JP4162334B2 - Dye-type polarizing film - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、新規なポリビニルアルコール又はその誘導体からなる偏光膜に関するものである。
【０００２】
【従来の技術】
光の透過・遮へい機能を有する偏光板は、光のスイッチング機能を有する液晶とともに液晶ディスプレイ（ＬＣＤ）の基本的な構成要素である。このＬＣＤの適用分野も初期の頃の電卓および時計等の小型機器から、ノートパソコン、ワープロ、液晶プロジェクタ、液晶テレビ、カーナビゲーションおよび屋内外の計測機器等の広範囲に広がり、使用条件も低温〜高温、低湿度〜高湿度の幅広い条件で使用されることから、偏光性能が高くかつ耐久性に優れた偏光板が求められている。
【０００３】
現在、偏光膜は延伸配向したポリビニルアルコール又はその誘導体のフィルムあるいは、ポリ塩化ビニルフィルムの脱塩酸又はポリビニルアルコールまたはその誘導体からなるフィルムの脱水によりポリエンを生成して配向せしめたポリエン系のフィルムなどの偏光膜基材に、偏光素子としてヨウ素や二色性染料を含有せしめて製造される。これらのうち、偏光素子としてヨウ素を用いたヨウ素系偏光膜は、初期偏光性能には優れるものの、水および熱に対して弱く、高温、高湿の状態で長時間使用する場合にはその耐久性に問題がある。耐久性を向上させるためにホルマリン、あるいは、ほう酸を含む水溶液で処理したり、また透湿度の低い高分子フィルムを保護膜として用いる方法などが考えられているが十分とはいえない。一方、偏光素子として二色性染料を用いた染料系偏光膜はヨウ素系偏光膜に比べ、耐湿性および耐熱性は優れるものの、一般に初期偏光性能が十分ではない。
【０００４】
また、高分子フィルムに数種の二色性染料を吸着・配向させてなる中性色の偏光膜において、２枚の偏光膜をその配向方向が直交するように重ね合わせた状態（直交位）で、可視光領域、特に４００〜７００ｎｍの波長領域における特定波長の光漏れ（色漏れ）があると、偏光膜を液晶パネルに装着したとき、暗状態において液晶表示の色相が変わってしまうことがある。そこで、偏光膜を液晶表示装置に装着したとき、暗状態において特定波長の色漏れによる液晶表示の変色を防止するためには、高分子フィルムに数種の二色性染料を吸着・配向させてなる中性色の偏光膜において、可視光領域、特に４００〜７００ｎｍの波長領域における直交位の透過率（直交透過率）を一様に低くしなければならない。
【０００５】
【発明が解決しようとする課題】
偏光膜の製造に用いられる染料としては、例えば特許第２８４４３６０号公報の実施例１に下記式（２）の水溶性染料が記載されている。
【０００６】
【化２】
しかしながら、前記従来の水溶性染料を含有してなる偏光膜は、偏光特性、吸収波長領域、色相等の観点から、需要家のニーズを十分に満足させるに至っていない。
【０００８】
本発明の目的の一つは、優れた偏光性能および耐湿性・耐熱性を有する高性能な偏光膜を提供することにある。さらに、本発明の他の目的は、高分子フィルムに二種類以上の二色性染料を吸着・配向せしめてなる中性色の偏光膜であって、可視光領域、特に４００〜７００ｎｍの波長領域における直交位の色もれがなく、優れた偏光性能及び耐湿性、耐熱性を有する高性能な偏光膜を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者らは、かかる目的を達成すべく鋭意研究を進めた結果、特定の染料を含有する偏光膜が、優れた偏光性能及び耐湿性、耐熱性を有することを見いだし、さらにはかかる特定の染料とともに、中性色を有する偏光膜とするための特定の選択された染料を含有させることにより、偏光性能及び耐久性に優れるとともに、可視光領域における色もれも少ない偏光膜が得られることを見いだし、本発明を完成した。 すなわち本発明は、
（１）遊離酸の形で下記式（１）
【００１０】
【化３】
（式中、Ｒ1 、Ｒ2 、Ｒ3、Ｒ4は各々独立に水素原子、メチル基、エチル基、メトキシ基、エトキシ基、アセチルアミノ基を表す。但しＲ1 、Ｒ2 、Ｒ3 、Ｒ4のすべてがメチル基もしくはメトキシ基の場合、及びＲ１ 、Ｒ３ がメチル基でかつＲ2、Ｒ4がメトキシ基の場合も除く。Ｒ５ はアミノ基またはヒドロキシ基を表す。）
で表される水溶性染料またはこの銅錯塩染料を含有することを特徴とするポリビニルアルコール又はその誘導体からなる偏光膜。
（２）さらに式（１）で表される水溶性染料またはこの銅錯塩染料以外の有機染料を少なくとも１種以上有することを特徴とする（１）に記載のポリビニルアルコール又はその誘導体からなる偏光膜、
に関する。
【００１２】
上記式（１）で表される水溶性染料またはその銅錯塩染料を一種以上含有してなる偏光膜は、偏光性能に優れ、しかも耐湿性、耐熱性に優れる特徴を有する。さらに上記式（１）で表される水溶性染料またはその銅錯塩染料を一種以上含有した偏光膜は別の有機染料を含有させることにより、偏光性能に優れ、しかも耐湿性、耐熱性に優れた特徴を有する中性色（グレー）の偏光膜が得られる。
【００１３】
【発明の実施の形態】
