JP3750292B2 - Light selective absorption resin molded product, method for producing the same, and optical filter - Google Patents

Description

【０００７】
【化２】

【０００８】
【化３】

【０００９】
【化４】

（式中、Ａ、Ｂ、ＣおよびＤは、水素原子または１価の有機基を示す。）
【００１０】
本発明において好ましく使用することのできるノルボルナン骨格を有する熱可塑性樹脂としては、例えば特開昭６０−１６８７０８号公報、特開昭６２−２５２４０６号公報、特開昭６２−２５２４０７号公報、特開平２−１３３４１３号公報、特開昭６３−１４５３２４号公報、特開昭６３−２６４６２６号公報、特開平１−２４０５１７号公報、特公昭５７−８８１５号公報などに記載されている樹脂などを挙げることができる。
【００１１】
これらの熱可塑性樹脂の好ましい具体例としては、下記一般式（５）で表される少なくとも１種のテトラシクロドデセン誘導体または該テトラシクロドデセンと共重合可能な不飽和環状化合物とをメタセシス重合して得られる重合体を水素添加して得られる水添重合体を挙げることができる。
【００１２】
【化５】

（式中Ａ〜Ｄは、前記に同じ。）
【００１３】
前記一般式（５）で表されるテトラシクロドデセン誘導体において、Ａ、Ｂ、ＣおよびＤのうちに極性基を含むことが、光選択吸収剤との相溶性、および耐熱性の点から好ましい。さらに、この極性基が−（ＣＨ２ ）ｎ ＣＯＯＲ３ （ここで、Ｒ３ 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、得られる水添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 ）ｎ ＣＯＯＲ３ で表される基は、一般式（Ｖ）のテトラシクロドデセン誘導体の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水添重合体の吸湿性が小さくなる点では好ましいが、得られる水添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 。
さらに、−（ＣＨ２ ）ｎ ＣＯＯＲ３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（Ｖ）のテトラシクロドデセン誘導体は、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（Ｖ）のテトラシクロドデセン誘導体は、その合成が容易な点で好ましい。具体的には、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１２，５ １７，１０］ドデカ−８−エンが好ましい。
【００１４】
これらのテトラシクロドデセン誘導体、あるいはこれと共重合可能な不飽和環状化合物の混合物は、例えば特開平４−７７５２０号公報第４頁右上欄第１２行〜第６頁右下欄第６行に記載された方法によって、メタセシス重合、水素添加され、本発明に使用される熱可塑性樹脂とすることができる。
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０．２〜５ｄｌ／ｇのものが好ましく、さらに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。
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。
【００１５】
本発明の熱可塑性樹脂組成物には、必要に応じて公知の酸化防止剤、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を添加することができる。
【００１６】
また、上記の熱可塑性樹脂組成物には、上記のような酸化防止剤の他に、必要に応じて紫外線吸収剤、例えばｐ―ｔ―ブチルフェニルサリシレート、２，２'−ジヒドロキシー４―メトキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシー４−メトキシベンゾフェノン、２−（２'−ジヒドロキシ−４'−ｍ―オクトキシフェニル）ベンゾトリアゾール；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】
本発明に用いられる光選択吸収剤は、通常に用いられている有機または無機の染料や顔料である。
それらの具体例としては、ニトロソ系、ニトロ系、モノアゾ系、ジアゾ系、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、アントラキノン系、フタロシアニン系などの染顔料、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、ツリウム等の有機化合物またはその塩などが挙げられる。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使用しても良い。
【００１８】
本発明の光選択吸収性樹脂成形品は、少なくとも可視光領域の光を遮断する特性を有するものである。ここで、かかる樹脂成形品は可視光領域外の光を同時に遮断するものであってもよい。従って、上記光選択吸収剤は、得られる光選択吸収性成形品が少なくとも３８０ｎｍ〜６００ｎｍに吸収波長領域を有しているように選択されるが、この範囲外の波長の光を一部吸収するものであってもよい。
【００１９】
本発明の光選択吸収性成形品は、（ａ）上記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を用いて射出成形、圧縮成形、押出成形など公知の成形手段により得る方法、（ｂ）熱可塑性ノルボルネン系樹脂を前記公知の成形手段によって成形品とした後、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、（ｃ）熱可塑性ノルボルネン系樹脂からなる成形品を光選択吸収剤を含む溶液に含浸する方法、同様に熱可塑性ノルボルネン系樹脂からなる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。可視光吸収剤が、０．００１重量部未満であると、目的とする機能が充分に発現し得ず、２０重量部を超えると可視光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い。
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。
【００２１】
（ｂ）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。光選択吸収剤の塗布量は、上記熱可塑性ノルボルネン系樹脂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。
【００２２】
（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である。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。光選択吸収剤の含浸量は、上記熱可塑性ノルボルネン系樹脂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。
【００２３】
本発明の光選択吸収性成形品は、光学フィルターとして、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や、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。
【００２４】
【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。
【００２５】
参考例１
特定単量体として、８―メチルー８―メトキシカルボニルテトラシクロ［４．４．０．１２，５．１７，１０］−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。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時間加熱撹拌して、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（ηinh）は０．４５であった。
【００２６】
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時間加熱撹拌した。
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。
【００２７】
参考例２
特定単量体として８−エチリデンテトラシクロ［４．４．０．１２，５．１７，１０］−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。
【００２８】
実施例１
参考例１で得られた水素添加重合体Ａ−１を１００重量部、 緑色着色剤ソルベントグリーン２８を０．５重量部、赤色着色剤ソルベントレッド５２を０．１重量部添加し、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。この平板について、全光線透過率、可視光吸収特性、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。
【００２９】
［可視光遮断性（％）］
分光光度計を用い、厚み１ｍｍの成形体が波長４００〜７５０ｎｍの光を遮断する度合いを測定し、以下の評価基準に従って可視光遮断性を評価した。
○ ：透過率が５％未満
△ ：透過率が５〜１０％
×：透過率が１０％以上
［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
［耐湿性］
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湿性を評価した。
○ ：ソリなどの変形がなく発光が均一であるもの
×：ソリなどの変形が顕著であり使用に耐えないもの
【００３０】
参考評価例１
熱可塑性ノルボルネン系樹脂Ａ−１のかわりに熱可塑性ノルボルネン系樹脂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と同様に平板を成形して評価を行った。評価結果を表１に示す。
【００３１】
比較例１
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。
【００３２】
【表１】

