[0027]
[Chemical formula 2]

[0028]
To this, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l), WCl modified with tBuOH / MeOH (tBuOH / MeOH / W = 0.35 / 0.3 / 1; molar ratio)₆3.7 parts of a solution (concentration 0.05 mol / l) was added, and the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a ring-opening polymer solution (a).
The polymerization conversion rate in this polymerization reaction is 97%, and the intrinsic viscosity (η_inh) Was 0.45.
4000 parts of this polymer solution (a) is put in an autoclave, and RuHCl (CO) [P (C₆H_Five)_Three]_Three0.48 parts are added and the hydrogen gas pressure is 100 kg / cm.²The mixture was heated and stirred for 3 hours under the reaction temperature of 165 ° C.
After the obtained reaction solution was cooled, the hydrogen gas pressure was released to obtain a hydrogenated polymer solution (b). The hydrogenated polymer thus obtained was poured into a large amount of methanol to solidify the polymer. The hydrogenated polymer A-1 thus obtained had a hydrogenation rate of substantially 100%.
[0029]
Reference example 2
As a specific monomer, 8-ethylidenetetracyclo [4.4.0.1^2,5. 1^7,10] A ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Reference Example 1 except that 200 parts of dodecene were used to obtain a hydrogenated polymer A-2.
[0030]
Example 1
100 parts of hydrogenated polymer A-1 obtained in Reference Example 1 and 0.5 part of green colorant Solvent Green 28 were added and mixed at a temperature of 280 ° C. using a 40 m / m extruder to form a pellet. A thermoplastic resin composition was produced.
Using this thermoplastic resin composition, injection molding was performed at a resin temperature of 320 ° C. and a mold temperature of 130 ° C. to obtain a flat plate having a thickness of 1 mm. A 300 nm film was formed on the flat plate surface by sputtering using indium tin oxide (ITO) to produce an optical filter. The optical filter was evaluated for near-infrared light transmittance, light blocking property, heat deformation property and moisture resistance. The evaluation results are shown in Table 1. Each measurement was performed as follows.
[0031]
Near-infrared light transmittance (%)
Using a spectrophotometer, the transmittance of near-infrared light having a wavelength of 950 nm was measured for an optical filter having a thickness of 1 mm.
Light blocking (%)
Using a spectrophotometer, the transmittance of visible light having a wavelength of 400 to 700 nm and infrared light having a wavelength of 2000 nm or more was measured for an optical filter having a thickness of 1 mm.
Thermal deformation
The appearance change of the molded product after being placed in a 120 ° C. air oven for 24 hours was visually observed, and the thermal deformability was evaluated according to the following evaluation criteria.
○: No deformation such as warp
X: Deformation such as warping is remarkable
durability
Durability was evaluated according to the following evaluation criteria based on the appearance of the molded product after being held at 80 ° C. and 90% relative humidity for 1000 hours.
○: Light emission is uniform with no layer peeling or bleed-out of the light selective absorbent from the molded product, or deformation of the molded product
X: Detachment or bleed-out of the light selective absorbent from the molded product, or deformation of the molded product is remarkable and cannot be used.
[0032]
Example 2
A resin solution having a concentration of 10% by weight obtained by dissolving 100 parts of the hydrogenated polymer A-1 and 0.1 part of the red colorant Solvent Red 52 in a dichloromethane / dichloroethane mixed solution was obtained.
On the other hand, 100 parts of the hydrogenated polymer A-1 obtained in Reference Example 1 and 0.5 part of the green colorant Solvent Green 28 were added, and the thermoplastic resin composition produced in the same manner as in Example 1 was used. Then, injection molding was performed at a resin temperature of 320 ° C. and a mold temperature of 130 ° C. using a commercially available injection molding machine to obtain a flat plate having a thickness of 1 mm. On the surface of the flat plate, the resin solution was applied and dried by spin coating to form a colored layer having a thickness of 300 nm to obtain an optical filter. This optical filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
[0033]
Comparative Example 1
A thermoplastic resin composition was produced in the same manner as in Example 1 except that the hydrogenated polymer A-2 was used in place of the hydrogenated polymer A-1, and an optical filter was molded in the same manner as in Example 1. Evaluation was performed. The evaluation results are shown in Table 1.
Comparative Example 2
In addition to the thermoplastic norbornene resin A-1, polymethyl methacrylate resin (PMMA) (trade name “Acrypet VH”, manufactured by Mitsubishi Rayon Co., Ltd.) was used, and the resin temperature was 230 ° C. and the mold temperature was 100 ° C. Produced a thermoplastic resin composition in the same manner as in Example 1, and molded and evaluated a flat plate in the same manner as in Example 1. The evaluation results are shown in Table 1.
[0034]
[Table 1]