本発明の偏光膜は、式（１）で表される水溶性染料またはこの銅錯塩染料を少なくとも一種含有する。式（１）おいて、スルホン酸基の置換位置はアゾ基に対してパラ位が好ましい。Ｒ1 、Ｒ2、Ｒ3、Ｒ4はそれぞれ独立に水素原子、メチル基、エチル基等の（Ｃ1〜Ｃ4）アルキル基、メトキシ基、エトキシ基等の（Ｃ1〜Ｃ4）アルコキシ基、アセチルアミノ基を表すが、Ｒ1 、Ｒ2 が水素原子、Ｒ3、Ｒ4がメチル基のものが特に好ましい。また、式（１）において、Ｒ5 はアミノ基またはヒドロキシ基であるが、アミノ基が特に好ましい。Ｒ5 の置換位置としては、−ＮＨＣＯ−基に対してパラ位が特に好ましい。次に本発明で使用する式（１）で表される水溶性染料の代表例を以下にあげる。
【００１４】
【化４】
式（１）で表される水溶性染料は,通常のアゾ染料の製法に従い,公知のジアゾ化、カップリング法で容易に製造できる。即ち、１個のスルホン酸基で置換されたアニリン類をジアゾ化し、置換基を有していてもよいアニリン類と一次カップリングさせ、モノアゾアミノ化合物を得る。次いで、このモノアゾアミノ化合物をジアゾ化し、置換基を有していてもよいアニリン類と２次カップリングさせ、ジスアゾアミノ化合物を得る。このジスアゾアミノ化合物をジアゾ化し、ベンゾイル基のフェニル核が１個のアミノ基またはヒドロキシ基で置換された、Ｎ−ベンゾイルＪ酸とアルカリ性で３次カップリングさせることにより式（１）の水溶性染料が得られる。さらに硫酸銅等を用いて常法により銅錯塩化すれば式（１）化合物の銅錯塩化物が得られる。
【００１６】
上記反応において、ジアゾ化工程はジアゾ成分の塩酸、硫酸などの鉱酸水溶液またはけん濁液に亜硝酸ナトリウムなどの亜硝酸塩を混合するという順法によるか、あるいはジアゾ成分の中性もしくは弱アルカリ性の水溶液に亜硝酸塩を加えておき、これと鉱酸を混合するという逆法によって行われる。ジアゾ化の温度は、−１０〜４０℃が適当である。また、アニリン類とのカップリング工程は塩酸、酢酸などの酸性水溶液と上記ジアゾ液を混合し、温度が−１０〜４０℃でＰＨ２〜７の酸性条件で行われる。
【００１７】
カップリングして得られたモノアゾ化合物及びジスアゾ化合物はそのままあるいは酸析や塩析により析出させ濾過して取り出すか、溶液またはけん濁液のまま次の工程へ進むこともできる。ジアゾニウム塩が難溶性でけん濁液となっている場合は濾過してプレスケーキとして次のジアゾ化工程で使うこともできる。
【００１８】
ジスアゾアミノ化合物のジアゾ化物と、置換されたＮ−ベンゾイルＪ酸との３次カップリング反応は、温度が−１０〜４０℃でＰＨ７〜１０のアルカリ性条件で行われる。反応終了後、塩析により析出させ濾過して取り出す。さらに銅錯塩化物とするには、その水溶液を硫酸銅、モノエタノールアミンと９５〜１００℃で反応させ、塩析等により析出させ濾過して取り出せばよい。また精製が必要な場合には、塩析を繰り返すかまたは有機溶媒を使用して水中から析出させればよい。
【００１９】
有機溶媒としては、例えばメタノール、エタノール等のアルコール類、アセトン等のケトン類等の水溶性有機溶媒があげられる。
【００２０】
式（１）で表される水溶性染料を合成するための出発原料である上記した１個のスルホン酸基で置換されたアニリン類としては、例えばスルファニル酸、メタニル酸、オルタニル酸が挙げられる。
【００２１】
カップリング成分である、置換基を有していてもよいアニリン類における置換基としては、メチル基、エチル基、メトキシ基、エトキシ基、アセチルアミノ基があげられる。これらの置換基は１つまたは２つ以上結合しても良い。その結合位置は、アミノ基に対して、２位、３位、２位と５位が好ましい。置換基を有していてもよいアニリン類としては、例えばアニリン、２ーメチルアニリン、３ーメチルアニリン、２ーエチルアニリン、３ーエチルアニリン、２、５ージメチルアニリン、２、５ージエチルアニリン、２ーメトキシアニリン、３ーメトキシアニリン、２ーメトキシー５ーメチルアニリン、２、５ージメトキシアニリン、２ーメトキシー５ーアセチルアミノアニリン、等が挙げられる。これらのアニリン類はアミノ基が保護されていても良い。
【００２２】
保護基としては、例えばそのωーメタンスルホン酸基があげられる。１次カップリングに使用するアニリン類と２次カップリングに使用するアニリン類は同じであっても異なっていても良い。
【００２３】
上記したベンゾイル基が１個のアミノ基またはヒドロキシ基で置換されたＮ−ベンゾイルＪ酸としては、Ｎ−（４′ーアミノベンゾイル）Ｊ酸、Ｎ−（２′ーアミノベンゾイル）Ｊ酸、Ｎ−（４′ーヒドロキシベンゾイル）Ｊ酸、Ｎ−（２′ーヒドロキシベンゾイル）Ｊ酸が挙げられる。これらの、ベンゾイル基が１個のアミノ基またはヒドロキシ基で置換されたＮ−ベンゾイルＪ酸は、Ｊ酸を公知の方法で、ニトロ基で置換された塩化ベンゾイルを用いてベンゾイル化した後、公知の方法によりニトロ化物を還元すれば、Ｒ５ がアミノ基である化合物が得られる。また公知の方法によりＲ５ がヒドロキシ基であるＮ−ベンゾイルＪ酸とすることもできる。
【００２４】
