JP4403473B2 - Near-infrared absorbing compound and near-infrared absorbing filter - Google Patents
Near-infrared absorbing compound and near-infrared absorbing filter Download PDFInfo
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- JP4403473B2 JP4403473B2 JP34363799A JP34363799A JP4403473B2 JP 4403473 B2 JP4403473 B2 JP 4403473B2 JP 34363799 A JP34363799 A JP 34363799A JP 34363799 A JP34363799 A JP 34363799A JP 4403473 B2 JP4403473 B2 JP 4403473B2
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Description
【０００１】
【発明の属する技術分野】
本発明は光学フィルターに関するもので、特に可視光線領域の透過率が高く、近赤外線を効率良く遮断することができる近赤外線吸収フィルタ−に関するものである。また、前記近赤外線吸収フィルタ−を得るための新規な近赤外線吸収化合物に関するものである。本発明の近赤外線吸収化合物を用いた近赤外線吸収フィルターは、例えばビデオカメラなどの光学機器の受光素子や撮像素子の受光感度補正や色調補正等、またキャッシュカードやＩＤカード等の偽造防止など、近赤外線を遮断する機能が必要な用途に広く適用することができる。また、太陽光線に含まれる近赤外線吸収の調光材料や植物育成の制御などの農業用資材や保護メガネ等の視覚保護医療材料、更には感光材料にも利用することができる。
【０００２】
【従来の技術】
従来から用いられてきた代表的な近赤外線吸収化合物および近赤外線吸収フィルタ−としては、下記のようなものが挙げられる。
【０００３】
▲１▼燐酸系ガラスに、銅や鉄などの金属イオンを含有したフィルタ−（特開昭６０−２３５７４０号公報、特開昭６２−１５３１４４号公報など）。
【０００４】
▲２▼基板上に屈折率の異なる層を積層し、透過光を干渉させることで特定の波長を透過させる干渉フィルタ−（特開昭５５−２１０９１号公報、特開昭５９−１８４７４５号公報など）。
【０００５】
▲３▼共重合体に銅イオンを含有するアクリル系樹脂フィルタ−（特開平６−３２４２１３号公報）。
【０００６】
▲４▼近赤外線吸収色素を含有する近赤外線吸収材料としては、次のようなものが使われてきた。
（１）特開平８−１２０１８６号公報、 特開平９−２７９１２５号公報、特開平８−１２０１８６号公報に示されているようなフタロシアニン系、ナフタロシアニン系色素を用いたもの。
（２）特開昭６０−４３６０５号公報、特開昭６１−１１５９５８号公報、特開昭６１−２９１６５１号公報、特開昭６２−１３２９６３号公報、特開平１−１７２４５８号公報、に示されているようなアントラキノン系色素を用いたもの。
（３）特開昭６０−２３６１３１号公報、特開平４−１７４４０３号公報に示されているようなアミニウム塩系色素を用いたもの。
（４）特開昭５７−２１４５８号公報、 特開昭６１−３２００３号公報、 特開昭６２−１８７３０２号公報、特公昭６１−３２００３号公報, 特開昭６１−３２００３号公報に示されているようなジチオール金属錯体系色素を用いたもの。
（５）特開平５−１７８８０８号公報、特開平５−２９５９６７号公報、特開平９−３１００３１号公報に示されているようなジインモニウム塩系色素を用いたもの。
【０００７】
しかしながら、従来使用されてきた上記▲１▼から▲３▼記載の近赤外線吸収フィルターには、それぞれ以下に示すような問題点があった。
【０００８】
前記▲１▼の方式の場合、近赤外領域に急峻な吸収が有り、赤外線遮断率は非常に良好であるが、可視領域の赤色の一部も大きく吸収してしまい、透過色は青色に見える。ディスプレー用途では色バランスを重視され、このような用途に使用するのは不適切である。また、ガラスであるために加工性にも問題がある。
【０００９】
前記▲２▼の方式の場合、光学特性は自由に設計でき、ほぼ設計通りの品質を有するフィルターを製造することが可能であるが、その為には、屈折率差のある層の積層枚数を非常に多くする必要があり、製造コストが高くなるなどの欠点がある。また、大面積を必要とする場合、全面積にわたって高い精度の膜厚均一性が要求されるため、製造が困難である。
【００１０】
前記▲３▼の方式の場合、前記▲１▼の方式の欠点であった加工性は改善される。しかし、前記▲１▼の方式と同様に、光学特性の設計の自由度が低い。また、可視領域の赤色部分にも吸収が有り、フィルターが青く見えてしまうという前記▲１▼の方式の問題点は変わらない。さらに、銅イオンの吸収が小さく、アクリル樹脂に含有できる銅イオン量も限られているため、アクリル樹脂を厚くしなければならないという問題点もある。
【００１１】
前記▲４▼の方式の場合、加工性や生産性に優れ、また安価で製造することができ、さらに光学特性の設計の自由度も比較的大きい。しかしながら、従来使用されてきた前記▲４▼記載の赤外線吸収色素には、それぞれ以下に示すような問題点があった。
【００１２】
前記（１）記載の赤外線吸収色素を使用した場合、可視領域の吸収が大きく、着色したものしか得られない。また、近赤外域の吸収巾が小さく近赤外線の遮断が不十分である。
【００１３】
前記（２）記載の赤外線吸収色素を使用した場合、前記（１）記載の赤外線吸収色素を使用した場合と同様、可視領域の吸収が大きく、着色したものになってしまう。
【００１４】
前記（３）記載の赤外線吸収色素を使用した場合、近赤外線領域の吸収巾は大きいものの、可視領域に大きな吸収があるため、着色が問題になる。
【００１５】
前記（４）記載の赤外線吸収色素を使用した場合、可視領域の吸収は他の色素に比べて小さいものの、近赤外線領域の吸収巾が小さく、近赤外線の遮断が不十分である。
【００１６】
前記（５）記載の赤外線吸収色素を使用した場合、可視領域の吸収は比較的小さいため着色の問題が小さく、近赤外線領域の吸収巾も広いといった利点がある。しかしながら、赤外線リモコンの波長域となる８００ｎｍから９００ｎｍの吸収が不十分であるという問題点がある。
【００１７】