[0035]
As is clear from Table 1, the light selective absorption molded article of the present invention is excellent in light selective absorption and excellent in heat resistance and moisture resistance.
On the other hand, in Comparative Example 1, since the bleed-out or peeling of the light selective absorbent from the molded product occurs during use under high temperature and high humidity, problems are likely to occur in actual use. Moreover, what uses PMMA for transparent base resin (comparative example 2) has a deformation | transformation by a heat | fever and humidity largely, and a use range and use conditions are restricted.
[0036]
Example 3
100 parts of the hydrogenated polymer obtained in Reference Example 1 and 0.5 parts by weight of the green colorant solvent green 28 were added, and the thermoplastic resin composition produced in the same manner as in Example 1 was used. A commercially available injection molding machine was used for injection molding at a resin temperature of 320 ° C. and a mold temperature of 130 ° C. to obtain a lens having an outer diameter of 7.4 mmφ, a lens surface thickness of 2.7 mm, and a peripheral portion thickness of 3.0 mm. A 300 nm film was formed on the surface of this lens by sputtering using indium tin oxide (ITO).
Using a spectrophotometer for this lens, the light transmission at each wavelength was measured. In the near-infrared region at a wavelength of 950 nm, the visible region light at a wavelength of 400 to 700 nm, and the infrared region light at a wavelength of 2000 nm, respectively. The light selective absorptivity was 1% and 2%.
[0037]
【The invention's effect】
The thermoplastic resin composition of the present invention is excellent in durability under high temperature and high humidity, and gives a molded article excellent in light selective absorption, so that it is used in a wide range of applications for the purpose of light selective absorption and transmission. be able to.

Claims (4)

A hydrogenated product of a polymer obtained by ring-opening polymerization of a monomer comprising at least one norbornene derivative represented by the following general formula (1) or a copolymerizable monomer copolymerizable with this monomer And a light-selective absorber that absorbs light in the ultraviolet / visible region in a resin-molded product in which a light-selective absorption layer is further formed on the surface of a molded product formed from a composition containing a photoselective absorber A light selective absorbent resin molded product in which one of an absorbent and a light selective absorbent that absorbs light in the infrared region is blended with a molded resin, and one of the layers is formed on the surface of the molded product to form a light selective absorption layer .

Wherein A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom or a monovalent organic group, and at least one of X and Y is a hydrogen atom and A group having polarity other than a hydrocarbon group is shown, and m is 0 to 2.) The light selective absorption resin molded product according to claim 1, wherein the light selective absorption layer is formed of at least one selected from the following (a) to (d).
(A) a coating containing a light selective absorbent applied to the surface of the molded product, (b) a material formed by layering the light selective absorbent on the surface of the molded product by vacuum deposition, ion plating or sputtering, (C) A product formed by impregnating a molded article with a solution containing a light selective absorbent, and (d) a film obtained by attaching a film containing a light selective absorbent to the surface of the molded article. An optical filter using the light selective absorption resin molded product according to claim 1. A lens using the light selective absorption resin molded product according to claim 1.