式（１）で表される化合物は単独で使用される他、それら同士、あるいは他の色素と配合することにより、各種の色相及び中性色を有する偏光素子または偏光板を製造することができる。配合する他の有機染料としては、本発明のトリスアゾ化合物の吸収波長領域と異なる波長領域に吸収特性を有する染料であって二色性の高いものであれば、いかなる染料であってもよく、例えば、シー．アイ．ダイレクト．イエロー１２、シー．アイ．ダイレクト．イエロー２８、シー．アイ．ダイレクト．イエロー４４、シー．アイ．ダイレクト．オレンジ２６、シー．アイ．ダイレクト．オレンジ３９、シー．アイ．ダイレクト．オレンジ１０７、シー．アイ．ダイレクト．レッド ２、シー．アイ．ダイレクト．レッド ３１、シー．アイ．ダイレクト．レッド ７９、シー．アイ．ダイレクト．レッド ８１、シー．アイ．ダイレクト．レッド ２４７ 、シー．アイ．ダイレクト．グリーン８０、シー．アイ．ダイレクト．グリーン５９および特開昭５９−１４５２５５号、特開昭６０−１５６７５９号、特開平３−１２６０６号の各公報に記載された染料等が挙げられ、これらの色素は遊離酸、あるいはアルカリ金属塩、アンモニウム塩、アミン類の塩として用いられる。
【００２５】
本発明の偏光膜は、式（１）で表されるトリスアゾ化合物を、偏光膜材料である高分子フィルムに公知の方法で含有せしめることにより、製造することができる。
【００２６】
本発明の偏光膜に使用する基材（高分子フィルム）は、ポリビニアルコールまたはその誘導体、これらのいずれかをエチレン、プロピレンのようなオレフィンや、クロトン酸、アクリル酸、メタクリル酸、マレイン酸のような不飽和カルボン酸などで変性したもの、ＥＶＡ（エチレン／ビニルアセテート）樹脂、ケン化ＥＶＡ樹脂、ナイロン樹脂、ポリエステル樹脂などからなるものが利用される。なかでも、ポリビニアルコールまたはその誘導体からなるフィルムが、染料の吸着性および配向性の点から、好適に用いられる。
【００２７】
このような高分子フィルムに式（１）で表されるトリスアゾ化合物を含有せしめるにあたっては、通常、高分子フィルムを染色する方法が採用される。染色は、例えば次のように行われる。まず、式（１）で表されるトリスアゾ化合物を水に溶解して染浴を調整する。染浴中の染料濃度は特に制限されないが、通常は０．００１〜１０重量％程度の範囲から選択される。また、必要により染色助剤を用いてもよく、例えば、芒硝を０．１〜１０重量％程度の濃度で用いるのが好適である。このようにして調整した染浴に高分子フィルムを浸漬し、染色を行う。染色温度は、好ましくは４０〜８０℃程度である。
【００２８】
式（１）で表されるトリスアゾ化合物の配向は、高分子フィルムを延伸することによって行われる。延伸する方法としては、例えば湿式法、乾式法など、公知のいずれの方法を用いてもよい。高分子フィルムの延伸は、染色の前に行ってもよい。式（１）で表されるトリスアゾ化合物を含有・配向せしめた高分子フィルムは、必要に応じて公知の方法によりホウ酸処理などの後処理が施される。このような後処理は、偏光膜の光線透過率および偏光度を向上させる目的で行われる。ホウ酸処理の条件は、用いる高分子フィルムの種類や用いる染料の種類によって異なるが、一般的にはホウ酸水溶液のホウ酸濃度を１〜１５重量％、好ましくは５〜１０重量％の範囲とし、処理は３０〜８０℃、好ましくは４０〜７５℃の温度範囲で行われる。更に必要に応じて、カチオン系高分子化合物を含む水溶液で、フィックス処理を併せて行ってもよい。
【００２９】
このようにして得られた染料系偏光膜は、その片面または両面に、光学的透明性および機械的強度に優れる保護膜を貼合して、偏光板とすることができる。保護膜を形成する材料は、従来から使用されているものでよく、例えば、セルロースアセテート系フィルムやアクリル系フィルムのほか、四フッ化エチレン／六フッ化プロピレン系共重合体のようなフッ素系フィルム、ポリエステル樹脂、ポリオレフィン樹脂またはポリアミド系樹脂からなるフィルムが用いられる。
【００３０】
また、式（１）で表されるトリスアゾ化合物に加えて前記の有機染料を少なくとも一種以上用いることによっても本発明のポリビニルアルコール又はその誘導体からなる偏光膜が得られる。この場合、それぞれの配合割合は特に限定されるものではないが、一般的には、式（１）で表される化合物の重量を基準として、前記の有機染料の少なくとも一種以上の合計で０、１〜１０重量部の範囲で用いるのが好ましい。このように構成した偏光膜は中性色を有し、可視光領域、特に４００〜７００ｎｍの波長領域において直交位の色もれがなく、偏光性能に優れ、さらに高温、高湿状態でも変色や偏光性能の低下を起こさないという特徴を有する。
【００３１】
このようにして、高い偏光性能を有し、且つ耐湿性、耐熱性に優れた偏光膜を得ることができる。また式（１）で表される水溶性染料と他の有機染料を併用することによって、耐湿性、耐熱性の優れた中性色の偏光膜を得ることができる。この場合、有機染料として前記した染料から一種以上を併用することによって、耐湿性、耐熱性に優れ、可視光領域における直交位での光もれの少ない偏光膜を得ることができる。
【００３２】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、これらは例示的なものであって、本発明をなんら限定するものではない。例中にある％および部は、特にことわらないかぎり重量基準である。
【００３３】
合成例１
４ーアミノアゾベンゼンー４′ースルフォン酸ナトリウム２９．９部を水６００部に加え７０℃として溶解する。冷却し３０℃以下で、３５％塩酸３２部を加え、次に亜硝酸ナトリウム６．９部を加え、２５〜２８℃で２時間攪拌する。そこへ２、５ジメチルアニリン１２．１部を加え、２５〜３０℃で２時間攪拌したのち、炭酸ナトリウムを加えてｐＨ３とし、さらに攪拌してカップリング反応を完結させ、濾過して、ジスアゾ化合物を得る。得られたジスアゾ化合物を水６００部に分散させたのち、３５％塩酸３２部を、次に亜硝酸ナトリウム６．９部を加え、２５〜３０℃で２時間攪拌してジアゾ化する。