近年、薄型大画面ディスプレイとしてプラズマディスプレイが注目されているが、プラズマディスプレイから不要な近赤外線が放出され、これが近赤外線リモコンを使う電子機器等の誤動作を起こす問題がある。従って、近赤外線を吸収する材料をプラズマディスプレイの前面に設置することが必要とされる。しかし、従来使用されてきた材料では、上記のような理由で、満足なものが提供されていないのが実状である。
【００１８】
【発明が解決しようとする課題】
本発明は、上記のような状況に鑑みなされたものであって、その目的は、波長８００ｎｍから１３００ｎｍにおける近赤外線領域において大きくて巾の広い吸収を有し、かつ可視領域の光透過性が高く、さらに可視領域に特定波長の大きな吸収を有しない、近赤外線吸収化合物を提供することにある。さらに、前記特性を有する近赤外線吸収化合物を用い、加工性および生産性に優れた近赤外線吸収フィルターを提供することにある。
【００１９】
【課題を解決するための手段】
本発明は、上記のような状況に鑑みなされたものであって、前記課題を解決することができた近赤外線吸収化合物および近赤外線吸収フィルターとは、以下の通りである。
【００２０】
本発明の第１の発明は、分子構造が下記一般式（１）で示される近赤外線吸収化合物である。
【化２】
【００２１】
第２の発明は、第１の発明に記載の近赤外線吸収化合物を高分子樹脂に分散させた樹脂組成物であって、前記樹脂組成物を基材上に積層することを特徴とする近赤外線吸収フィルターである。
第３の発明は、第２の発明に記載の基材が可視光線領域において実質的に吸収を有しないことを特徴とする近赤外線吸収フィルターである。
【００２２】
第４の発明は、前記基材が透明なポリエステルフィルムであることを特徴とする第３の発明に記載の近赤外線吸収フィルターである。
第５の発明は、プラズマディスプレイの前面に設置することを特徴とする第２〜４の発明に記載の近赤外線吸収フィルターである。
【００２３】
【発明の実施の形態】
以下、本発明の実施の形態を詳細に説明する。
【００２４】
本発明において、前記の一般式（１）で示される近赤外線吸収化合物は、文献に記載の方法（Shigeru Sasaki and Masahiko Iyoda, Chemistry Letters ,１９９５年）にしたがって、例えば下記構造式（２）で示される化合物を合成し、この化合物を酸化することにより得ることができる。酸化は、ＡｇＣｌＯ4、ＡｇＳｂＦ6、ＡｇＢＦ4、ＡｇＮＯ3のような酸化剤により、容易に行うことができる。
【００２５】
【化３】
【００２６】
前記の一般式（１）で示される本発明の近赤外線吸収化合物は、近赤外線領域に大きな吸収を持ち、且つ吸収巾が大きい。また、可視領域の透過率が高く、光学用途として適している。また、置換基Ｒにより、吸収波長域の微調整、高分子樹脂への溶解性の制御を行うことができる。
【００２７】
本発明の近赤外線吸収化合物において、前記の一般式（１）の置換基Ｒはすべてが同一である。また、置換基Ｒは窒素原子の４位に置換することが好ましい。前記置換基Ｒとしては、アルキル基、アルコキシ基、フッ素が挙げられる。Ｘ − は中性化のためにカウンターイオンを示す。
【００２８】
アルキル基としては、ｎ−ブチル基が挙げられる。
【００３０】
またアルコキシ基としては、ｎ−ブトキシが挙げられる。
【００３１】
本発明の近赤外線吸収フィルターは、近赤外線吸収層を基材に積層させた構成からなる。近赤外線吸収層は、分子構造が前記の一般式（１）で示される近赤外線吸収化合物と高分子樹脂とを主な構成成分とし、高分子樹脂に近赤外線吸収化合物を分散させて使用される。本発明ではこのような構成とすることで、近赤外線吸収層の厚み及び前記の一般式（１）で示される近赤外線吸収化合物の含有量のコントロールが容易であり、そのため、近赤外領域の吸収の大きさや可視領域の透過率を制御することができ、光学特性の設計の自由度が大きくすることができる。
【００３２】
また、近赤外線吸収層の基材への積層方法は得に限定されるわけではないが、基材上に高速でコーティングできるグラビアコート法、リバースコート法、キスロールコート法、ロールコート法で設けることができ、加工性、生産性という点も優れる。
本発明の近赤外線吸収層には、分子構造が前記の一般式（１）で示される近赤外線吸収化合物を少なくとも１種以上含有していることが必要である。吸収波長が異なる２種以上の近赤外線吸収化合物を併用する場合、これらの近赤外線吸収化合物が分子間で相互作用等をおこさなければ、混合した状態で近赤外線吸収層に含有させてもかまわない。分子間で相互作用等を起こす場合には、それぞれ単独で使用することが必要である。その場合、吸収波長が異なる近赤外線吸収化合物をそれぞれ単独で含有させた複数の近赤外線吸収層を基材に積層してもかまわない。この積層は基材の両面でも良いし、片面に複数層積層しても良い。
【００３３】
本発明の近赤外線吸収フィルターの近赤外線吸収層には、分子間の相互作用等を示さなければ、前記の一般式（１）で示される化合物以外に、近赤外領域の吸収領域の巾を広げ、かつ吸収強度を高くすることを目的として、他の近赤外線吸化合物を含有させてもよい。
【００３４】
他の近赤外線吸収化合物としては、フタロシアニン系化合物、ジチオ−ル金属錯体系化合物、ジインモニウム塩系化合物などが好適である。例えば、フタロシアニン系化合物としては、日本触媒社製Excolor IR-1、IR-2、IR-3、IR-4、TXEX-805K、TXEX-809K、TXEX-810K、TXEX-811K、TXEX-812Kなどが例示される。また、ジチオール金属錯体系化合物としては、三井化学社製SIR‐128、SIR‐130、SIR‐132、SIR‐159などが例示される。さらに、ジインモニウム塩系化合物としては、日本化薬社製 IRG-022、IRG-023などが挙げられる。
【００３５】
上記の他の近赤外線吸収化合物は一例であり、特に限定されない。また、必要に応じて、さらに他の種類の色素を混合しても良い。
【００３６】
前記の近赤外線吸収層の構成成分である高分子樹脂としては、前記の一般式（１）で示される本発明の近赤外線吸収化合物を均一に分散できるものであれば特に限定されないが、ポリエステル系、アクリル系、ポリアミド系、ポリウレタン系、ポリオレフィン系、ポリカ−ボネ−ト系樹脂が好適である。
【００３７】
