JP4174192B2 - Homeotropic alignment liquid crystal composition, method for producing homeotropic alignment liquid crystal film, and homeotropic alignment liquid crystal film - Google Patents
Homeotropic alignment liquid crystal composition, method for producing homeotropic alignment liquid crystal film, and homeotropic alignment liquid crystal film Download PDFInfo
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- JP4174192B2 JP4174192B2 JP2001136848A JP2001136848A JP4174192B2 JP 4174192 B2 JP4174192 B2 JP 4174192B2 JP 2001136848 A JP2001136848 A JP 2001136848A JP 2001136848 A JP2001136848 A JP 2001136848A JP 4174192 B2 JP4174192 B2 JP 4174192B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、ホメオトロピック配向液晶性組成物および当該ホメオトロピック配向液晶性組成物を用いたホメオトロピック配向液晶フィルムの製造方法に関する。また本発明は当該製造方法により得られるホメオトロピック配向液晶フィルム、さらには光学フィルムと上記光学フィルムを用いた液晶表示装置に関する。ホメオトロピック配向液晶フィルムは単独でまたは他のフィルムと組み合わせて、位相差フィルム、視角補償フィルム、光学補償フィルム、楕円偏光フィルム等の光学フィルムとして使用できる。
【０００２】
【従来の技術】
液晶化合物のホメオトロピック配向は、液晶相の分子長軸が平均して薄膜（液晶相）を形成する基板に対して実質的に垂直である場合に生じる。自発的にホメオトロピック配向する物質は非常に僅かしかなく、従って、かかる配向を生じさせるためには、一般的に垂直配向剤が用いられる。垂直配向剤によりホメオトロピック配向させることができる液晶化合物としては、たとえば、ネマチック液晶化合物が知られている。かかる液晶化合物の配向技術にかかわる概説は、例えば、化学総説４４（表面の改質，日本化学会編，１５６〜１６３頁）に記載されている。
【０００３】
前記液晶化合物をホメオトロピック配向させるうる垂直配向剤としては各種の有機系または無機系配向剤が知られているが、慣用されている配向剤の多くはガラス基板上で有効に作用するようにデザインされている。
【０００４】
このような慣用の有機系配向剤としては、たとえば、レシチン、シラン系界面活性剤、ｎ−オクタデシルトリエトキシシラン、チタネート系界面活性剤、ピリジニウム塩系高分子界面活性剤、ヘキサデシルトリメチルアンモニウムハライドまたはクロム錯体などがあげられる。これら有機系配向剤は、活性成分が非常に少量（代表的には１％よりも少ない量）となるように適当な揮発性溶剤に溶解され、次いで例えばスピンコーティングまたはその他周知の塗工方法によって基板上に塗工された後、揮発性溶剤を蒸発させることにより、ガラス基板上に有機配向剤の薄膜として形成される。これら有機系配向剤は、極性のガラス表面に引き付けられると考えられる極性末端基とガラス表面に対して垂直に配列する無極性の長鎖状アルキル鎖を有することを特徴とするものであり、このような表面上において液晶化合物にホメオトロピック配向を生じさせる。
【０００５】
また無機系配向剤としては、例えば、ガラス基板上にＳｉＯX またはＩｎ2 Ｏ3 ／ＳｎＯ2 を垂直角度で蒸着させたものが知られており、液晶化合物にホメオトロピック配向を生じさせる。その他、アルキル側鎖付ポリイミド膜も液晶ディスプレイなどのホメオトロピック配向膜として用いられている。
【０００６】
しかしながら、前記慣用の配向剤は、いずれもガラス基板上においてのみ液晶化合物にホメオトロピック配向を与えるものであり、プラスチックフィルムやプラスチックシート等のポリマー物質からなる基板上での配向にはあまり有効に作用するものではない。ポリマー物質からなる基板の表面は前記慣用されている配向剤の極性末端基に対する親和性に乏しいものと推測され、それゆえ、一般的には、ホメオトロピック配向を全然示さないか、またはほんの僅かに配向を示すに留まる。また、アルキル側鎖付ポリイミド膜の形成には高温での熱処理が必要であるが、ポリイミド配向膜を焼成するに耐えることができ、光学用途として使用できる透明プラスチックフィルムはほんの僅かである。
【０００７】
【発明が解決しようとする課題】
これに対し本出願人は、液晶性フラグメント側鎖を含有するモノマーユニット（ａ）と非液晶性フラグメント側鎖を含有するモノマーユニット（ｂ）を含有する側鎖型液晶ポリマーが、垂直配向膜を使用することなく基板上でホメオトロピック配向させることができ、これによりホメオトロピック配向液晶フィルムを製造できることを見出している（特願２０００−３７０９７８）。しかし、これら側鎖型液晶ポリマーは垂直配向膜を使用することなく基板上でフィルムを形成しているため、液晶フィルムのＴｇが低く設計されている。これら液晶フィルムには液晶ディプレイ等の用途として用いうる耐久性の向上が望まれている。
【０００８】
本発明は、垂直配向膜を使用することなく、基板上で、耐久性に優れたホメオトロピック配向液晶フィルムを形成できるホメオトロピック配向液晶性組成物を提供すること、またホメオトロピック配向液晶性組成物を用いてホメオトロピック配向液晶フィルムの製造方法を提供すること、また前記製造方法により得られたホメオトロピック配向液晶フィルムを提供することを目的とする。さらには基板上に垂直配向膜を介することなくホメオトロピック配向液晶フィルム層を有する光学フィルムと上記光学フィルムを用いた液晶表示装置を提供することを目的とする。
【０００９】
【課題を解消するための手段】
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、以下に示すホメオトロピック配向液晶性組成物により前記目的を達成できることを見出し本発明を完成するに至った。
【００１０】