【００３４】
一方、４′ーアミノベンゾイルＪ酸３５．８部を水２５０部に加え、炭酸ナトリウムで弱アルカリ性として溶解し、この液に先に得られたジスアゾ化合物のジアゾ化物を中性〜弱アルカリ性を保って注入し、攪拌して、カップリング反応を完結させる。塩化ナトリウムで塩析し、濾過して化合物Ｎｏ．１のトリスアゾ化合物の水溶性染料を得た。
【００３５】
合成例２
スルファニル酸１７．３部を水５００部に加え、水酸化ナトリウムで溶解する。冷却し１０℃以下で、３５％塩酸３２部を加え、次に亜硝酸ナトリウム６．９部を加え、５〜１０℃で１時間攪拌する。そこへ希塩酸水に溶解したＰークレシジン１３．７部を加え、１０〜１５℃で攪拌しながら、炭酸ナトリウムを加えてｐＨ３とし、さらに攪拌してカップリング反応を完結させ、濾過して、モノアゾ化合物を得る。得られたモノアゾ化合物を水６００部に分散させたのち、３５％塩酸３２部を、次に亜硝酸ナトリウム６．９部を加え、２５〜３０℃で２時間攪拌する。そこへ希塩酸水に溶解した２、５ジメトキシアニリン１５．３部を加え、２０〜３０℃で攪拌しながら、炭酸ナトリウムを加えてｐＨ３とし、さらに攪拌してカップリング反応を完結させ、濾過して、ジスアゾ化合物を得る。得られたジスアゾ化合物を水６００部に分散させたのち、３５％塩酸３２部を、次に亜硝酸ナトリウム６．９部を加え、２５〜３０℃で２時間攪拌してジアゾ化する。
【００３６】
一方、４′ーアミノベンゾイルＪ酸３５．８部を水２５０部に加え、炭酸ナトリウムで弱アルカリ性として溶解し、この液に先に得られたジスアゾ化合物のジアゾ化物を中性〜弱アルカリ性を保って注入し、攪拌して、カップリング反応を完結させる。塩化ナトリウムで塩析し、濾過して化合物Ｎｏ．２のトリスアゾ化合物の水溶性染料を得た。
【００３７】
合成例３
合成例２で得られた化合物４０部を水５００部に分散させ、結晶硫酸銅１５部およびモノエタノールアミン１５部を加えて９５℃に加熱し、１０時間反応させる。反応液に塩化ナトリウムを加えて塩析し、濾過して、化合物Ｎｏ．３の銅錯塩染料を得た。
【００３８】
実施例１
合成例１で得られた化合物Ｎｏ．１の染料の０．０３％および芒硝０．１％の濃度とした４５℃の水溶液に、厚さ７５μｍのポリビニルアルコールを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で５０℃で５倍に延伸し、緊張状態を保ったまま水洗、乾燥して偏光膜を得た。得られた偏光膜は、極大吸収波長５５０ｎｍであり、この偏光膜は高い偏光度を有し、しかも、高温且つ高湿の状態でも長時間にわたる耐久性を示した。
【００３９】
実施例２
合成例３で得られた化合物Ｎｏ．３の銅錯塩染料の０．０３％および芒硝０．１％の濃度とした４５℃の水溶液に、厚さ７５μｍのポリビニルアルコールを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で５０℃で５倍に延伸し、緊張状態を保ったまま水洗、乾燥して偏光膜を得た。得られた偏光膜は、極大吸収波長６３０ｎｍであり、この偏光膜は高い偏光度を有し、しかも、高温且つ高湿の状態でも長時間にわたる耐久性を示した。
【００４０】
実施例３
合成例１で得られた化合物Ｎ０．１の染料０．０４％、シー・アイダイレクト・オレンジ３９を０．０３％、特開平３ー１２６０６号公報、実施例１において公開されている下記構造式（３）で示される染料０．０４％、特開昭６０ー１５６７５９号公報、実施例３８において公開されている下記（４）構造式で示される染料０．０３％および芒硝を０．１％の濃度とした４５℃の水溶液に、厚さ７５μｍのポリビニルアルコールを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で５０℃で５倍に延伸し、緊張状態を保ったまま水洗、乾燥して偏光膜を得た。得られた偏光膜は中性色であり、高い偏光度を有し、しかも、高温且つ高湿の状態でも長時間にわたる耐久性を示した。
【００４１】
【化５】
実施例４
合成例１〜３で得られた、化合物Ｎｏ．１の染料０．０３％、化合物Ｎｏ．２の染料の０．０４％、化合物Ｎｏ．３の染料の０．０４％、シー．アイ．ダイレクト．オレンジ３９を０．０３％、および芒硝を０．１％の濃度とした４５℃の水溶液に、厚さ７５μｍのポリビニルアルコールを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で５０℃で５倍に延伸し、緊張状態を保ったまま水洗、乾燥して中性色の偏光膜を得た。得られた偏光膜は、中性色であり、高い偏光度を有し、しかも、高温且つ高湿の状態でも長時間にわたる耐久性を示した。
【００４３】
【発明の効果】
本発明のトリスアゾ化合物は、染料、特に偏光膜用の染料として有用である。そしてこの化合物を含有する偏光膜は、ヨウ素を用いた偏光膜に匹敵する高い偏光性能を有し、且つ耐久性にも優れるので、各種液晶表示体、なかでも高い偏光性能と耐久性を必要とする車載用途、各種環境で用いられる工業計器類の表示用途に好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polarizing film comprising a novel polyvinyl alcohol or a derivative thereof .