また、前記基材としては、透明性が高いことはもちろんのこと、コスト、取り扱いやすさという点で、プラスチックフィルムが好ましい。具体的には、ポリエステル系、アクリル系、セルロ−ス系、ポリエチレン系、ポリプロピレン系、ポリオレフィン系、ポリ塩化ビニル系、ポリカ−ボネ−ト、フェノ−ル系、ウレタン系樹脂から形成されたフィルムが挙げられるが、物理的特性、光学特性、耐薬品性、環境負荷などの観点から、ポリエステルフィルムが好ましい。ポリエステルフィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン−２，６−ナフタレート又はこれらの樹脂の構成成分を主成分とする共重合体から形成された二軸配向ポリエステルフィルムが好ましく、中でもポリエチレンテレフタレートから形成された二軸配向ポリエチレンテレフタレートフィルムが特に好ましい。
【００３８】
また、上記ポリエステル系樹脂には、各種の添加剤が含有されていても良い。添加剤として、例えば、帯電防止剤、ＵＶ吸収剤、安定剤等が挙げられる。また、基材ポリエステルフィルム中には、透明性の点から、易滑性付与を目的とした不活性粒子を実質上含有させないことが好ましい。
【００３９】
また、基材フィルムと近赤外線吸収層との密着性を良くするために、前記基材フィルムには近赤外線吸収層を積層する面に予め易接着層を積層しておくことが好ましい。なかでも、未延伸または一軸延伸後のポリエステルフィルムの少なくとも片面に易接着層を設け、その後少なくとも一軸方向に延伸・熱固定処理するインラインコート法により積層することが特に好ましい。インラインコート法により積層された易接着層に、適切な粒径の微粒子を含有させることにより滑り性をもたせておけば、良好なハンドリング性（滑り性、巻き取り性など）、耐スクラッチ性を付与することができる。このため、二軸配向ポリエステル中に微粒子を含有させる必要がなく、全光線透過率が８９％以上の高透明なフィルムを得ることができる。
【００４０】
前記易接着層の樹脂としては、共重合ポリエステル系樹脂、ポリウレタン系樹脂、アクリル系樹脂、スチレン−マレイン酸グラフトポリエステル樹脂、アクリルグラフトポリエステル樹脂などが挙げられ、少なくとも１種以上を使用することが好ましい。なかでも、共重合ポリエステル系樹脂及びポリウレタン系樹脂からなる樹脂、スチレン−マレイン酸グラフトポリエステル樹脂が特に好ましい。
【００４１】
本発明において、近赤外線吸収組成物をバインダ−樹脂に分散させた樹脂組成物を基材上に積層する方法は、共押出し法、コーティング法などが挙げられるが、特に限定されない。なかでも、コーティング法は、厚み均一性、コストの点で好ましい。コーティング法の場合、コ−ティング時のコ−ティング液に用いる溶剤は、本発明で用いる近赤外線吸収色素とバインダ−樹脂を均一に分散できるものであれば何でもよい。例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸プロピル、メタノ−ル、エタノ−ル、イソプロピルアルコール、エチルセロソルブ、ブチルセロソルブ、ベンゼン、トルエン、キシレン、テトラヒドロフラン、ｎ−ヘキサン、ｎ−ヘプタン、塩化メチレン、クロロホロム、Ｎ，Ｎ−ジメチルホルムアミド、水などが挙げられるが、これらに限定されるものではない。
【００４２】
【実施例】
次に、本発明の近赤外線吸収化合物および近赤外線吸収フィルターの製造方法について、基材としてポリエチレンテレフタレート（以下ＰＥＴと略称する）を使用した例にして説明するが、当然これに限定されるものではない。実施例及び比較例中の「部」は、特に断らない限り、「重量部」のことである。また、本明細書に記載の分光特性は、自記分光光度計（日立Ｕ−３５００型）を用いて測定したものであり、測定した波長は１５００〜２００ｎｍの範囲である。
【００４３】
実施例１
下記構造式（３）で示される化合物を文献の方法（Shigeru Sasaki and Masahiko Iyoda, Chemistry Letters，１９９５年）によって合成した。次に、下記構造式（３）で示される化合物１部をアセトン２０部に溶かし、さらに該化合物に対し、２倍モル量のヘキサフルオロアンチモン酸銀を加えた。室温で２時間攪拌したのち、析出した銀をろ別し、ろ液をエーテルで薄めて析出した固体を集め、エーテルおよびヘキサンで洗浄し、下記構造式（４）で示される近赤外線吸収化合物０．５部を得た。この近赤外線吸収化合物を塩化メチレン溶液に溶解し、１０ｍｇ／ｌの溶液を調整し、１ｃｍ長の石英セルに入れて分光光度計により透過率を測定した。表２に示されるように、下記構造式（４）で示される近赤外線吸収化合物は、可視領域の５５０ｎｍの透過率が高く、８００ｎｍから９００ｎｍの近赤外線領域の吸収も大きかった。
【００４４】
【化４】
【００４５】
【化５】
【００４６】
実施例２
また、上記近赤外線吸収化合物を分散する高分子樹脂を以下の要領で製造した。
温度計、撹拌機を備えたオ−トクレ−ブ中に、
テレフタル酸ジメチル １３６重量部、
イソフタル酸ジメチル ５８重量部
エチレングリコール ９６重量部、
トリシクロデカンジメタノール １３７重量部
三酸化アンチモン ０．０９重量部
を仕込み１７０〜２２０℃で１８０分間加熱してエステル交換反応を行った。次いで、反応系の温度を２４５℃まで昇温し、系の圧力を１．３３〜１３．３ｈＰａとして１８０分間反応を続けることにより、共重合ポリエステル樹脂（Ａ１）を得た。共重合ポリエステル樹脂（Ａ１）の固有粘度は０．４０ｄｌ／ｇ、ガラス転移温度は９０℃であった。
【００４７】
上記共重合ポリエステル樹脂（Ａ１）の、ＮＭＲ分析による共重合組成比は、酸成分として、テレフタル酸が７１モル％、イソフタル酸が２９モル％であり、アルコール成分として、エチレングリコールが２８モル％、トリシクロデカンジメタノールが７２モル％であった。
【００４８】
次に、この共重合ポリエステル樹脂（Ａ１）、実施例１に記載の構造式（４）で示される近赤外線吸収化合物、及び溶剤を、表１に示すような組成でフラスコにいれ、加熱しながら攪拌し、近赤外線吸収化合物及び共重合ポリエステル樹脂（Ａ１）を溶解した。この溶解液を近赤外線吸収層用塗布液とした。
【００４９】
【表１】
次に、上記で調合した塗布液を、厚み１００μｍの高透明二軸配向ポリエチレンテレフタレートフィルム基材（東洋紡績（株）社製、コスモシャインＡ４１００）に、グラビアロ−ルにより片面にコ−ティングし、１５０℃の熱風をフィルム表面に風速５ｍ／ｓで送りながら１分間乾燥して近赤外線吸収フィルターを製造した。乾燥後のコ−ト層（近赤外線吸収層）の厚さは８．０μｍであった。得られた近赤外線吸収フィルターの分光特性を表１に示す。表１に示されるように、得られた近赤外線吸収フィルターは可視領域の５５０ｎｍの透過率が高く、８００ｎｍから９００ｎｍの近赤外線領域の吸収も大きかった。
【００５１】
実施例３