【００３３】
表１から明らかなように、本発明の熱可塑性樹脂組成物は可視光遮断性に優れ、しかも耐熱性や耐湿性に優れた成形品を与えるものである。
これらに対し、透明基材樹脂にＰＭＭＡを用いたもの（比較例）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。
【００３４】
参考評価例２
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、赤色着色剤ソルベントレッド５２を０．１重量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、上記樹脂溶液を塗布・乾燥して着色層を形成した。
この平板について分光光度計を用い、厚み１ｍｍの成形体が波長４００〜７５０ｎｍの光を遮断する度合いを測定した結果、透過率５％以下の極めて良好な光遮断性を示した。
【００３５】
【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、しかも光遮断性に優れた成形品を与えるので、光遮断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.
[0002]
[Prior art]
A molded article that selectively absorbs light of a specific wavelength is known. For example, the light receiving part of a remote control mechanism (hereinafter referred to as remote control) used for remote control of various electrical appliances such as AV equipment and air conditioners is blocked from visible light in order to avoid malfunction of the equipment due to ambient light. A filter that selectively transmits infrared light is provided.
Such a filter is obtained by coating a surface of a transparent plate made of glass or plastic with a coating such as a colorant or a light absorber, and a desired material obtained by blending a transparent material itself with a colorant or a light absorber. Although the latter can be obtained by molding a material comprising a composition having the above optical properties, the latter is particularly widely used for general-purpose equipment because of its advantage that it is easy to handle and has little deterioration over time.
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. Since the thermoplastic acrylic resin has a low heat deformation temperature of about 80 ° C. and a relatively high water absorption rate, the molded product may be deformed under high temperature and high humidity, and there is a problem that the application range is limited.
[0003]
[Problems to be solved by the invention]
The present invention has been made against the background of the problems of the prior art described above. It is an object of the present invention to provide a resin molded article that is excellent in moldability, workability, heat resistance, moisture resistance, and provides an optical filter with a wide range of applications. To do.
[0004]
[Means to solve the problem]
The present invention provides a light selective absorption resin molded article comprising a thermoplastic norbornene resin and an optical filter comprising the same.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic norbornene resin used in the present invention has a norbornane skeleton in its repeating unit.
Examples of the thermoplastic resin include norbornane skeletons represented by the following general formulas (1) to (4).
[0006]
[Chemical 1]