[0002]
[Prior art]
A polarizing plate having a light transmission / shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal having a light switching function. This LCD can be used in a wide range from small devices such as calculators and watches in the early days to notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring devices. Since it is used in a wide range of low humidity to high humidity, a polarizing plate having high polarization performance and excellent durability is required.
[0003]
At present, the polarizing film is a stretched and oriented polyvinyl alcohol film or a derivative film thereof, or a polyene film obtained by orienting a polyene film by dehydrochlorination of a polyvinyl chloride film or dehydration of a film made of polyvinyl alcohol or a derivative thereof . The polarizing film substrate is manufactured by containing iodine or a dichroic dye as a polarizing element. Among these, an iodine-based polarizing film using iodine as a polarizing element is excellent in initial polarization performance, but is weak against water and heat, and is durable when used at a high temperature and high humidity for a long time. There is a problem. In order to improve the durability, methods such as treatment with an aqueous solution containing formalin or boric acid or using a polymer film having low moisture permeability as a protective film are considered, but it is not sufficient. On the other hand, although a dye-type polarizing film using a dichroic dye as a polarizing element is superior in moisture resistance and heat resistance to an iodine-type polarizing film, the initial polarizing performance is generally not sufficient.
[0004]
In addition, in a neutral color polarizing film formed by adsorbing and orienting several dichroic dyes on a polymer film, the two polarizing films are stacked so that their orientation directions are orthogonal (orthogonal position) If there is light leakage (color leakage) of a specific wavelength in the visible light region, particularly in the wavelength region of 400 to 700 nm, the hue of the liquid crystal display may change in the dark state when the polarizing film is attached to the liquid crystal panel. is there. Therefore, when a polarizing film is mounted on a liquid crystal display device, several dichroic dyes are adsorbed and oriented on the polymer film to prevent discoloration of the liquid crystal display due to color leakage at a specific wavelength in the dark state. In the neutral color polarizing film, the transmissivity (orthogonal transmissivity) in the orthogonal position in the visible light region, particularly in the wavelength region of 400 to 700 nm, must be uniformly reduced.
[0005]
[Problems to be solved by the invention]
As a dye used for manufacturing the polarizing film, for example, a water-soluble dye represented by the following formula (2) is described in Example 1 of Japanese Patent No. 2844360.
[0006]
[Chemical 2]
However, the conventional polarizing film containing the water-soluble dye does not sufficiently satisfy the needs of consumers from the viewpoints of polarization characteristics, absorption wavelength region, hue, and the like.
[0008]
One of the objects of the present invention is to provide a high-performance polarizing film having excellent polarization performance, moisture resistance and heat resistance. Furthermore, another object of the present invention is a neutral color polarizing film obtained by adsorbing and orienting two or more kinds of dichroic dyes on a polymer film, and has a visible light region, particularly a wavelength region of 400 to 700 nm. It is an object of the present invention to provide a high-performance polarizing film that has no color shift at right angles and has excellent polarization performance, moisture resistance, and heat resistance.
[0009]
[Means for Solving the Problems]
As a result of diligent research to achieve such an object, the present inventors have found that a polarizing film containing a specific dye has excellent polarization performance, moisture resistance, and heat resistance, and furthermore, the specific film. By including a specific selected dye for forming a polarizing film having a neutral color together with the dye, a polarizing film having excellent polarization performance and durability and less color leakage in the visible light region can be obtained. And the present invention was completed. That is, the present invention
(1) In the form of free acid, the following formula (1)
[0010]
[Chemical 3]
(Wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or an acetylamino group, provided that R 1 , R 2 , R 3 , Except when all of R 4 are methyl groups or methoxy groups, and when R 1 and R 3 are methyl groups and R 2 and R 4 are methoxy groups, R 5 represents an amino group or a hydroxy group.)
A polarizing film comprising polyvinyl alcohol or a derivative thereof, which contains a water-soluble dye represented by the formula (1) or a copper complex dye.
(2) The polarizing film comprising polyvinyl alcohol or a derivative thereof according to (1), further comprising at least one water-soluble dye represented by formula (1) or an organic dye other than the copper complex dye ,
About.
[0012]
A polarizing film comprising one or more water-soluble dyes represented by the above formula (1) or a copper complex dye thereof has excellent polarization performance and excellent moisture resistance and heat resistance. Furthermore, the polarizing film containing at least one water-soluble dye represented by the above formula (1) or its copper complex dye has excellent polarization performance, moisture resistance, and heat resistance by containing another organic dye. A neutral color (gray) polarizing film having characteristics can be obtained.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The polarizing film of the present invention contains at least one water-soluble dye represented by the formula (1) or a copper complex dye. In the formula (1), the substitution position of the sulfonic acid group is preferably para to the azo group. R 1, R 2, R 3 , R 4 are each independently a hydrogen atom, a methyl group, (C 1 ~C 4), such as ethyl alkyl group, a methoxy group, such as an ethoxy group (C 1 ~C 4) alkoxy A group and an acetylamino group, wherein R 1 and R 2 are hydrogen atoms, and R 3 and R 4 are particularly preferably methyl groups. In the formula (1), R 5 is an amino group or a hydroxy group, and an amino group is particularly preferable. As the substitution position of R 5, the para position with respect to the —NHCO— group is particularly preferable. Next, typical examples of the water-soluble dye represented by the formula (1) used in the present invention are listed below.