すなわち、本発明は、垂直配向膜の設けられていない基板上でホメオトロピック配向液晶層を形成しうる側鎖型液晶ポリマーであり、下記の一般式（ａ）で表されるモノマーユニットと下記の一般式（ｂ）で表されるモノマーユニットとを含有する側鎖型液晶ポリマーと、光重合性液晶化合物を含有してなることを特徴とするホメオトロピック配向液晶性組成物、に関する。
一般式（ａ）：
【化２Ａ】
一般式（ｂ）：
【化２Ｂ】
【化２Ｃ】
【００１１】
上記本発明のホメオトロピック配向液晶性組成物が側鎖型液晶ポリマーのほかに含有する光重合性液晶化合物は、熱処理により液晶状態として、たとえば、ネマチック液晶層を発現させて側鎖型液晶ポリマーとともにホメオトロピック配向させることができ、その後に光重合性液晶化合物を重合または架橋させることによりホメオトロピック配向液晶フィルムの耐久性を向上させることができる。
【００１２】
前記ホメオトロピック配向液晶性組成物において、側鎖型液晶ポリマーが、液晶性フラグメント側鎖を含有するモノマーユニット（ａ）と非液晶性フラグメント側鎖を含有するモノマーユニット（ｂ）を含有する側鎖型液晶ポリマーであることが好ましい。
【００１３】
前記側鎖型液晶ポリマーは、垂直配向膜を用いずに、液晶ポリマーのホメオトロピック配向を実現することができる。当該側鎖型液晶ポリマーは、通常の側鎖型液晶ポリマーが有する液晶性フラグメント側鎖を含有するモノマーユニット（ａ）の他に、アルキル鎖等を有する非液晶性フラグメント側鎖を含有するモノマーユニット（ｂ）を有しており、非液晶性フラグメント側鎖を含有するモノマーユニット（ｂ）の作用により、垂直配向膜を用いなくても、たとえば熱処理により液晶状態としネマチック液晶相を発現させ、ホメオトロピック配向を示すようになったものと推察する。
【００１４】
また、本発明は、垂直配向膜の設けられていない基板上に、前記ホメオトロピック配向液晶性組成物を塗工し、さらに当該液晶性組成物を液晶状態においてホメオトロピック配向させ、その配向状態を維持した状態で固定化した後、光照射することを特徴とするホメオトロピック配向液晶フィルムの製造方法、に関する。
【００１５】
前記液晶性組成物を垂直配向膜を用いずに、ホメオトロピック配向させた後、熱を除去しガラス化させ、ホメオトロピック配向した液晶ポリマー層を固定化した後、光照射により光重合性液晶化合物を重合または架橋させることにより耐久性に優れたホメオトロピック配向液晶フィルムを得ることができる。
【００１６】
前記ホメオトロピック配向液晶フィルムの製造方法において、基板は、ポリマー物質、ガラス基板、金属等の各種材質のものを用いることができる。また、ポリマー物質が、プラスチックシートまたはプラスチックフィルムとして用いられる。本発明の製造方法に用いられる基板の種類に制限はなく、ガラス基板、ポリマー物質、金属を特に制限なく使用することができ、またポリマー物質はプラスチックシートまたはプラスチックフィルムとして用いることができる。
【００１７】
また本発明は、前記製造方法により得られたホメオトロピック配向液晶フィルム、に関する。
【００１８】
また本発明は、垂直配向膜の設けられていない基板上に、前記ホメオトロピック配向液晶性組成物がホメオトロピック配向し、固定したホメオトロピック配向液晶フィルム層が設けられている光学フィルム、に関する。
【００１９】
さらには本発明は、前記光学フィルムを適用した液晶表示装置、に関する。
【００２０】
【発明の実施の形態】
本発明においてホメオトロピック配向液晶層を形成しうる液晶ポリマーとしては、液晶性フラグメント側鎖を含有するモノマーユニット（ａ）と非液晶性フラグメント側鎖を含有するモノマーユニット（ｂ）を含有する側鎖型液晶ポリマーが用いられる。
【００２１】
前記モノマーユニット（ａ）はネマチック液晶性を有する側鎖を有するものであり、一般式（ａ）：
【化３Ａ】
で表される。
【００２２】
またモノマーユニット（ｂ）は、直鎖状側鎖を有するものであり、一般式（ｂ）：
【化３Ｂ】
【化３Ｃ】
で表される。
【００２３】
また、モノマーユニット（ａ）とモノマーユニット（ｂ）の割合は、特に制限されるものではなく、モノマーユニットの種類によっても異なるが、モノマーユニット（ｂ）の割合が多くなると側鎖型液晶ポリマーが液晶モノドメイン配向性を示さなくなるため、（ｂ）／｛（ａ）十（ｂ）｝＝０．０１〜０．８（モル比）とするのが好ましい。特に０．１〜０．５とするのがより好ましい。
【００２４】
前記側鎖型液晶ポリマーの重量平均分子量は、２千〜１０万であるのが好ましい。重量平均分子量をかかる範囲に調整することにより液晶ポリマーとしての性能を発揮する。側鎖型液晶ポリマーの重量平均分子量が過少では配向層の成膜性に乏しくなる傾向があるため、重量平均分子量は２．５千以上とするのがより好ましい。一方、重量平均分子量が過多では液晶としての配向性に乏しくなって均一な配向状態を形成しにくくなる傾向があるため、重量平均分子量は５万以下とするのがより好ましい。
【００２５】
なお、側鎖型液晶ポリマーは、前記モノマーユニット（ａ）、モノマーユニット（ｂ）に対応するアクリル系モノマーまたはメタクリル系モノマーを共重合することにより調製できる。なお、モノマーユニット（ａ）、モノマーユニット（ｂ）に対応するモノマーは公知の方法により合成できる。共重合体の調製は、例えばラジカル重合方式、カチオン重合方式、アニオン重合方式などの通例のアクリル系モノマー等の重合方式に準じて行うことができる。なお、ラジカル重合方式を適用する場合、各種の重合開始剤を用いうるが、そのうちアゾビスイソブチロニトリルや過酸化ベンゾイルなどの分解温度が高くもなく、かつ低くもない中間的温度で分解するものが好ましく用いられる。
【００２６】
光重合性液晶化合物は、光重合性官能基として、たとえば、アクリロイル基またはメタアクリロイル基等の不飽和二重結合を少なくとも１つ有する液晶性化合物であり、ネマチック液晶性のものが賞用される。かかる光重合性液晶化合物としては、前記モノマーユニット（ａ）となるアクリレートやメタクリレートを例示できる。光重合性液晶化合物として、耐久性を向上させるには、光重合性官能基を２つ以上有するものが好ましい。このような光重合性液晶化合物として、たとえば、下記化４：
【化４】
【００２７】
液晶性組成物中の光重合性液晶化合物と側鎖型液晶ポリマーの比率は、特に制限されず、得られるホメオトロピック配向液晶フィルムの耐久性等を考慮して適宜に決定されるが、通常、光重合性液晶化合物：側鎖型液晶ポリマー（重量比）＝０．１：１〜３０：１程度が好ましく、特に０．５：１〜２０：１が好ましく、さらには１：１〜１０：１が好ましい。
【００２８】
前記液晶性組成物中には、通常、光重合開始剤を含有する。光重合開始剤は各種のものを特に制限なく使用できる。光重合開始剤としては、たとえば、チバスペシャリフィケミカルズ社製のイルガキュア（Ｉｒｇａｃｕｒｅ）９０７，同１８４、同６５１、同３６９などを例示できる。光重合開始剤の添加量は、光重合液晶化合物の種類、液晶性組成物の配合比等を考慮して、液晶性組成物のホメオトロピック配向性を乱さない程度に加えられる。通常、光重合性液晶化合物１００重量部に対して、０．５〜３０重量部程度が好ましい。特に３〜１５重量部が好ましい。
