JP3783787B2 - Polymerizable liquid crystal composition and method for producing optical anisotropic body - Google Patents
Polymerizable liquid crystal composition and method for producing optical anisotropic body Download PDFInfo
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- JP3783787B2 JP3783787B2 JP03820095A JP3820095A JP3783787B2 JP 3783787 B2 JP3783787 B2 JP 3783787B2 JP 03820095 A JP03820095 A JP 03820095A JP 3820095 A JP3820095 A JP 3820095A JP 3783787 B2 JP3783787 B2 JP 3783787B2
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- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 3
- KMGDYKOGDOVDCW-UHFFFAOYSA-N CC1CC=C(C)CC1 Chemical compound CC1CC=C(C)CC1 KMGDYKOGDOVDCW-UHFFFAOYSA-N 0.000 description 2
- RPMUDXVQHUECRE-UHFFFAOYSA-N CC1COC(C)OC1 Chemical compound CC1COC(C)OC1 RPMUDXVQHUECRE-UHFFFAOYSA-N 0.000 description 2
- IBJUDLXJKAKXMG-UHFFFAOYSA-N CCC[N]1(C)(C)=CC(C)CNC1C Chemical compound CCC[N]1(C)(C)=CC(C)CNC1C IBJUDLXJKAKXMG-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【産業上の利用分野】
本発明は、液晶ディスプレイの光学補償板や偏光プリズム等の材料として有用な重合性液晶組成物、これを重合してなる光学異方体及びその製造方法に関する。
【０００２】
【従来の技術】
近年、液晶ディスプレイ素子の表示品位の向上と軽量化の両立に対する要求から、補償板として内部の分子の配向構造が制御された高分子フィルムが求められている。これに応える技術として、液晶性高分子を用いる方法（特開平３−２８８２２号公報、特開平４−３０２２号公報、特開平４−５５８１３号公報、特開平５−２７２３５号公報、特開平５−６１０３９号公報）や、２官能液晶性アクリレート化合物又は組成物を用いる方法（特開平３−１４０２９号公報）が知られているが、これらの技術はフィルム内部の分子の配向構造の均一性や、フィルムの耐熱性に問題があった。この問題を解決するために本発明者等は、室温において液晶性を有する重合性液晶組成物とその組成物を光重合して得られる内部の配向構造が制御された高分子フィルム（光学異方体）を先に提案した。該発明では重合性液晶組成物を１枚の基板に担持させるか、又は２枚の基板に挟持させた後、光重合を行ない光学異方体を製造している。この際に、１枚の基板を用いる製造方法では、２枚の基板を用いる製造方法と比較して製造コストを低くすることができる。しかしながら、１枚の基板用いる製造方法は、２枚の基板を用いる製造方法と比較して光学異方体の膜厚制御が難しいため、光学異方体の膜厚むらが生じ易いという欠点もあった。
【０００３】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、重合性液晶組成物の重合によって光学異方体を製造する際に、光学異方体の膜厚むらの発生を低減することが可能な重合性液晶組成物を提供することにある。また、これを光重合することにより得られる光学異方体、及びその製造方法をも提供する。
【０００４】
【課題を解決するための手段】
本発明者等は上記課題を解決するために、重合性液晶組成物に着目して鋭意研究を重ねた結果、本発明を提供するに至った。