[0014]
[Formula 4]
The water-soluble dye represented by the formula (1) can be easily produced by a known diazotization or coupling method in accordance with a conventional azo dye production method. That is, an aniline substituted with one sulfonic acid group is diazotized and primary-coupled with an aniline optionally having a substituent to obtain a monoazoamino compound. Next, this monoazoamino compound is diazotized and secondarily coupled with an aniline which may have a substituent to obtain a disazoamino compound. The disazoamino compound is diazotized, and the water-soluble dye of formula (1) is obtained by alkaline and tertiary coupling with N-benzoyl J acid in which the phenyl nucleus of the benzoyl group is substituted with one amino group or hydroxy group. Is obtained. Further, copper complex chloride of the formula (1) can be obtained by copper complex chloride using copper sulfate or the like by a conventional method.
[0016]
In the above reaction, the diazotization step is carried out by a conventional method of mixing a nitrite such as sodium nitrite with a mineral acid aqueous solution or suspension of diazo component such as hydrochloric acid or sulfuric acid, or a neutral or weak alkaline solution of diazo component. Nitrite is added to the aqueous solution and mixed with mineral acid. The temperature for diazotization is suitably -10 to 40 ° C. In addition, the coupling step with anilines is performed by mixing an acidic aqueous solution such as hydrochloric acid and acetic acid with the diazo solution and at a temperature of −10 to 40 ° C. under acidic conditions of PH 2 to 7.
[0017]
The monoazo compound and the disazo compound obtained by the coupling can be taken out as they are, or precipitated by aciding out or salting out and filtered, or can be taken to the next step as a solution or suspension. When the diazonium salt is hardly soluble and is in a suspension, it can be filtered and used as a press cake in the next diazotization step.
[0018]
The tertiary coupling reaction between a diazotized compound of a disazoamino compound and a substituted N-benzoyl J acid is performed under alkaline conditions of a temperature of -10 to 40 ° C and a pH of 7 to 10. After completion of the reaction, it is precipitated by salting out and filtered out. Further, in order to obtain a copper complex chloride, the aqueous solution is reacted with copper sulfate and monoethanolamine at 95 to 100 ° C., precipitated by salting out, etc., filtered and taken out. When purification is required, salting out may be repeated or precipitated from water using an organic solvent.
[0019]
Examples of the organic solvent include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
[0020]
Examples of the anilines substituted with one sulfonic acid group as a starting material for synthesizing the water-soluble dye represented by the formula (1) include sulfanilic acid, metanilic acid, and alternic acid.
[0021]
Examples of the substituent in the aniline which may have a substituent, which is a coupling component, include a methyl group, an ethyl group, a methoxy group, an ethoxy group, and an acetylamino group. One or more of these substituents may be bonded. The bonding positions are preferably 2-position, 3-position, 2-position and 5-position with respect to the amino group. Examples of anilines which may have a substituent include aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2-methoxyaniline, 3- Examples include methoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 2-methoxy-5-acetylaminoaniline, and the like. These anilines may have an amino group protected.
[0022]
Examples of the protecting group include the ω-methanesulfonic acid group. The anilines used for the primary coupling and the anilines used for the secondary coupling may be the same or different.
[0023]
Examples of the N-benzoyl J acid in which the benzoyl group is substituted with one amino group or hydroxy group include N- (4′-aminobenzoyl) J acid, N- (2′-aminobenzoyl) J acid, N -(4'-hydroxybenzoyl) J acid and N- (2'-hydroxybenzoyl) J acid. These N-benzoyl J acids in which the benzoyl group is substituted with one amino group or hydroxy group are obtained by benzoylating the J acid with benzoyl chloride substituted with a nitro group by a known method, If the nitrate is reduced by the above method, a compound in which R5 is an amino group can be obtained. Moreover, it can also be set as N-benzoyl J acid whose R5 is a hydroxy group by a well-known method.
[0024]
The compound represented by the formula (1) can be used alone, or by blending with each other or with other dyes, polarizing elements or polarizing plates having various hues and neutral colors can be produced. . As other organic dyes to be blended, any dye may be used as long as it is a dye having absorption characteristics in a wavelength region different from the absorption wavelength region of the trisazo compound of the present invention and has high dichroism, for example, , See. Ai. direct. Yellow 12, sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, sea. Ai. direct. Orange 107, sea. Ai. direct. Red 2, sea. Ai. direct. Red 31, sea. Ai. direct. Red 79, Sea. Ai. direct. Red 81, Sea. Ai. direct. Red 247, Sea. Ai. direct. Green 80, Sea. Ai. direct. Green 59 and dyes described in JP-A-59-145255, JP-A-60-156759, JP-A-3-12606, and the like. These dyes are free acids or alkali metal salts, Used as ammonium salts and amine salts.
[0025]
The polarizing film of the present invention can be produced by incorporating a trisazo compound represented by the formula (1) into a polymer film that is a polarizing film material by a known method.
[0026]
The base material (polymer film) used in the polarizing film of the present invention is polyvinyl alcohol or a derivative thereof, and any of these is an olefin such as ethylene or propylene, crotonic acid, acrylic acid, methacrylic acid or maleic acid. Those modified with such unsaturated carboxylic acid, EVA (ethylene / vinyl acetate) resin, saponified EVA resin, nylon resin, polyester resin and the like are used. Especially, the film which consists of polyvinyl alcohol or its derivative (s) is used suitably from the point of the adsorptivity and orientation of a dye.
[0027]
In order to incorporate such a polymer film with the trisazo compound represented by the formula (1), a method of dyeing the polymer film is usually employed. For example, the staining is performed as follows. First, the trisazo compound represented by the formula (1) is dissolved in water to prepare a dye bath. The dye concentration in the dye bath is not particularly limited, but is usually selected from the range of about 0.001 to 10% by weight. Further, a dyeing assistant may be used if necessary. For example, it is preferable to use sodium sulfate at a concentration of about 0.1 to 10% by weight. Dyeing is performed by immersing the polymer film in the dye bath thus prepared. The dyeing temperature is preferably about 40 to 80 ° C.