下記構造式（５）で表わされる近赤外線吸収化合物を、実施例１に記載の合成方法と同様にして合成した。次に、この近赤外線吸収化合物を用いた以外は、実施例２と同様の方法で近赤外線吸収フィルターを製造し、分光特性を測定した。表１に示されるように、得られた近赤外線吸収フィルターは可視領域の５５０ｎｍの透過率が高く、８００ｎｍから９００ｎｍの吸収も大きかった。
【００５２】
【化６】
【００５３】
実施例４
下記構造式（６）で示される近赤外線吸収化合物を実施例１に記載の合成方法と同様にして合成した。次に、この近赤外線吸収化合物を用いた以外は、実施例２と同様の方法で近赤外線吸収フィルターを製造し、分光特性を測定した。表１に示されるように、得られた近赤外線吸収フィルターは可視領域の５５０ｎｍの透過率が高く、８００ｎｍから９００ｎｍの吸収も大きかった。
【００５４】
【化７】
比較例１
近赤外線吸収化合物として、ジインモニウム塩系化合物（日本化薬社製、ＩＲＧ−０２２）に変更する以外は、実施例１と同様の方法で分光特性を測定した。表１に示されるように、上記ジインモニウム塩系化合物は可視領域の５５０ｎｍの透過率は高いものの、８００ｎｍから９００ｎｍの近赤外領域の吸収が不十分であった。
【００５６】
比較例２
近赤外線吸収化合物として、ジインモニウム塩系化合物（日本化薬社製、ＩＲＧ−０２２）に変更する以外は、実施例２と同様の方法で分光特性を測定した。表１に示されるように、得られた近赤外線吸収フィルターは可視領域の５５０ｎｍの透過率は高いものの、８００ｎｍから９００ｎｍの近赤外領域の吸収が不十分であった。
【００５７】
【表２】
【発明の効果】
以上説明したように、本発明の近赤外線吸収化合物および近赤外線吸収フィルタ−は、近赤外線領域に大きくて、巾の広い吸収を有し、しかも可視領域の光線透過性が高く、さらに環境安定性及び耐久性にも優れているため、プラズマディスプレイ用の近赤外線吸収フィルタ−をはじめ、波長選択調光材料、視覚保護医療材料、その他光通信ならびに光検出に障害を防止する近赤外線カットフィルター、近赤外線感光材料、農業用波長選択近赤外線カットフィルターなどに好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical filter, and more particularly to a near-infrared absorption filter that has a high transmittance in the visible light region and can efficiently block near-infrared rays. The present invention also relates to a novel near-infrared absorbing compound for obtaining the near-infrared absorbing filter. The near-infrared absorption filter using the near-infrared absorbing compound of the present invention is, for example, a light-receiving sensitivity correction or color tone correction of a light-receiving element or an image pickup element of an optical device such as a video camera, and counterfeiting prevention such as a cash card or an ID card It can be widely applied to uses that require a function of blocking near infrared rays. Further, it can also be used as a dimming material for absorbing near infrared rays contained in sunlight, agricultural materials such as plant growth control, visual protection medical materials such as protective glasses, and photosensitive materials.
[0002]
[Prior art]
Examples of typical near-infrared absorbing compounds and near-infrared absorbing filters that have been conventionally used include the following.
[0003]
(1) Filters containing metal ions such as copper and iron in phosphoric acid glass (Japanese Patent Laid-Open Nos. 60-235740 and 62-153144).
[0004]
(2) Interference filters that transmit a specific wavelength by laminating layers having different refractive indexes on a substrate and causing transmitted light to interfere (Japanese Patent Laid-Open Nos. 55-21091, 59-184745, etc.) ).
[0005]
(3) An acrylic resin filter containing copper ions in a copolymer (Japanese Patent Laid-Open No. 6-324213).
[0006]
(4) The following materials have been used as near-infrared absorbing materials containing near-infrared absorbing pigments.
(1) Those using phthalocyanine and naphthalocyanine dyes as disclosed in JP-A-8-120186, JP-A-9-279125, and JP-A-8-120186.