【０００５】
即ち、本発明は少なくとも２つの６員環を有する液晶性骨格を部分構造として有する環状アルコール、フェノール又は芳香族ヒドロキシ化合物のアクリル酸又はメタクリル酸エステルである単官能アクリレート又は単官能メタクリレート及び界面活性剤を含有し、液晶相を示すことを特徴とする重合性液晶組成物を提供する。
【０００６】
また、本発明の重合性液晶組成物を用いて
（１）基板に配向処理を施す第１工程
（２）前記基板の配向処理を施した面に、重合性液晶組成物を塗布する第２工程
（３）前記重合性液晶組成物を重合させて光学異方体を形成する第３工程
を有する光学異方体の製造方法、及びこれより得られた光学異方体をも提供する。
【０００７】
以下、本発明の重合性液晶組成物について更に詳細に説明する。
本発明の重合性液晶組成物は、界面活性剤を含有することにより重合性液晶組成物の表面張力を下げたものである。したがって、本発明の重合性液晶組成物は、基板に塗布する際のレベリング性が向上し、膜厚むらの発生を低減できる特徴を有する。また、少なくとも２つの６員環を有する液晶性骨格を部分構造として有する環状アルコール、フェノール又は芳香族ヒドロキシ化合物のアクリル酸又はメタクリル酸エステルである単官能アクリレート又は単官能メタクリレートを含有することから、液晶相を室温付近で発現させることができ、そのため重合性液晶組成物を配向させた状態での光重合の際に、意図しない熱重合の誘起を避け、均一な配向状態の固定化が可能であるという特徴も有する。
【０００８】
本発明の重合性液晶組成物に含有される界面活性剤は、イオン性界面活性剤、非イオン性界面活性剤の区別はないが、重合性液晶組成物に含有される界面活性剤以外の成分との相溶性が良好である必要がある。含有することができる界面活性剤としては、アルキルカルボン酸塩、アルキルリン酸塩、アルキルスルホン酸塩、フルオロアルキルカルボン酸塩、フルオロアルキルリン酸塩、フルオロアルキルスルホン酸塩、ポリオキシエチレン誘導体、フルオロアルキルエチレンオキシド誘導体、ポリエチレングリコール誘導体、アルキルアンモニウム塩、フルオロアルキルアンモニウム塩類、シリコーン誘導体等をあげることができる。更に具体的には「ＭＥＧＡＦＡＣ Ｆ−１１０」、「ＭＥＧＡＦＡＣ Ｆ−１１３」、「ＭＥＧＡＦＡＣ Ｆ−１２０」、「ＭＥＧＡＦＡＣ Ｆ−８１２」、「ＭＥＧＡＦＡＣ Ｆ−１４２Ｄ」、「ＭＥＧＡＦＡＣ Ｆ−１４４Ｄ」、「ＭＥＧＡＦＡＣ Ｆ−１５０」、「ＭＥＧＡＦＡＣ Ｆ−１７１」、「ＭＥＧＡＦＡＣ Ｆ−１７３」、「ＭＥＧＡＦＡＣ Ｆ−１７７」、「ＭＥＧＡＦＡＣ Ｆ−１８３」、「ＭＥＧＡＦＡＣ Ｆ−１９５」、「ＭＥＧＡＦＡＣ Ｆ−８２４」、「ＭＥＧＡＦＡＣ Ｆ−８３３」（以上、大日本インキ化学工業株式会社製）、「Ｌ−７７」、「Ｌ−７２０」、「Ｌ−７２２」、「Ｌ−７００１」、「Ｌ−７００２」、「Ｌ−７６０２」、「Ｌ−７６０４」、「Ｌ−７６０５」、「Ｌ−７６０７Ｎ」、「Ｙ−７００６」、「ＦＺ−２１０４」、「ＦＺ−２１１０」、「ＦＺ−２１２０」、「ＦＺ−２１６１」、「ＦＺ−２１６２」、「ＦＺ−２１６３」、「ＦＺ−２１６４」、「ＦＺ−２１６５」、「ＦＺ−２１６６」、「ＦＺ−２１７１」（以上、日本ユニカー株式会社製）等の例をあげることができる。
【０００９】
本発明の重合性液晶組成物中における界面活性剤の好ましい添加量は、重合性液晶組成物中に含有される界面活性剤以外の成分や、使用温度等によって異なるが、重合性液晶組成物中の総量が０．０１〜１０重量％の範囲にあることが好ましく、０．０３〜５重量％の範囲にあることが特に好ましい。含有量が０．０１重量％より低いときは目的とする効果が得にくく、１０重量％より高いときは、重合性液晶組成物の液晶性が著しく損なわれてしまうため好ましくない。
【００１０】
本発明の重合性液晶組成物に含有される前記アクリレート又はメタクリレート化合物（以下、本発明に係わる重合性化合物とする。）は、詳しくは一般式（Ｉ）
【００１１】
【化４】
（式中、Ｘは水素原子又はメチル基を表わし、６員環Ａ、Ｂ及びＣはそれぞれ独立的に、
【００１３】
【化５】