[0028]
Orientation of the trisazo compound represented by the formula (1) is performed by stretching a polymer film. As a stretching method, any known method such as a wet method or a dry method may be used. The polymer film may be stretched before dyeing. The polymer film containing and orienting the trisazo compound represented by the formula (1) is subjected to post-treatment such as boric acid treatment by a known method as necessary. Such post-processing is performed for the purpose of improving the light transmittance and the degree of polarization of the polarizing film. The conditions for the boric acid treatment vary depending on the type of polymer film used and the type of dye used, but generally the boric acid concentration of the boric acid aqueous solution is in the range of 1 to 15% by weight, preferably 5 to 10% by weight. The treatment is carried out in the temperature range of 30 to 80 ° C, preferably 40 to 75 ° C. Further, if necessary, the fixing treatment may be performed together with an aqueous solution containing a cationic polymer compound.
[0029]
The dye-type polarizing film thus obtained can be used as a polarizing plate by bonding a protective film excellent in optical transparency and mechanical strength on one or both sides. The material for forming the protective film may be a conventionally used material, for example, a cellulose acetate film or an acrylic film, or a fluorine film such as a tetrafluoroethylene / hexafluoropropylene copolymer. A film made of polyester resin, polyolefin resin or polyamide resin is used.
[0030]
Moreover, the polarizing film which consists of the polyvinyl alcohol of this invention or its derivative (s) can also be obtained by using at least one or more of the above organic dyes in addition to the trisazo compound represented by the formula (1). In this case, the blending ratio of each is not particularly limited, but in general, based on the weight of the compound represented by the formula (1), the total of at least one of the above organic dyes is 0. It is preferable to use in the range of 1 to 10 parts by weight. The polarizing film thus configured has a neutral color, has no color shift at an orthogonal position in the visible light region, particularly in the wavelength region of 400 to 700 nm, is excellent in polarization performance, and can be discolored even at high temperature and high humidity. It has the feature of not causing a decrease in polarization performance.
[0031]
In this way, a polarizing film having high polarization performance and excellent moisture resistance and heat resistance can be obtained. Moreover, the neutral color polarizing film excellent in moisture resistance and heat resistance can be obtained by using the water-soluble dye represented by the formula (1) in combination with another organic dye. In this case, by using one or more of the above dyes as the organic dye, it is possible to obtain a polarizing film having excellent moisture resistance and heat resistance and less light leakage at an orthogonal position in the visible light region.
[0032]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these are illustrations and do not limit this invention at all. In the examples,% and parts are based on weight unless otherwise specified.
[0033]
Synthesis example 1
Add 29.9 parts of sodium 4-aminoazobenzene-4'-sulfonate to 600 parts of water and dissolve at 70 ° C. Cool and add 30 parts of 35% hydrochloric acid at 30 ° C or lower, then add 6.9 parts of sodium nitrite and stir at 25-28 ° C for 2 hours. Thereto, 12.1 parts of 2,5 dimethylaniline was added and stirred at 25-30 ° C. for 2 hours, then sodium carbonate was added to adjust to pH 3, and further stirred to complete the coupling reaction, filtered, and the disazo compound Get. After the obtained disazo compound is dispersed in 600 parts of water, 32 parts of 35% hydrochloric acid and then 6.9 parts of sodium nitrite are added, and the mixture is stirred at 25-30 ° C. for 2 hours for diazotization.
[0034]
On the other hand, 35.8 parts of 4'-aminobenzoyl J acid is added to 250 parts of water and dissolved with sodium carbonate to weak alkalinity. The diazo compound of the disazo compound obtained previously in this liquid is kept neutral to weakly alkaline. Pour and stir to complete the coupling reaction. Salting out with sodium chloride, filtering, compound No. A water-soluble dye of 1 trisazo compound was obtained.
[0035]
Synthesis example 2
Add 17.3 parts of sulfanilic acid to 500 parts of water and dissolve with sodium hydroxide. Cool to 10 ° C or lower, add 32 parts of 35% hydrochloric acid, then add 6.9 parts of sodium nitrite and stir at 5-10 ° C for 1 hour. Thereto was added 13.7 parts of P-cresidine dissolved in dilute hydrochloric acid, and while stirring at 10 to 15 ° C., sodium carbonate was added to adjust the pH to 3, further stirring to complete the coupling reaction, filtration, and monoazo compound Get. After the obtained monoazo compound is dispersed in 600 parts of water, 32 parts of 35% hydrochloric acid and then 6.9 parts of sodium nitrite are added and stirred at 25-30 ° C. for 2 hours. Thereto was added 15.3 parts of 2,5 dimethoxyaniline dissolved in dilute hydrochloric acid, and while stirring at 20-30 ° C., sodium carbonate was added to pH 3, and further stirred to complete the coupling reaction, filtered. To obtain a disazo compound. After the obtained disazo compound is dispersed in 600 parts of water, 32 parts of 35% hydrochloric acid and then 6.9 parts of sodium nitrite are added, and the mixture is stirred at 25-30 ° C. for 2 hours for diazotization.
[0036]
On the other hand, 35.8 parts of 4'-aminobenzoyl J acid is added to 250 parts of water and dissolved with sodium carbonate to weak alkalinity. The diazo compound of the disazo compound obtained previously in this liquid is kept neutral to weakly alkaline. Pour and stir to complete the coupling reaction. Salting out with sodium chloride, filtering, compound No. A water-soluble dye of 2 trisazo compounds was obtained.
[0037]
Synthesis example 3
40 parts of the compound obtained in Synthesis Example 2 are dispersed in 500 parts of water, 15 parts of crystalline copper sulfate and 15 parts of monoethanolamine are added, heated to 95 ° C., and reacted for 10 hours. Sodium chloride was added to the reaction solution for salting out, followed by filtration. 3 copper complex dye was obtained.