(2) As disclosed in JP-A-60-43605, JP-A-61-115958, JP-A-61-291651, JP-A-62-132963, JP-A-1-172458. Using anthraquinone dyes.
(3) Those using aminium salt dyes as disclosed in JP-A-60-236131 and JP-A-4-174403.
(4) As disclosed in JP-A-57-21458, JP-A-61-32003, JP-A-62-187302, JP-B-61-22003, JP-A-61-32003 Using a dithiol metal complex dye.
(5) A dye using a diimmonium salt dye as disclosed in JP-A-5-178808, JP-A-5-295967 and JP-A-9-310031.
[0007]
However, the near-infrared absorption filters described in the above (1) to (3), which have been conventionally used, have the following problems.
[0008]
In the case of the method (1), there is a steep absorption in the near infrared region and the infrared blocking rate is very good, but a part of the red color in the visible region is also absorbed greatly, and the transmitted color is blue. appear. In display applications, color balance is important, and it is inappropriate to use in such applications. Moreover, since it is glass, there exists a problem also in workability.
[0009]
In the case of the above method (2), the optical characteristics can be freely designed, and it is possible to manufacture a filter having a quality almost as designed. For that purpose, the number of layers having a difference in refractive index is set. There is a disadvantage that it is necessary to increase the number very much and the manufacturing cost becomes high. Further, when a large area is required, it is difficult to manufacture because a highly accurate film thickness uniformity is required over the entire area.
[0010]
In the case of the method (3), the workability which was a drawback of the method (1) is improved. However, like the method (1), the degree of freedom in designing optical characteristics is low. Further, the problem of the method (1) in which the red portion in the visible region is also absorbed and the filter looks blue is not changed. Furthermore, since the absorption of copper ions is small and the amount of copper ions that can be contained in the acrylic resin is limited, there is a problem that the acrylic resin must be thickened.
[0011]
The method (4) is excellent in workability and productivity, can be manufactured at low cost, and has a relatively high degree of freedom in designing optical characteristics. However, the infrared absorbing dyes described in the above item (4), which have been conventionally used, have the following problems.
[0012]
When the infrared absorbing dye described in the above (1) is used, absorption in the visible region is large and only a colored one can be obtained. Moreover, the absorption range in the near infrared region is small, and the blocking of the near infrared ray is insufficient.
[0013]
When the infrared absorbing dye described in the above (2) is used, as in the case where the infrared absorbing dye described in the above (1) is used, absorption in the visible region is large and the dye is colored.