を表わし、ｎは０又は１の整数を表わし、ｍは１から４の整数を表わし、Ｙ1及びＹ2はそれぞれ独立的に、単結合、−ＣＨ2ＣＨ2−、−ＣＨ2Ｏ−、−ＯＣＨ2−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（ＣＨ2）4−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−、−ＯＣＨ2ＣＨ2ＣＨ2−、−ＣＨ2＝ＣＨＣＨ2ＣＨ2−又は−ＣＨ2ＣＨ2ＣＨ＝ＣＨ−を表わし、Ｙ3は単結合、−ＣＯＯ−、−ＯＣＯ−を表わし、Ｒは水素原子、ハロゲン原子、シアノ基、炭素原子数１〜２０のアルキル基、アルコキシ基、アルケニル基又はアルケニルオキシ基を表わす。）で表わされる。
【００１５】
上記一般式（Ｉ）において、６員環Ａ、Ｂ及びＣはそれぞれ独立的に
【００１６】
【化６】
を表わし、ｍは１又は２の整数を表わし、Ｙ1及びＹ2はそれぞれ独立的に、単結合又は−Ｃ≡Ｃ−を表わし、Ｒはハロゲン原子、シアノ基、炭素原子数１〜２０のアルキル基、アルコキシル基又はアルケニル基を表わすことが好ましい。
【００１８】
本発明に係わる重合性化合物の代表的なものの例と、その相転移温度を示すが、本発明で使用することができる重合性化合物は、これらの化合物に限定されるものではない。
【００１９】
【化７】
【化８】
【化９】
（上記中、シクロヘキサン環はトランスシクロヘキサン環を表わし、また相転移温度スキームのＣは結晶相、Ｎはネマチック相、Ｓはスメクチック相、Ｉは等方性液体相を表わし、数字は相転移温度を表わす。）
本発明に係わる重合性化合物は、単独で用いても、２種以上の化合物を混合して用いてもよい。
【００２３】
また、本発明の重合性液晶組成物には重合性官能基を有していない液晶化合物を、重合性液晶組成物中の総量が１０重量％を超えない範囲で添加してもよい。重合性官能基を有していない液晶化合物としてはネマチック液晶化合物、スメクチック液晶化合物、コレステリック液晶化合物等の通常この技術分野で液晶と認識されるものであれば特に制限なく用いることができるが、その添加量が増えるに従い、重合性液晶組成物を光重合して得られる光学異方体の機械的強度が低下する傾向にあるので、添加量を適宜調整する必要がある。
【００２４】
また、液晶性を示さない重合性の化合物も添加することができる。このような化合物としては、通常この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであればよいが、アクリレート化合物が特に好ましい。
【００２５】
これらの液晶化合物又は重合性化合物は適宜選択して組み合わせて添加してもよいが、少なくとも得られる重合性液晶組成物の液晶性が失われないように、各成分の添加量を調整することが必要である。
【００２６】
また、本発明の重合性液晶組成物には、その重合反応性を向上させることを目的として、光重合開始剤や増感剤を添加してもよい。ここで、使用することができる光重合開始剤としては、例えば、公知のベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類等を挙げることができる。その添加量は、重合性液晶組成物中の含有量が１０重量％以下の範囲であることが好ましく、５重量％以下が特に好ましい。
【００２７】
また、本発明の重合性液晶組成物には、その保存安定性を向上させるために、安定剤を添加してもよい。ここで使用することができる安定剤としては公知のヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール等を挙げることができる。その安定剤の添加量は、重合性液晶組成物中の総量が０．０５重量％以下の範囲であることが好ましい。
【００２８】
また、本発明の重合性液晶組成物には、光学異方体に２色性を付与するために、２色性色素を添加してもよい。使用することができる二色性色素は、アゾ系、アゾキシ系、アントラキノン系、ペリレン系等があり、これらの色素を単独又は混合して用いることができる。このような二色性色素としては、例えば、「ＬＳＹ−１１６」、「ＬＳＲ−４０１」、「ＬＳＲ−４０６」、「ＬＳＲ−４２６」、「ＬＳＢ−２７８」、「ＬＳＢ−３５０」（以上、三菱化学株式会社製）、「ＳＩ−２０９」、「Ｍ−７１０」、「Ｍ−３６１」、「Ｍ−８６」、「Ｍ−６１８」、「ＳＩ−２５２」、「Ｍ−７７７」、「Ｍ−３７０」、「Ｍ−１３７」、「Ｍ−１４１」、「Ｍ−４３８」、「Ｍ−４１２」、「Ｍ−３４」、「Ｍ−４３０」、「Ｍ−４０６」、「Ｓ−３０１」、「Ｓ−３０４」、「Ｍ−６７６」（以上、三井東圧株式会社製）を挙げることができる。これらの２色性色素の添加する場合の添加量は、製造する光学異方体の用途によるが、重合性液晶組成物中の総量が０．１〜１０重量％の範囲になるように調整するのが好ましく、０．２〜２重量％の範囲が特に好ましい。