[0007]
[Chemical 2]

[0008]
[Chemical 3]

[0009]
[Formula 4]

(In the formula, A, B, C and D represent a hydrogen atom or a monovalent organic group.)
[0010]
Examples of the thermoplastic resin having a norbornane skeleton that can be preferably used in the present invention include JP-A-60-168708, JP-A-62-252406, JP-A-62-2252407, and JP-A-2 -133413, JP-A-63-145324, JP-A-63-264626, JP-A-1-240517, JP-B-57-8815, and the like. it can.
[0011]
Preferable specific examples of these thermoplastic resins include metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (5) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. A hydrogenated polymer obtained by hydrogenating a polymer obtained in this manner can be mentioned.
[0012]
[Chemical formula 5]

(In the formula, A to D are the same as above.)
[0013]
In the tetracyclododecene derivative represented by the general formula (5), it is preferable that A, B, C and D contain a polar group from the viewpoints of compatibility with the photoselective absorber and heat resistance. . Furthermore, it is obtained that this polar group is a group represented by-(CH2) nCOOR3 (wherein R3 is a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 10). The hydrogenated polymer is preferable because it has a high glass transition temperature. In particular, the group represented by-(CH2) nCOOR3 is preferably contained in one molecule of the tetracyclododecene derivative of the general formula (V). In the above general formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms. However, as the number of carbon atoms increases, it is preferable in that the hygroscopic property of the obtained hydrogenated polymer is reduced, but the glass of the obtained hydrogenated polymer. From the viewpoint of balance with the transition temperature, 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 in particular, a methyl group, an ethyl group, or a cyclohexyl group. Preferred.
Further, a tetracyclododecene derivative of the general formula (V) in which a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to a carbon atom to which a group represented by-(CH2) nCOOR3 is bonded is: It is preferable because it reduces hygroscopicity. In particular, the tetracyclododecene derivative of the general formula (V) in which the substituent is a methyl group or an ethyl group is preferable in terms of easy synthesis. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,517,10] dodec-8-ene is preferable.
[0014]
These tetracyclododecene derivatives or mixtures of unsaturated cyclic compounds copolymerizable therewith are disclosed in, for example, JP-A-4-77520, page 4, upper right column, line 12 to page 6, lower right column, line 6. By the method described, metathesis polymerization and hydrogenation can be made into the thermoplastic resin used in the present invention.
In the present invention, the hydrogenated polymer preferably has an intrinsic viscosity ([η] inh) measured at 30 ° C. in chloroform of 0.2 to 5 dl / g, more preferably 0.3 to 1.5 dl / g. It is desirable to be in the range of g.
When [η] inh is in the above range, the resulting resin has a good balance of moldability, heat resistance, and mechanical properties.
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.
The hydrogenation rate of the hydrogenated polymer is 50% or more, preferably 90% or more, more preferably 98% or more as measured by 60 MHz and 1H-NMR. 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
[0015]
The thermoplastic resin composition of the present invention may contain a known antioxidant, for example, 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di, if necessary. -T-butyl-5,5'-dimethylphenylmethane, tetrakis [methylene-3- (3,5-di-t-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-tert-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-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxpiro [5,5] undecane, tris (2,4-di- t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-) Methylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite can be added.
[0016]
In addition to the above-described antioxidant, the thermoplastic resin composition includes an ultraviolet absorber such as pt-butylphenyl salicylate, 2,2′-dihydroxy-4-methoxy, as necessary. Benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2′-dihydroxy-4′-m-octoxyphenyl) benzotriazole; stabilizer, antistatic agent, flame retardant, impact resistance An improving elastomer or the like can be added. In addition, additives such as a plasticizer and a softener can be added for the purpose of improving moldability and processability.
[0017]
The photoselective absorber used in the present invention is a commonly used organic or inorganic dye or pigment.
Specific examples thereof include nitroso, nitro, monoazo, diazo, diphenylmethane, triphenylmethane, xanthate, azine, triazine, triazole, quinoline, indigo, anthraquinone, phthalocyanine And organic compounds such as nickel, cobalt, praseodymium, neodymium, samarium, europium, dysprosium, holmium, thulium, and salts thereof. 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.
[0018]
The light selective absorption resin molded product of the present invention has a characteristic of blocking light in at least the visible light region. Here, such a resin molded product may simultaneously block light outside the visible light region. Therefore, the light selective absorbent is selected so that the resulting light selective absorbent molded article has an absorption wavelength region of at least 380 nm to 600 nm, but partially absorbs light having a wavelength outside this range. It may be a thing.
[0019]