【００２９】
前記液晶性組成物を塗工する基板は、ガラス基板、金属箔、プラスチックシートまたはプラスチックフィルムのいずれの形状でもよい。基板の厚さは、通常、１０〜１０００μｍ程度である。
【００３０】
プラスチックフィルムは配向させる温度で変化しないものであれば特に制限はなく、たとえば、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロース、トリアセチルセルロース等のセルロース系ポリマー、ポリカーボネート系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー等の透明ポリマーからなるフィルムがあげられる。またポリスチレン、アクリロニトリル・スチレン共重合体等のスチレン系ポリマー、ポリエチレン、ポリプロピレン、環状ないしノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体等のオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー等の透明ポリマーからなるフィルムもあげられる。さらにイミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマーや前記ポリマーのブレンド物等の透明ポリマーからなるフィルムなどもあげられる。これらのなかでも水素結合性の高いプラスチックフィルムが好ましい。
【００３１】
また金属フィルムとしては、例えばアルミニウムなどから形成される当該フィルムが挙げられる。
【００３２】
プラスチックフィルムとしては、特にゼオノア（商品名，日本ゼオン（株）製）、ゼオネックス（商品名，日本ゼオン（株）製）、アートン（商品名，ＪＳＲ（株）製）などのノルボルネン構造を有するポリマー物質からなるプラスチックフィルムが光学的にも優れた特性を有する。これらポリマー物質（プラスチックフィルム）は光学異方性が非常に小さいため、プラスチックフィルム上に形成された前記液晶性組成物の配向液晶フィルム層は、当該配向液晶フィルム層を別のプラスチックフィルムヘ転写することなく、そのままホメオトロピック配向位相差フィルムとして液晶ディスプレイの光学補償用途等の光学フィルムに用いることができる。また、光学異方性を有するプラスチックフィルムやアルミホイルなどの金属フィルム上に形成した前記液晶性組成物の配向液晶フィルム層に関しては、前記液晶性組成物を配向液晶フィルム化した後、ノルボルネン構造を有するフィルムやセルローストリアセテートなどの透明で光学異方性の小さいプラスチックフィルム上に直接または粘着剤もしくは接着剤を介して転写することにより、光学補償フィルム等の光学フィルムに利用することができる。
【００３３】
前記液晶性組成物を基板に塗工する方法は、当該液晶性組成物を溶媒に溶解した溶液を用いる溶液塗工方法または当該液晶性組成物を溶融して溶融塗工する方法が挙げられるが、この中でも溶液塗工方法にて支持基板上に液晶性組成物溶液を塗工する方法が好ましい。
【００３４】
溶液を調製する際に用いられる溶媒としては、液晶性組成物や基板の種類により異なり一概には言えないが、通常、クロロホルム、ジクロロメタン、ジクロロエタン、テトラクロロエタン、トリクロロエチレン、テトラクロロエチレン、クロロベンゼンなどのハロゲン化炭化水素類、フェノール、パラクロロフェノールなどのフェノール類、ベンゼン、トルエン、キシレン、メトキシベンゼン、１，２−ジメトキベンゼンなどの芳香族炭化水素類、その他、アセトン、酢酸エチル、ｔｅｒｔ−ブチルアルコール、グリセリン、エチレングリコール、トリエチレングリコール、エチレンブリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、エチルセルソルブ、ブチルセルソルブ、２−ピロリドン、Ｎ−メチル−２−ピロリドン、ピリジン、トリエチルアミン、テトラヒドロフラン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、アセトニトリル、ブチロニトリル、二硫化炭素などを用いることができる。溶液の濃度は、用いる液晶性組成物の溶解性や最終的に目的とする配向液晶フィルムの膜厚に依存するため一概には言えないが、通常３〜５０重量％、好ましくは７〜３０重量％の範囲である。
【００３５】
塗工された前記液晶性組成物からなるホメオトロピック配向液晶フィルム層の厚みは１〜１０μｍ程度とするのが好ましい。なお、特にホメオトロピック配向液晶フィルムの膜厚を精密に制御する必要がある場合には、膜厚が基板に塗工する段階でほぼ決まるため、溶液の濃度、塗工膜の膜厚などの制御は特に注意を払う必要がある。
【００３６】
上記の溶媒を用いて所望の濃度に調整した液晶性組成物溶液を、基板上に塗工する方法としては、例えばスピンコート法、バーコート法などを採用することができる。塗工後、溶媒を除去し、基板上に液晶性組成物層を形成させる。溶媒の除去条件は、特に限定されず、溶媒をおおむね除去でき、液晶性組成物層が流動したり、流れ落ちたりさえしなければ良い。通常、室温での乾燥、乾燥炉ての乾燥、ホットプレート上での加熱などを利用して溶媒を除去する。
【００３７】
次いで、支持基板上に形成された液晶性組成物層を液晶状態とし、ホメオトロピック配向させる。たとえば、液晶性組成物が液晶温度範囲になるように熱処理を行い、液晶状態においてホメオトロピック配向させる。熱処理方法としては、上記の乾燥方法と同様の方法で行うことができる。熱処理温度は、使用する液晶性組成物と支持基板の種類により異なるため一概には言えないが、通常６０〜３００℃、好ましくは７０〜２００℃の範囲において行う。また熱処理時間は、熱処理温度および使用する液晶性組成物や基板の種類によって異なるため一概には言えないが、通常１０秒〜２時間、好ましくは２０秒〜３０分の範囲で選択される。１０秒より短い場合ホメオトロピック配向形成が十分に進行しないおそれがある。
【００３８】
熱処理終了後、冷却操作を行う。冷却操作としては、熱処理後のホメオトロピック配向液晶層を、熱処理操作における加熱雰囲気中から、室温中に出すことによって行うことができる。また空冷、水冷などの強制冷却を行ってもよい。前記液晶性組成物のホメオトロピック液晶配向層は、液晶ポリマーのガラス転移温度以下に冷却することにより配向が固定化される。
【００３９】