[0038]
Example 1
Compound No. obtained in Synthesis Example 1 Polyvinyl alcohol having a thickness of 75 μm was immersed in an aqueous solution at 45 ° C. having a concentration of 0.03% of 1 dye and 0.1% of sodium sulfate for 4 minutes. This film was stretched 5 times at 50 ° C. in a 3% boric acid aqueous solution, washed with water and dried while maintaining a tension state, to obtain a polarizing film. The obtained polarizing film had a maximum absorption wavelength of 550 nm, and this polarizing film had a high degree of polarization, and also exhibited durability over a long period of time even at high temperature and high humidity.
[0039]
Example 2
Compound No. obtained in Synthesis Example 3 Polyvinyl alcohol having a thickness of 75 μm was immersed in an aqueous solution at 45 ° C. having a concentration of 0.03% of the copper complex dye 3 and 0.1% of sodium sulfate for 4 minutes. This film was stretched 5 times at 50 ° C. in a 3% boric acid aqueous solution, washed with water and dried while maintaining a tension state, to obtain a polarizing film. The obtained polarizing film had a maximum absorption wavelength of 630 nm, and this polarizing film had a high degree of polarization, and also exhibited durability over a long period of time even in a high temperature and high humidity state.
[0040]
Example 3
0.04% of the dye of compound N0.1 obtained in Synthesis Example 1 and 0.03% of C.I.Direct Orange 39, the following structural formula disclosed in JP-A-3-12606, Example 1 0.04% of the dye represented by (3), 0.03% of the dye represented by the following (4) structural formula disclosed in JP-A-60-156759 and Example 38, and 0.1% of mirabilite Polyvinyl alcohol having a thickness of 75 μm was immersed for 4 minutes in a 45 ° C. aqueous solution having the above concentration. This film was stretched 5 times at 50 ° C. in a 3% boric acid aqueous solution, washed with water and dried while maintaining a tension state, to obtain a polarizing film. The obtained polarizing film had a neutral color, had a high degree of polarization, and exhibited durability over a long period of time even at high temperatures and high humidity.
[0041]
[Chemical formula 5]
Example 4
Compound Nos. Obtained in Synthesis Examples 1 to 3 1 dye 0.03%, compound no. 0.04% of the dye of No. 2, Compound No. 0.04% of the dye of No. 3, Ai. direct. Polyvinyl alcohol having a thickness of 75 μm was immersed in an aqueous solution at 45 ° C. with an orange 39 concentration of 0.03% and mirabilite concentration of 0.1% for 4 minutes. This film was stretched 5 times at 50 ° C. in a 3% boric acid aqueous solution, washed with water and dried while maintaining a tension state to obtain a neutral color polarizing film. The obtained polarizing film was a neutral color, had a high degree of polarization, and exhibited durability over a long period of time even at high temperatures and high humidity.
[0043]
【The invention's effect】
The trisazo compound of the present invention is useful as a dye, particularly as a dye for a polarizing film. And since the polarizing film containing this compound has high polarizing performance comparable to the polarizing film using iodine, and excellent in durability, various liquid crystal displays, especially high polarizing performance and durability are required. It is suitable for in-vehicle use and display use of industrial instruments used in various environments.
Claims (2)
で表される水溶性染料またはこの銅錯塩染料を含有することを特徴とするポリビニルアルコールまたはその誘導体からなる偏光膜。The following formula (1) in the form of free acid is applied to the polarizing film substrate.
A polarizing film comprising polyvinyl alcohol or a derivative thereof, which contains a water-soluble dye represented by the formula (1) or a copper complex dye.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21114899A JP4162334B2 (en) | 1999-07-26 | 1999-07-26 | Dye-type polarizing film |
| TW089113874A TW440715B (en) | 1999-07-14 | 2000-07-12 | Dyeing polarizing film and polarizing plate |
| CNB008100969A CN1175289C (en) | 1999-07-14 | 2000-07-12 | Polarizer comprising dye |
| KR1020017016279A KR100653318B1 (en) | 1999-07-14 | 2000-07-12 | Polarizer comprising dye |
| CA2379139A CA2379139C (en) | 1999-07-14 | 2000-07-12 | Dye type polarizing plate |
| EP00946278A EP1203969B1 (en) | 1999-07-14 | 2000-07-12 | Polarizer comprising dye |
| PCT/JP2000/004658 WO2001006281A1 (en) | 1999-07-14 | 2000-07-12 | Polarizer comprising dye |
| KR1020067014918A KR100730227B1 (en) | 1999-07-14 | 2000-07-12 | Polarizer comprising dye |
| DE60020976T DE60020976T2 (en) | 1999-07-14 | 2000-07-12 | DYER POLARIZER |
| US10/018,851 US6790490B1 (en) | 1999-07-14 | 2000-07-12 | Dye type polarizing plate |
| HK02108755.6A HK1047319B (en) | 1999-07-14 | 2002-12-02 | A polyvinyl alcohol type polarizing film, a polyvinyl alcohol type polarizing plate and a color liquid crystal projector having the polarizing plate |
| US10/898,817 US7108897B2 (en) | 1999-07-14 | 2004-07-26 | Dye type polarizing plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21114899A JP4162334B2 (en) | 1999-07-26 | 1999-07-26 | Dye-type polarizing film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001033627A JP2001033627A (en) | 2001-02-09 |
| JP4162334B2 true JP4162334B2 (en) | 2008-10-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21114899A Expired - Lifetime JP4162334B2 (en) | 1999-07-14 | 1999-07-26 | Dye-type polarizing film |
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| Country | Link |
|---|---|
| JP (1) | JP4162334B2 (en) |
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