The light selective absorptive molded article of the present invention is known as (a) injection molding, compression molding, extrusion molding or the like using a resin composition obtained by blending a predetermined light selective absorbent with the thermoplastic norbornene resin. A method obtained by molding means, (b) a method in which a thermoplastic norbornene-based resin is formed into a molded product by the known molding means, and then a paint containing a light selective absorbent is applied to the surface of the molded product, and (c) a thermoplastic norbornene A method of impregnating a molded article made of a resin with a solution containing a light selective absorbent, a method of sticking a film containing a light selective absorbent on the surface of a molded article made of a thermoplastic norbornene resin, or a combination thereof. It's okay.
[0020]
In the method (a), in the resin composition obtained by blending a predetermined photoselective absorber with the thermoplastic norbornene resin, the blending amount of the photoselective absorber is based on 100 parts by weight of the thermoplastic norbornene resin. The amount is preferably 0.001 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. If the visible light absorber is less than 0.001 part by weight, the intended function cannot be sufficiently exhibited, and if it exceeds 20 parts by weight, the compatibility between the visible light absorber and the thermoplastic norbornene resin is poor. Therefore, it is difficult to obtain a uniform molded product such as bleeding on the surface or uneven color.
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.
[0021]
In the method (b), the light selective absorbent applied to the molded article made of the thermoplastic norbornene resin may be one kind or two or more kinds. 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 properties. . The application amount of the light selective absorbent is preferably 0.001 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the thermoplastic norbornene resin.
[0022]
In the method (c), the solution impregnated with the molded product is a solution obtained by dispersing a light selective dispersive dye in water, or a solution in which various solvents are added to improve adhesion. 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. The impregnation amount of the light selective absorbent is preferably 0.001 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic norbornene resin.
[0023]
The optically selective absorptive molded product of the present invention is an optical filter, such as a television receiver, a VTR, other AV devices, a window material for a remote control light-receiving part of household appliances such as an air conditioner, a single-lens reflex camera, a compact camera It can be used for a wide range of applications such as autofocus window materials such as camera-integrated VTRs, automatic doors, and security-related sensor window materials.
[0024]
【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.
[0025]
Reference example 1
As specific monomer, 250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene, 41 parts of 1-hexene and 750 parts of toluene were replaced with nitrogen. The reaction vessel was charged and heated to 60 ° C. To this, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l), a WCl6 solution modified with tBuOH / MeOH (tBuOH / MeOH / W = 0.35 / 0.3 / 1; molar ratio) ( 3.7 parts of 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 was 97%, and the intrinsic viscosity (ηinh) of the polymer was 0.45.
[0026]
4000 parts of this polymer solution (a) is put in an autoclave, and 30.48 parts of RuHCl (CO) [P (C6H5) 3] is added thereto. The hydrogen gas pressure is 100 kg / cm2, and the reaction temperature is 165 ° C. Stir for hours.
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%.
[0027]
Reference example 2
Ring-opening polymerization reaction, hydrogen as in Reference Example 1 except that 200 parts of 8-ethylidenetetracyclo [4.4.0.12, 5.17,10] -3-dodecene was used as the specific monomer Addition reaction was performed to obtain a hydrogenated polymer A-2.
[0028]
Example 1
100 parts by weight of the hydrogenated polymer A-1 obtained in Reference Example 1, 0.5 part by weight of the green colorant Solvent Green 28 and 0.1 part by weight of the red colorant Solvent Red 52 were added, and the temperature was 280 ° C. Were mixed using a 40 m / m extruder to produce a pellet-shaped thermoplastic resin composition.
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. This flat plate was evaluated for total light transmittance, visible light absorption characteristics, thermal deformation and moisture resistance. The evaluation results are shown in Table 1. Each measurement was performed as follows.
[0029]
[Visible light blocking property (%)]
Using a spectrophotometer, the degree to which a molded product having a thickness of 1 mm blocks light having a wavelength of 400 to 750 nm was measured, and the visible light blocking property was evaluated according to the following evaluation criteria.
○: Transmittance is less than 5% Δ: Transmittance is 5-10%
×: Transmittance of 10% or more [thermal deformability]
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.
○: Deformation such as warp is not observed at all ×: Deformation such as warp is remarkable [moisture resistance]
The moisture resistance 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.
○: No warp or other deformation and uniform light emission ×: Warp or other deformation is remarkable and cannot withstand use [0030]
Reference evaluation example 1
A thermoplastic resin composition was produced in the same manner as in Example 1 except that the thermoplastic norbornene resin A-2 was used in place of the thermoplastic norbornene resin A-1, and a flat plate was molded in the same manner as in Example 1. And evaluated. The evaluation results are shown in Table 1.
[0031]
Comparative Example 1
In place of 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.
[0032]
[Table 1]