このように固定化されたホメオトロピック液晶配向層に対して、光照射を行い光重合性液晶化合物を重合または架橋させて光重合性液晶化合物を固定化して、耐久性を向上したホメオトロピック配向液晶フィルムを得る。光照射は、たとえば、紫外線照射により行う。紫外線照射条件は、十分に反応を促進するために、不活性気体雰囲気中とすることが好ましい。通常、約８０〜１６０ｍＷ／ｃｍ2 の照度を有する高圧水銀紫外ランプが代表的に用いられる。メタハライドＵＶランプや白熱管などの別種ランプを使用することもできる。なお、紫外線照射時の液ｈ層表面温度が液晶温度範囲内になるように、コールドミラー、水冷その他の冷却処理あるいはライン速度を速くするなどして適宜に調整する。
【００４０】
このようにして液晶性組成物の薄膜が生成され、配向性を維持したまま固定化することにより、ホメオトロピック配向した配向液晶フィルムが得られる。当該配向液晶層は同一の方向で配向された分子を有する。従ってこの配向液晶層の配向ベクトルの凍結または安定化およびその異方性物性の保存が達成されることは周知であり、このような薄膜はそれらの光学的性質が確認され、各種の用途で使用される。前記配向液晶層は一軸性の正の複屈折率を有する薄膜である。
【００４１】
以上のようにして得られるホメオトロピック配向液晶層の配向は、当該液晶層の光学位相差を垂直入射から傾けた角度で測定することによって量化することができる。ホメオトロピック配向液晶フィルムの場合、この位相差値は垂直入射について対称的である。光学位相差の測定には数種の方法を利用することができ、例えば自動複屈折測定装置（オーク製）および偏光顕微鏡（オリンパス製）を利用することができる。このホメオトロピック配向液晶フィルムはクロスニコル偏光子間で黒色に見える。
【００４２】
こうして得られたホメオトロピック配向液晶フィルムは、基板から剥離して用いてもよいし、剥離することなく基板上に形成された配向液晶層としてそのまま用いてもよい。
【００４３】
また、ホメオトロピック配向液晶フィルムは光学フィルムとして用いられる。例えば、一軸配向した位相差フィルムを基材としてホメオトロピック配向液晶フィルムを作製すると、広視野角の位相差フィルが得られ、これをＳＴＮ型液晶表示装置に適用することにより、液晶表示装置の表示特性、特に視野角特性を著しく向上させることができる。
【００４４】
【実施例】
以下に実施例をあげて本発明の一態様について説明するが、本発明は実施例に限定されないことはいうまでもない。
【００４５】
実施例１
【化５】
【００４６】
（ホメオトロピック配向性）
サンプル（基板付きホメオトロピック配向液晶フィルム）をクロスニコルさせた偏光顕微鏡により、当該フィルム表面に対し垂直な方向からサンプルを観察したところ、正面からは何も見えなかった。これによりホメオトロピック配向を確認した。すなわち光学位相差が発生していないことがわかった。このフィルムを傾けて斜めから光を入射し、同様にクロスニコルで観察したところ、光の透過が観測された。また、同フィルムの光学位相差を自動複屈折測定装置により測定した。左３０°から測定したとき３０ｎｍであった。
【００４７】
（耐久性試験）
サンプル（基板付きホメオトロピック配向液晶フィルム）を９０℃の乾燥炉内に１２０時間投入する耐熱試験、６０℃／９０％ＲＨの条件下に１２０時間放置する湿熱試験、および偏光フィルムに粘着剤を介してホメオトロピック配向液晶フィルムを９０℃の乾燥炉内に２時間投入する耐熱粘着試験の３種の試験を行う、投入前後の物性を比較した。３種の試験のいずれにおいても試験前後において何ら変化が認められなかった。
【００４８】
実施例２
実施例１において、プラスチックフィルムのポリマー材料として、ノルボルネン系ポリマー（商品名アートン，ＪＳＲ（株）製）を用いた以外は実施例１と同様にしてホメオトロピック配向液晶フィルムを作製した。また、実施例１と同様にして、サンプルのホメオトロピック配向性を確認した。また、耐久性試験の３種の試験のいずれにおいても試験前後において何ら変化が認められなかった。
【００４９】
実施例３
実施例１において、基板として、プラスチックフィルムの代わりにガラス基板（１ｍｍ）を用いた以外は実施例１と同様にしてホメオトロピック配向液晶フィルムを作製した。また、実施例１と同様にして、サンプルのホメオトロピック配向を確認した。また、耐久性試験の３種の試験のいずれにおいても試験前後において何ら変化が認められなかった。
【００５０】
実施例４
実施例１において、側鎖型液晶ポリマーの使用量を２．５重量部、光重合性液晶化合物の使用量を２２．５重量部に変え、基板として、プラスチックフィルムの代わりにガラス基板（１ｍｍ）を用いた以外は実施例１と同様にしてホメオトロピック配向液晶フィルムを作製した。また、実施例１と同様にして、サンプルのホメオトロピック配向を確認した。また、耐久性試験の３種の試験のいずれにおいても試験前後において何ら変化が認められなかった。
【００５１】
参考例１
実施例１において、光重合性液晶化合物および光重合開始剤を使用せず、側鎖型液晶ポリマーのみを２５重量部使用した以外は実施例１と同様にしてホメオトロピック配向液晶フィルムを作製した。また、実施例１と同様にして、サンプルのホメオトロピック配向を確認した。しかし、耐久性試験の３種の試験のいずれにおいても試験後に配向の乱れなどの変化を確認した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a homeotropic alignment liquid crystal composition and a method for producing a homeotropic alignment liquid crystal film using the homeotropic alignment liquid crystal composition. The present invention also relates to a homeotropic alignment liquid crystal film obtained by the production method, and further to an optical film and a liquid crystal display device using the optical film. The homeotropic alignment liquid crystal film can be used alone or in combination with other films as an optical film such as a retardation film, a viewing angle compensation film, an optical compensation film, and an elliptically polarizing film.