[0014]
When the infrared absorbing dye described in the above (3) is used, although the absorption width in the near infrared region is large, coloring is a problem because of the large absorption in the visible region.
[0015]
When the infrared absorbing dye described in the above (4) is used, the absorption in the visible region is smaller than that of other dyes, but the absorption width in the near infrared region is small and the blocking of the near infrared ray is insufficient.
[0016]
When the infrared absorbing dye described in the above (5) is used, there is an advantage that the absorption problem in the visible region is relatively small so that the problem of coloring is small and the absorption range in the near infrared region is wide. However, there is a problem that absorption from 800 nm to 900 nm, which is the wavelength range of the infrared remote controller, is insufficient.
[0017]
In recent years, plasma displays have attracted attention as thin large-screen displays. However, unnecessary near-infrared rays are emitted from the plasma display, which causes a malfunction of electronic devices using a near-infrared remote controller. Therefore, it is necessary to install a material that absorbs near infrared rays on the front surface of the plasma display. However, the materials that have been used in the past are not satisfactory because of the above reasons.
[0018]
[Problems to be solved by the invention]
The present invention has been made in view of the situation as described above, and its purpose is to have a large and wide absorption in the near-infrared region at a wavelength of 800 nm to 1300 nm and a high light transmittance in the visible region. Another object is to provide a near-infrared absorbing compound that does not have a large absorption at a specific wavelength in the visible region. Furthermore, it is providing the near-infrared absorption filter excellent in workability and productivity using the near-infrared absorption compound which has the said characteristic.
[0019]
[Means for Solving the Problems]
This invention is made | formed in view of the above situations, Comprising: The near-infrared absorption compound and the near-infrared absorption filter which were able to solve the said subject are as follows.
[0020]
1st invention of this invention is a near-infrared absorption compound whose molecular structure is shown by following General formula (1).
[Chemical formula 2]
[0021]
2nd invention is a resin composition which disperse | distributed the near-infrared absorption compound as described in 1st invention to polymer resin, Comprising: The said infrared rays are laminated | stacked on a base material, The near infrared rays characterized by the above-mentioned. Absorption filter.
3rd invention is a near-infrared absorption filter characterized by the base material as described in 2nd invention having substantially no absorption in visible region.
[0022]
A fourth invention is the near-infrared absorption filter according to the third invention, wherein the base material is a transparent polyester film.
A fifth invention is the near-infrared absorption filter according to the second to fourth inventions, which is installed on the front surface of the plasma display.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0024]
In the present invention, the near-infrared absorbing compound represented by the general formula (1) is represented by, for example, the following structural formula (2) according to a method described in the literature (Shigeru Sasaki and Masahiko Iyoda, Chemistry Letters, 1995). Can be obtained by synthesizing the compound and oxidizing the compound. Oxidation can be easily performed with an oxidizing agent such as AgClO 4 , AgSbF 6 , AgBF 4 , AgNO 3 .
[0025]
[Chemical 3]
[0026]
The near-infrared absorbing compound of the present invention represented by the general formula (1) has a large absorption in the near-infrared region and a large absorption width. Further, it has a high transmittance in the visible region and is suitable for optical applications. Further, the substituent R can finely adjust the absorption wavelength region and control the solubility in the polymer resin.
[0027]
In the near infrared absorbing compound of the present invention, the substituents R of the above general formula (1) is Ru all identical der. The substituent R is preferably substituted at the 4-position of the nitrogen atom. Examples of the substituent R, an alkyl group, an alkoxy group, and fluorine. X − represents a counter ion for neutralization.
[0028]
The alkyl groups include n- butyl group.
[0030]
Moreover , n-butoxy is mentioned as an alkoxy group .
[0031]
The near-infrared absorption filter of this invention consists of a structure which laminated | stacked the near-infrared absorption layer on the base material. The near-infrared absorbing layer includes a near-infrared absorbing compound having a molecular structure represented by the general formula (1) and a polymer resin as main components, and is used by dispersing the near-infrared absorbing compound in the polymer resin. . In the present invention, such a configuration makes it easy to control the thickness of the near-infrared absorbing layer and the content of the near-infrared absorbing compound represented by the general formula (1). The degree of absorption and the transmittance in the visible region can be controlled, and the degree of freedom in designing optical characteristics can be increased.
[0032]
Further, the method of laminating the near infrared absorbing layer on the base material is not limited to obtaining, but it is provided by gravure coating method, reverse coating method, kiss roll coating method, roll coating method which can be coated on the base material at high speed. It is also excellent in terms of workability and productivity.
The near-infrared absorbing layer of the present invention needs to contain at least one near-infrared absorbing compound having a molecular structure represented by the general formula (1). When two or more near-infrared absorbing compounds having different absorption wavelengths are used in combination, the near-infrared absorbing layer may be contained in a mixed state as long as these near-infrared absorbing compounds do not interact with each other. . In the case of causing an interaction between molecules, it is necessary to use them individually. In that case, a plurality of near-infrared absorbing layers each containing a near-infrared absorbing compound having a different absorption wavelength may be laminated on the substrate. This lamination may be performed on both sides of the substrate, or a plurality of layers may be laminated on one side.