[0033]
As is clear from Table 1, the thermoplastic resin composition of the present invention provides a molded article having excellent visible light blocking properties and excellent heat resistance and moisture resistance.
On the other hand, those using PMMA as the transparent base resin (comparative example) are greatly deformed by heat and humidity and have limited application range and use conditions.
[0034]
Reference evaluation example 2
100 parts of the hydrogenated polymer obtained in Reference Example 1, 0.5 part by weight of the green colorant Solvent Green 28, and 0.1 part by weight of the red colorant Solvent Red 52 are dissolved in a dichloromethane / dichloroethane mixed solution. A resin solution having a concentration of 10% by weight was obtained.
On the other hand, the hydrogenated polymer A-1 obtained in Reference Example 1 was used for injection molding at a resin temperature of 320 ° C. and a mold temperature of 130 ° C. with 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 to form a colored layer.
The flat plate was measured using a spectrophotometer to measure the degree of blocking of light having a wavelength of 400 to 750 nm by a molded product having a thickness of 1 mm. As a result, it showed extremely good light blocking properties with a transmittance of 5% or less.
[0035]
【The invention's effect】
Since the thermoplastic resin composition of the present invention provides a molded article having excellent durability under high temperature and high humidity and excellent light blocking properties, it can be used in a wide range of applications for light blocking purposes.

Claims (4)

Obtained by hydrogenating a polymer obtained by metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (5) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. A photoselective absorbent resin molded product obtained by molding a resin composition containing a hydrogenated polymer (excluding those containing an aromatic ring) and a photoselective absorbent.

(In the formula, A, B, C and D represent a hydrogen atom or a monovalent organic group, provided that A, B, C and D include a polar group.)   In general formula (5), the polar group contained in A, B, C and D is — (CH 2) n COOR 3 (where R 3 is a hydrocarbon group having 1 to 20 carbon atoms, and n is 0 to 10). The light selective absorption resin molded product according to claim 1, which is a group represented by: Obtained by hydrogenating a polymer obtained by metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (5) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. Extruded molding using a resin composition obtained by adding a photoselective absorbent to a hydrogenated polymer (excluding those containing an aromatic ring), a photoselective absorbent resin molded product Manufacturing method.

(In the formula, A, B, C and D represent a hydrogen atom or a monovalent organic group, provided that A, B, C and D include a polar group.) The optical filter which consists of a light selective absorption resin molding in any one of Claims 1-2.