[0002]
[Prior art]
Homeotropic alignment of a liquid crystal compound occurs when the molecular major axis of the liquid crystal phase is substantially perpendicular to the substrate forming a thin film (liquid crystal phase) on average. There are very few materials that spontaneously homeotropically align, and therefore vertical alignment agents are generally used to produce such alignment. As a liquid crystal compound that can be homeotropically aligned by a vertical alignment agent, for example, a nematic liquid crystal compound is known. An outline of the liquid crystal compound alignment technique is described in, for example, Chemical Review 44 (Surface Modification, Edited by The Chemical Society of Japan, pages 156 to 163).
[0003]
Various organic or inorganic alignment agents are known as vertical alignment agents capable of homeotropic alignment of the liquid crystal compound, but many of the commonly used alignment agents are designed to work effectively on a glass substrate. Has been.
[0004]
Examples of such conventional organic alignment agents include lecithin, silane surfactants, n-octadecyltriethoxysilane, titanate surfactants, pyridinium salt polymer surfactants, hexadecyltrimethylammonium halides, or And chromium complex. These organic alignment agents are dissolved in a suitable volatile solvent so that the active ingredient is very small (typically less than 1%) and then, for example, by spin coating or other well known coating methods. After coating on the substrate, the volatile solvent is evaporated to form a thin film of an organic alignment agent on the glass substrate. These organic alignment agents are characterized by having polar end groups thought to be attracted to the polar glass surface and nonpolar long-chain alkyl chains arranged perpendicular to the glass surface. A homeotropic alignment is generated in the liquid crystal compound on such a surface.
[0005]
In addition, as the inorganic alignment agent, for example, one obtained by depositing SiO x or In 2 O 3 / SnO 2 on a glass substrate at a vertical angle is known, and causes homeotropic alignment in the liquid crystal compound. In addition, polyimide films with alkyl side chains are also used as homeotropic alignment films for liquid crystal displays and the like.
[0006]
However, all of the above conventional alignment agents give homeotropic alignment to the liquid crystal compound only on the glass substrate, and are not so effective for alignment on a substrate made of a polymer material such as a plastic film or a plastic sheet. Not what you want. The surface of the substrate made of a polymeric material is presumed to have a poor affinity for the polar end groups of the conventional alignment agents and therefore generally exhibits no or only a slight homeotropic alignment. It remains to show the orientation. In addition, the formation of the alkyl side chain-attached polyimide film requires a heat treatment at a high temperature, but it can withstand the baking of the polyimide alignment film, and there are only a few transparent plastic films that can be used for optical applications.
[0007]
[Problems to be solved by the invention]
In contrast, the applicant of the present application described that the side-chain type liquid crystal polymer containing the monomer unit (a) containing the liquid crystalline fragment side chain and the monomer unit (b) containing the non-liquid crystalline fragment side chain has a vertical alignment film. It has been found that homeotropic alignment can be performed on a substrate without using it, whereby a homeotropic alignment liquid crystal film can be produced (Japanese Patent Application No. 2000-370978). However, since these side chain type liquid crystal polymers form a film on a substrate without using a vertical alignment film, the Tg of the liquid crystal film is designed to be low. These liquid crystal films are desired to have improved durability that can be used for applications such as liquid crystal displays.
[0008]
The present invention provides a homeotropic alignment liquid crystal composition capable of forming a homeotropic alignment liquid crystal film having excellent durability on a substrate without using a vertical alignment film, and also provides a homeotropic alignment liquid crystal composition. An object of the present invention is to provide a method for producing a homeotropic alignment liquid crystal film using the above-described method, and to provide a homeotropic alignment liquid crystal film obtained by the production method. Furthermore, it aims at providing the liquid crystal display device using the optical film which has a homeotropic alignment liquid crystal film layer on a board | substrate without a vertical alignment film, and the said optical film.
[0009]
[Means for solving problems]
As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by the following homeotropic alignment liquid crystalline composition, and have completed the present invention.
[0010]
That is, the present invention is a side chain type liquid crystal polymer capable of forming a homeotropic alignment liquid crystal layer on a substrate not provided with a vertical alignment film. The monomer unit represented by the following general formula (a) and the following The present invention relates to a side-chain liquid crystal polymer containing a monomer unit represented by the general formula (b) and a homeotropic alignment liquid crystalline composition characterized by containing a photopolymerizable liquid crystal compound.
General formula (a):
[Chemical 2A]
General formula (b):
[Chemical 2B]
[Chemical 2C]
[0011]
The photopolymerizable liquid crystal compound contained in the homeotropic alignment liquid crystalline composition of the present invention in addition to the side chain type liquid crystal polymer is converted into a liquid crystal state by heat treatment, for example, by developing a nematic liquid crystal layer and together with the side chain type liquid crystal polymer. Homeotropic alignment can be performed, and then the durability of the homeotropic alignment liquid crystal film can be improved by polymerizing or crosslinking the photopolymerizable liquid crystal compound.
[0012]
In the homeotropic alignment liquid crystalline composition, the side chain type liquid crystal polymer contains a monomer unit (a) containing a liquid crystalline fragment side chain and a side chain containing a monomer unit (b) containing a non-liquid crystalline fragment side chain. A liquid crystal polymer is preferable.