[0033]
If the near-infrared absorption layer of the near-infrared absorption filter of the present invention does not show an intermolecular interaction or the like, in addition to the compound represented by the general formula (1), the width of the absorption region in the near-infrared region is increased. For the purpose of spreading and increasing the absorption strength, other near infrared ray absorbing compounds may be contained.
[0034]
As other near infrared ray absorbing compounds, phthalocyanine compounds, dithiol metal complex compounds, diimmonium salt compounds and the like are suitable. For example, as phthalocyanine compounds, Excat IR-1, IR-2, IR-3, IR-4, TXEX-805K, TXEX-809K, TXEX-810K, TXEX-811K, TXEX-812K manufactured by Nippon Shokubai Co., Ltd. Illustrated. Examples of the dithiol metal complex compound include SIR-128, SIR-130, SIR-132 and SIR-159 manufactured by Mitsui Chemicals. Further, examples of the diimmonium salt compound include IRG-022 and IRG-023 manufactured by Nippon Kayaku Co., Ltd.
[0035]
The other near-infrared absorbing compounds described above are examples and are not particularly limited. Moreover, you may mix another type of pigment | dye as needed.
[0036]
The polymer resin that is a constituent component of the near infrared absorbing layer is not particularly limited as long as it can uniformly disperse the near infrared absorbing compound of the present invention represented by the general formula (1). Acrylic, polyamide, polyurethane, polyolefin, and polycarbonate resins are preferred.
[0037]
The base material is preferably a plastic film in terms of cost and ease of handling as well as high transparency. Specifically, films formed from polyester, acrylic, cellulose, polyethylene, polypropylene, polyolefin, polyvinyl chloride, polycarbonate, phenol, and urethane resins Although mentioned, a polyester film is preferable from the viewpoints of physical properties, optical properties, chemical resistance, environmental load, and the like. As the polyester film, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate or a biaxially oriented polyester film formed from a copolymer mainly composed of these resin components is preferable. The formed biaxially oriented polyethylene terephthalate film is particularly preferable.
[0038]
Moreover, the said polyester-type resin may contain various additives. Examples of the additive include an antistatic agent, a UV absorber, and a stabilizer. Further, it is preferable that the base polyester film does not substantially contain inert particles for the purpose of imparting slipperiness from the viewpoint of transparency.
[0039]
Moreover, in order to improve the adhesiveness of a base film and a near-infrared absorption layer, it is preferable to laminate | stack an easily bonding layer previously on the surface which laminates | stacks a near-infrared absorption layer in the said base film. Among them, it is particularly preferable to laminate by an in-line coating method in which an easy-adhesion layer is provided on at least one surface of an unstretched or uniaxially stretched polyester film and then stretched and heat-set in at least a uniaxial direction. If the easy-adhesion layer laminated by the in-line coating method is made slippery by containing fine particles with an appropriate particle size, good handling properties (sliding property, winding property, etc.) and scratch resistance are imparted. can do. For this reason, it is not necessary to contain fine particles in the biaxially oriented polyester, and a highly transparent film having a total light transmittance of 89% or more can be obtained.
[0040]
Examples of the resin for the easy-adhesion layer include copolymer polyester resins, polyurethane resins, acrylic resins, styrene-maleic acid graft polyester resins, acrylic graft polyester resins, and the like. Preferably, at least one kind is used. . Among these, a resin composed of a copolyester resin and a polyurethane resin, and a styrene-maleic acid graft polyester resin are particularly preferable.
[0041]
In the present invention, a method of laminating a resin composition obtained by dispersing a near-infrared absorbing composition in a binder resin on a substrate includes a coextrusion method and a coating method, but is not particularly limited. Of these, the coating method is preferable in terms of thickness uniformity and cost. In the case of the coating method, the solvent used in the coating solution at the time of coating may be any as long as it can uniformly disperse the near infrared absorbing dye and binder resin used in the present invention. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, methanol, ethanol, isopropyl alcohol, ethyl cellosolve, butyl cellosolve, benzene, toluene, xylene, tetrahydrofuran, n-hexane, n-heptane, methylene chloride , Chloroform, N, N-dimethylformamide, water and the like, but are not limited thereto.
[0042]
【Example】
Next, the method for producing the near-infrared absorbing compound and the near-infrared absorbing filter of the present invention will be described using an example in which polyethylene terephthalate (hereinafter abbreviated as PET) is used as a base material. Absent. “Parts” in Examples and Comparative Examples means “parts by weight” unless otherwise specified. Moreover, the spectral characteristics described in this specification are measured using a self-recording spectrophotometer (Hitachi U-3500 type), and the measured wavelength is in the range of 1500 to 200 nm.
[0043]
Example 1
A compound represented by the following structural formula (3) was synthesized by a literature method (Shigeru Sasaki and Masahiko Iyoda, Chemistry Letters, 1995). Next, 1 part of a compound represented by the following structural formula (3) was dissolved in 20 parts of acetone, and a 2-fold molar amount of silver hexafluoroantimonate was added to the compound. After stirring at room temperature for 2 hours, the precipitated silver is filtered off, the filtrate is diluted with ether, the precipitated solid is collected, washed with ether and hexane, and the near infrared absorbing compound 0 represented by the following structural formula (4) is collected. .5 parts were obtained. This near-infrared absorbing compound was dissolved in a methylene chloride solution to prepare a 10 mg / l solution, placed in a 1 cm long quartz cell, and the transmittance was measured with a spectrophotometer. As shown in Table 2, the near-infrared absorbing compound represented by the following structural formula (4) had a high transmittance at 550 nm in the visible region and a large absorption in the near-infrared region from 800 nm to 900 nm.