[0013]
The side-chain liquid crystal polymer can realize homeotropic alignment of the liquid crystal polymer without using a vertical alignment film. The side chain type liquid crystal polymer is a monomer unit containing a non-liquid crystalline fragment side chain having an alkyl chain in addition to the monomer unit (a) containing a liquid crystalline fragment side chain of a normal side chain type liquid crystal polymer. (B), the monomer unit (b) containing a non-liquid crystalline fragment side chain allows the nematic liquid crystal phase to be expressed by a heat treatment, for example, without the use of a vertical alignment film, thereby producing a homeo It is presumed that the tropic orientation has been exhibited.
[0014]
In the present invention, the homeotropic alignment liquid crystalline composition is coated on a substrate not provided with a vertical alignment film, and the liquid crystalline composition is homeotropically aligned in a liquid crystal state, and the alignment state is changed. It is related with the manufacturing method of a homeotropic alignment liquid crystal film characterized by light-irradiating after fixing in the maintained state.
[0015]
The liquid crystalline composition is homeotropically aligned without using a vertical alignment film, then heat is removed to vitrify, and the homeotropically aligned liquid crystal polymer layer is fixed, and then a photopolymerizable liquid crystal compound is irradiated by light irradiation. By polymerizing or crosslinking, a homeotropic alignment liquid crystal film having excellent durability can be obtained.
[0016]
In the method for producing the homeotropic alignment liquid crystal film, the substrate may be made of various materials such as a polymer material, a glass substrate, and a metal. Polymeric materials are also used as plastic sheets or plastic films. There is no restriction | limiting in the kind of board | substrate used for the manufacturing method of this invention, A glass substrate, a polymer substance, and a metal can be especially used without a restriction | limiting, and a polymer substance can be used as a plastic sheet or a plastic film.
[0017]
The present invention also relates to a homeotropic alignment liquid crystal film obtained by the production method.
[0018]
The present invention also relates to an optical film in which a homeotropic alignment liquid crystal film layer in which the homeotropic alignment liquid crystalline composition is homeotropically aligned and fixed is provided on a substrate not provided with a vertical alignment film.
[0019]
Furthermore, the present invention relates to a liquid crystal display device to which the optical film is applied.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
As the liquid crystal polymer capable of forming a homeotropic alignment liquid crystal layer in the present invention contains a monomer unit containing a liquid-crystalline fragment side chain (a) and a monomer unit containing a non-liquid crystalline fragment side chain (b) side A chain type liquid crystal polymer is used.
[0021]
The monomer unit (a) are those having a side chain with nematic liquid crystalline, single general formula (a):
[Chemical 3A]
It is represented by
[0022]
The monomer units (b) are those having a linear side chain, mono- general formula (b):
[Chemical 3B]
[Chemical 3C]
It is represented by
[0023]
Further, the ratio of the monomer unit (a) to the monomer unit (b) is not particularly limited and varies depending on the type of the monomer unit. However, when the ratio of the monomer unit (b) is increased, the side chain type liquid crystal polymer is changed. Since the liquid crystal monodomain orientation is not exhibited, it is preferable that (b) / {(a) + (b)} = 0.01 to 0.8 (molar ratio). In particular, 0.1 to 0.5 is more preferable.
[0024]
The side chain type liquid crystal polymer preferably has a weight average molecular weight of 2,000 to 100,000. By adjusting the weight average molecular weight to such a range, performance as a liquid crystal polymer is exhibited. When the weight average molecular weight of the side chain type liquid crystal polymer is too small, the film forming property of the alignment layer tends to be poor. Therefore, the weight average molecular weight is more preferably 2.5000 or more. On the other hand, if the weight average molecular weight is excessive, the orientation as a liquid crystal tends to be poor and it becomes difficult to form a uniform alignment state. Therefore, the weight average molecular weight is more preferably 50,000 or less.
[0025]
The side chain liquid crystal polymer can be prepared by copolymerizing an acrylic monomer or a methacrylic monomer corresponding to the monomer unit (a) and the monomer unit (b). The monomers corresponding to the monomer unit (a) and the monomer unit (b) can be synthesized by a known method. The copolymer can be prepared, for example, according to a polymerization method such as a conventional acrylic monomer such as a radical polymerization method, a cationic polymerization method, and an anionic polymerization method. When applying the radical polymerization method, various polymerization initiators can be used. Among them, decomposition temperatures such as azobisisobutyronitrile and benzoyl peroxide are not high and are not low. Those are preferably used.
[0026]
The photopolymerizable liquid crystal compound is a liquid crystal compound having at least one unsaturated double bond such as an acryloyl group or a methacryloyl group as a photopolymerizable functional group. . Examples of such photopolymerizable liquid crystal compounds include acrylates and methacrylates that serve as the monomer unit (a). As the photopolymerizable liquid crystal compound, those having two or more photopolymerizable functional groups are preferable for improving durability. As such a photopolymerizable liquid crystal compound, for example,
[Formula 4]
[0027]
The ratio of the photopolymerizable liquid crystal compound and the side chain type liquid crystal polymer in the liquid crystal composition is not particularly limited and is appropriately determined in consideration of the durability of the obtained homeotropic alignment liquid crystal film. Photopolymerizable liquid crystal compound: side chain type liquid crystal polymer (weight ratio) = about 0.1: 1 to 30: 1 is preferable, 0.5: 1 to 20: 1 is particularly preferable, and 1: 1 to 10: is more preferable. 1 is preferred.
[0028]
The liquid crystalline composition usually contains a photopolymerization initiator. Various photopolymerization initiators can be used without particular limitation. Examples of the photopolymerization initiator include Irgacure 907, 184, 651, and 369 manufactured by Ciba Specialty Chemicals. The addition amount of the photopolymerization initiator is added to such an extent that the homeotropic orientation of the liquid crystalline composition is not disturbed in consideration of the type of the photopolymerized liquid crystal compound, the blending ratio of the liquid crystalline composition, and the like. Usually, about 0.5-30 weight part is preferable with respect to 100 weight part of photopolymerizable liquid crystal compounds. 3 to 15 parts by weight is particularly preferable.
[0029]
The substrate on which the liquid crystalline composition is applied may have any shape of a glass substrate, a metal foil, a plastic sheet, or a plastic film. The thickness of the substrate is usually about 10 to 1000 μm.
[0030]
The plastic film is not particularly limited as long as it does not change with the orientation temperature. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate polymers, polymethyl Examples thereof include a film made of a transparent polymer such as an acrylic polymer such as methacrylate. Styrene polymers such as polystyrene and acrylonitrile / styrene copolymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, olefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, nylon and aromatic polyamides, etc. Examples thereof include films made of transparent polymers such as amide polymers. Furthermore, imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers Examples thereof include a film made of a transparent polymer such as a polymer, an epoxy-based polymer, and a blend of the aforementioned polymers. Among these, a plastic film having a high hydrogen bonding property is preferable.
[0031]
Moreover, as a metal film, the said film formed from aluminum etc. is mentioned, for example.
[0032]
As plastic films, polymers having a norbornene structure such as ZEONOR (trade name, manufactured by ZEON CORPORATION), ZEONEX (trade name, manufactured by ZEON CORPORATION), Arton (trade name, manufactured by JSR Corporation), etc. A plastic film made of a substance has excellent optical properties. Since these polymer substances (plastic films) have very small optical anisotropy, the aligned liquid crystal film layer of the liquid crystalline composition formed on the plastic film transfers the aligned liquid crystal film layer to another plastic film. Without any modification, it can be used as an optical film for optical compensation of a liquid crystal display as a homeotropic alignment retardation film. In addition, with respect to the aligned liquid crystal film layer of the liquid crystalline composition formed on a metal film such as a plastic film or aluminum foil having optical anisotropy, the norbornene structure is formed after the liquid crystalline composition is converted into an aligned liquid crystal film. It can be used for an optical film such as an optical compensation film by transferring directly or via a pressure-sensitive adhesive or adhesive onto a transparent plastic film having a small optical anisotropy such as a cellulose triacetate.
[0033]
Examples of the method of applying the liquid crystalline composition to the substrate include a solution coating method using a solution in which the liquid crystalline composition is dissolved in a solvent, or a method of melting and applying the liquid crystalline composition. Of these, the method of coating the liquid crystalline composition solution on the support substrate by the solution coating method is preferable.
[0034]
The solvent used in preparing the solution differs depending on the liquid crystal composition and the type of the substrate, and cannot generally be said, but usually halogenated carbonization such as chloroform, dichloromethane, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, etc. Hydrogens, phenols such as phenol and parachlorophenol, aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, and 1,2-dimethoxybenzene, others, acetone, ethyl acetate, tert-butyl alcohol, glycerin , Ethylene glycol, triethylene glycol, ethylene brickol monomethyl ether, diethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, 2-pyrrolidone, N-methyl-2-pyrrole Emissions, pyridine, triethylamine, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, can be used acetonitrile, butyronitrile, carbon disulfide and the like. Although the concentration of the solution depends on the solubility of the liquid crystal composition to be used and the film thickness of the final oriented liquid crystal film, it cannot be generally stated, but is usually 3 to 50% by weight, preferably 7 to 30% by weight. % Range.
[0035]
The thickness of the homeotropic alignment liquid crystal film layer made of the coated liquid crystalline composition is preferably about 1 to 10 μm. In particular, when it is necessary to precisely control the film thickness of the homeotropic alignment liquid crystal film, the film thickness is almost determined at the stage of coating on the substrate, so control of the solution concentration, the film thickness of the coating film, etc. Need to pay special attention.
[0036]
As a method for applying a liquid crystalline composition solution adjusted to a desired concentration using the above-mentioned solvent onto a substrate, for example, a spin coating method, a bar coating method, or the like can be employed. After coating, the solvent is removed, and a liquid crystalline composition layer is formed on the substrate. The conditions for removing the solvent are not particularly limited, as long as the solvent can be largely removed and the liquid crystalline composition layer does not flow or even flow down. Usually, the solvent is removed by drying at room temperature, drying in a drying oven, heating on a hot plate, or the like.
[0037]
Next, the liquid crystalline composition layer formed on the supporting substrate is brought into a liquid crystal state and homeotropic aligned. For example, heat treatment is performed so that the liquid crystal composition is in the liquid crystal temperature range, and homeotropic alignment is performed in the liquid crystal state. The heat treatment can be performed by the same method as the above drying method. The heat treatment temperature varies depending on the liquid crystal composition to be used and the type of the support substrate, and thus cannot be generally described, but is usually 60 to 300 ° C, preferably 70 to 200 ° C. The heat treatment time varies depending on the heat treatment temperature and the type of liquid crystal composition used and the type of substrate, and cannot be generally specified, but is usually selected in the range of 10 seconds to 2 hours, preferably 20 seconds to 30 minutes. If it is shorter than 10 seconds, homeotropic alignment formation may not proceed sufficiently.
[0038]
After the heat treatment is completed, a cooling operation is performed. As the cooling operation, the homeotropic alignment liquid crystal layer after the heat treatment can be performed by taking it out from the heating atmosphere in the heat treatment operation to room temperature. Moreover, you may perform forced cooling, such as air cooling and water cooling. The alignment of the homeotropic liquid crystal alignment layer of the liquid crystalline composition is fixed by cooling to a temperature lower than the glass transition temperature of the liquid crystal polymer.
[0039]
The homeotropic alignment liquid crystal with improved durability is obtained by irradiating the homeotropic liquid crystal alignment layer thus fixed with light to polymerize or crosslink the photopolymerizable liquid crystal compound to fix the photopolymerizable liquid crystal compound. Get a film. Light irradiation is performed by, for example, ultraviolet irradiation. The ultraviolet irradiation conditions are preferably in an inert gas atmosphere in order to sufficiently promote the reaction. Usually, a high-pressure mercury ultraviolet lamp having an illuminance of about 80 to 160 mW / cm 2 is typically used. Different types of lamps such as metahalide UV lamps and incandescent tubes can also be used. It should be noted that the liquid h layer surface temperature at the time of ultraviolet irradiation is appropriately adjusted by, for example, a cold mirror, water cooling, or other cooling treatment, or by increasing the line speed.