[0044]
[Formula 4]
[0045]
[Chemical formula 5]
[0046]
Example 2
Moreover, the polymer resin which disperse | distributes the said near-infrared absorption compound was manufactured in the following ways.
In an autoclave equipped with a thermometer and a stirrer,
136 parts by weight of dimethyl terephthalate,
Dimethyl isophthalate 58 parts by weight ethylene glycol 96 parts by weight,
Tricyclodecane dimethanol (137 parts by weight) and antimony trioxide (0.09 parts by weight) were charged, and the mixture was heated at 170 to 220 ° C. for 180 minutes to conduct a transesterification reaction. Subsequently, the temperature of the reaction system was raised to 245 ° C., and the reaction was continued for 180 minutes with the pressure of the system being 1.33 to 13.3 hPa, to obtain a copolymerized polyester resin (A1). The intrinsic viscosity of the copolyester resin (A1) was 0.40 dl / g, and the glass transition temperature was 90 ° C.
[0047]
The copolymerization composition ratio of the copolymerized polyester resin (A1) by NMR analysis was as follows: 71 mol% terephthalic acid and 29 mol% isophthalic acid as the acid component, 28 mol% ethylene glycol as the alcohol component, Tricyclodecane dimethanol was 72 mol%.
[0048]
Next, the copolymerized polyester resin (A1), the near-infrared absorbing compound represented by the structural formula (4) described in Example 1 and the solvent are placed in a flask with the composition shown in Table 1 and heated. The mixture was stirred to dissolve the near-infrared absorbing compound and the copolyester resin (A1). This solution was used as a near-infrared absorbing layer coating solution.
[0049]
[Table 1]
Next, the coating liquid prepared above was coated on one side with a gravure roll on a 100 μm thick highly transparent biaxially oriented polyethylene terephthalate film base (Toyobo Co., Ltd., Cosmo Shine A4100), A near-infrared absorbing filter was manufactured by drying for 1 minute while sending hot air of 150 ° C. to the film surface at a wind speed of 5 m / s. The thickness of the coated layer (near infrared absorbing layer) after drying was 8.0 μm. Table 1 shows the spectral characteristics of the obtained near-infrared absorption filter. As shown in Table 1, the obtained near-infrared absorption filter had a high transmittance at 550 nm in the visible region, and also had a large absorption in the near-infrared region from 800 nm to 900 nm.
[0051]
Example 3
A near-infrared absorbing compound represented by the following structural formula (5) was synthesized in the same manner as the synthesis method described in Example 1. Next, a near-infrared absorption filter was produced in the same manner as in Example 2 except that this near-infrared absorbing compound was used, and the spectral characteristics were measured. As shown in Table 1, the obtained near-infrared absorption filter had a high transmittance of 550 nm in the visible region, and had a large absorption from 800 nm to 900 nm.
[0052]
[Chemical 6]
[0053]
Example 4
A near-infrared absorbing compound represented by the following structural formula (6) was synthesized in the same manner as the synthesis method described in Example 1. Next, a near-infrared absorption filter was produced in the same manner as in Example 2 except that this near-infrared absorbing compound was used, and the spectral characteristics were measured. As shown in Table 1, the obtained near-infrared absorption filter had a high transmittance of 550 nm in the visible region, and had a large absorption from 800 nm to 900 nm.
[0054]
[Chemical 7]
Comparative Example 1
Spectral characteristics were measured in the same manner as in Example 1 except that the near-infrared absorbing compound was changed to a diimmonium salt compound (Nippon Kayaku Co., Ltd., IRG-022). As shown in Table 1, the diimmonium salt-based compound had high transmittance at 550 nm in the visible region, but had insufficient absorption in the near infrared region from 800 nm to 900 nm.
[0056]
Comparative Example 2
Spectral characteristics were measured in the same manner as in Example 2, except that the near-infrared absorbing compound was changed to a diimmonium salt compound (Nippon Kayaku Co., Ltd., IRG-022). As shown in Table 1, although the obtained near-infrared absorption filter had a high transmittance at 550 nm in the visible region, the absorption in the near-infrared region from 800 nm to 900 nm was insufficient.
[0057]
[Table 2]
【The invention's effect】
As described above, the near-infrared absorbing compound and the near-infrared absorbing filter of the present invention have a large absorption in the near-infrared region, wide absorption, high light transmittance in the visible region, and environmental stability. In addition, because of its excellent durability, it also includes near-infrared absorption filters for plasma displays, wavelength-selective light-modulating materials, visual protection medical materials, and other near-infrared cut filters that prevent obstacles to optical communication and light detection. It is suitable for an infrared photosensitive material, an agricultural wavelength selective near infrared cut filter, and the like.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
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| JP34363799A JP4403473B2 (en) | 1999-12-02 | 1999-12-02 | Near-infrared absorbing compound and near-infrared absorbing filter |
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| KR100515594B1 (en) * | 2003-07-11 | 2005-09-21 | 주식회사 엘지화학 | Near infrared absorbing film and plasma display filter comprising the same |
| KR100788258B1 (en) * | 2005-06-02 | 2007-12-27 | 주식회사 에이스 디지텍 | Thin film type PD filter and image display device using same |
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