[0040]
In this way, a thin film of a liquid crystalline composition is produced, and an aligned liquid crystal film having homeotropic alignment can be obtained by fixing it while maintaining the alignment. The alignment liquid crystal layer has molecules aligned in the same direction. Therefore, it is well known that the alignment vector of this alignment liquid crystal layer can be frozen or stabilized and its anisotropic properties can be preserved. Such thin films have been confirmed for their optical properties and can be used in various applications. Is done. The alignment liquid crystal layer is a thin film having a uniaxial positive birefringence.
[0041]
The orientation of the homeotropic alignment liquid crystal layer obtained as described above can be quantified by measuring the optical phase difference of the liquid crystal layer at an angle inclined from normal incidence. In the case of homeotropic alignment liquid crystal films, this retardation value is symmetric with respect to normal incidence. Several methods can be used to measure the optical phase difference. For example, an automatic birefringence measuring device (manufactured by Oak) and a polarizing microscope (manufactured by Olympus) can be used. This homeotropic alignment liquid crystal film appears black between the crossed Nicol polarizers.
[0042]
The homeotropic alignment liquid crystal film thus obtained may be used after being peeled off from the substrate, or may be used as it is as an alignment liquid crystal layer formed on the substrate without being peeled off.
[0043]
The homeotropic alignment liquid crystal film is used as an optical film. For example, when a homeotropically oriented liquid crystal film is produced using a uniaxially oriented retardation film as a base material, a retardation film having a wide viewing angle is obtained. By applying this to a STN type liquid crystal display device, the display of the liquid crystal display device is obtained. Characteristics, particularly viewing angle characteristics, can be significantly improved.
[0044]
【Example】
Examples of the present invention will be described below with reference to examples, but the present invention is not limited to the examples.
[0045]
Example 1
[Chemical formula 5]
[0046]
(Homeotropic orientation)
When the sample (homeotropic alignment liquid crystal film with a substrate) was crossed Nicol and the sample was observed from a direction perpendicular to the film surface, nothing was seen from the front. This confirmed homeotropic orientation. That is, it was found that no optical phase difference occurred. When this film was tilted and light was incident from an oblique direction and observed in the same manner with crossed Nicols, light transmission was observed. The optical retardation of the film was measured with an automatic birefringence measuring device. It was 30 nm when measured from the left 30 °.
[0047]
(Durability test)
A sample (homeotropic alignment liquid crystal film with a substrate) is put into a drying oven at 90 ° C. for 120 hours, a heat resistance test in which the sample is left to stand for 60 hours at 60 ° C./90% RH, and a polarizing film through an adhesive. The three properties of the heat-resistant adhesion test in which the homeotropic alignment liquid crystal film was placed in a drying oven at 90 ° C. for 2 hours were compared. In all three tests, no change was observed before and after the test.
[0048]
Example 2
In Example 1, a homeotropic alignment liquid crystal film was produced in the same manner as in Example 1 except that a norbornene-based polymer (trade name: Arton, manufactured by JSR Corporation) was used as the polymer material for the plastic film. In addition, the homeotropic orientation of the sample was confirmed in the same manner as in Example 1. Further, no change was observed before and after the test in any of the three types of durability tests.
[0049]
Example 3
In Example 1, a homeotropic alignment liquid crystal film was produced in the same manner as in Example 1 except that a glass substrate (1 mm) was used instead of the plastic film as the substrate. Further, the homeotropic orientation of the sample was confirmed in the same manner as in Example 1. Further, no change was observed before and after the test in any of the three types of durability tests.
[0050]
Example 4
In Example 1, the amount of the side chain type liquid crystal polymer used was changed to 2.5 parts by weight and the amount of the photopolymerizable liquid crystal compound used was changed to 22.5 parts by weight. As a substrate, a glass substrate (1 mm) was used instead of a plastic film. A homeotropic alignment liquid crystal film was produced in the same manner as in Example 1 except that was used. Further, the homeotropic orientation of the sample was confirmed in the same manner as in Example 1. Further, no change was observed before and after the test in any of the three types of durability tests.
[0051]
Reference example 1
In Example 1, a homeotropic alignment liquid crystal film was produced in the same manner as in Example 1 except that the photopolymerizable liquid crystal compound and the photopolymerization initiator were not used and only 25 parts by weight of the side chain type liquid crystal polymer was used. Further, the homeotropic orientation of the sample was confirmed in the same manner as in Example 1. However, in any of the three types of durability tests, changes such as disorder of orientation were confirmed after the tests.
Claims (7)
一般式（ａ）：
一般式（ｂ）：
General formula (a):
General formula (b):
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| JP2001136848A JP4174192B2 (en) | 2001-05-08 | 2001-05-08 | Homeotropic alignment liquid crystal composition, method for producing homeotropic alignment liquid crystal film, and homeotropic alignment liquid crystal film |
| US09/990,075 US6885423B2 (en) | 2000-12-06 | 2001-11-21 | Method for manufacturing homeotropic alignment liquid crystal film |
| TW090129318A TW499574B (en) | 2000-12-06 | 2001-11-27 | Method for manufacturing homeotropic alignment liquid crystal film, homeotropic alignment liquid crystalline composition and homeotropic alignment liquid crystal film |
| KR1020010076616A KR100767902B1 (en) | 2000-12-06 | 2001-12-05 | Method for manufacturing homeotropic alignment liquid crystal film, homeotropic alignment liquid crystalline composition and homeotropic alignment liquid crystal film |
| NL1019506A NL1019506C2 (en) | 2000-12-06 | 2001-12-06 | A method of making a homeotrophically positioned liquid crystal film, a homeotrophically positioned crystalline composition, and a homeotrophically positioned liquid crystal film. |
| US11/038,986 US7037443B2 (en) | 2000-12-06 | 2005-01-20 | Homeotropic alignment liquid crystal film |
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| JP2001136848A JP4174192B2 (en) | 2001-05-08 | 2001-05-08 | Homeotropic alignment liquid crystal composition, method for producing homeotropic alignment liquid crystal film, and homeotropic alignment liquid crystal film |
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