【００２９】
更に、本発明の重合性液晶組成物には、重合性液晶組成物を光重合させて製造される光学異方体中に液晶分子骨格の螺旋構造を導入する目的で、光学活性化合物を添加してもよい。ここで使用することができる光学活性化合物は、それ自体が液晶性を示す必要はなく、また重合性官能基を有していても、有していなくてもよい。またそのねじれの向きは使用する目的によって適宜選択することができる。そのような光学活性化合物としては、例えば、光学活性基としてコレステリル基を有するペラルゴン酸コレステロール、ステアリン酸コレステロール、光学活性基として２−メチルブチル基を有する「ＣＢ−１５」、「Ｃ−１５」（以上ＢＤＨ社製）、「Ｓ１０８２」（メルク社製）、「ＣＭ−１９」、「ＣＭ−２０」、「ＣＭ」（以上チッソ社製）、光学活性基として１−メチルヘプチル基を有する「Ｓ−８１１」（メルク社製）、「ＣＭ−２１」、「ＣＭ−２２」（以上チッソ社製）を挙げることができる。この光学活性化合物の添加量は、製造される光学異方体の用途により適宜調整するのが好ましい。
【００３０】
次に、上記重合性液晶組成物の重合により得られる光学異方体の製造方法について更に詳細に説明する。本発明の製造方法は、
（１）基板に配向処理を施す第１工程
（２）前記基板の配向処理を施した面に、重合性液晶組成物を塗布する第２工程
（３）前記重合性液晶組成物を重合させて光学異方体を形成する第３工程
を有するものである。
【００３１】
重合性液晶組成物の一定方向への配向は、重合性液晶組成物を塗布する基板として、例えば、基板表面を布等でラビング処理したものや、あるいは基板表面へのＳｉＯ2を斜方蒸着したものを用いれば達成することができる。また、このような配向処理を施した基板を用いない場合には、電場又は磁場を利用する方法を挙げることができる。これらの配向手段は単独で用いても、また組み合わせて用いてもよい。その中でも、基板表面を布等でラビング処理した基板を用いる方法は、その簡便性から特に好ましい。
【００３２】
このとき使用することができる基板は、有機材料、無機材料を問わずに用いることができる。具体的な例を挙げると有機材料としては、例えば、ポリエチレンテレフタレート、ポリカーボネート、ポリイミド、ポリメタクリル酸メチル、ポリスチレン、ポリエチレン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリアリレート、ポリスルホン、セルロース、ポリエーテルエーテルケトン、また無機材料としては例えば、シリコン、ガラス等を挙げることができる。また偏光フィルムを基板として用いると、偏光フィルムに直接光学異方体を作り込むことが可能であり、このようにして得られる光学異方体は、楕円偏光フィルムとして、液晶ディスプレイの構成部品として好適に用いることができる。
【００３３】
これらの基板を布等でラビングすることによって適当な配向性を得られないときは、公知の方法に従ってポリイミド薄膜又はポリビニルアルコール薄膜等の有機薄膜を基板表面に形成し、これを布等でラビングしてもよい。また通常のＴＮ又はＳＴＮセルで使用されているようなプレチルト角を与えるポリイミド薄膜を積極的に用いることは、光学異方体の内部構造を更に精密に制御できることから特に好ましい。また、電場によって配向状態を制御する場合には、電極層を有する基板を使用することができ、この場合は電極上に前述のポリイミド薄膜等の有機薄膜を形成することが好ましい。なお、本発明の重合性液晶組成物において、含有する界面活性剤によっては、液晶分子を配列させるものもあるので、このような液晶材料を用いる場合は、特に基板に配向処理を施さなくてもよい。
【００３４】
重合の方法としては、迅速な重合の進行が望ましいので、紫外線又は電子線等のエネルギー線を前述の基板に照射することによって、光重合させる方法が好ましい。エネルギー線は、本発明の重合性液晶組成物を塗布した基板面又は塗布していない基板面のどちらから照射してもよいが、塗布していない基板面に照射する場合、用いる基板は透明性を有していなければならない。また、重合時の温度は、本発明で使用する重合性液晶組成物の液晶状態が保持される温度でなければならないが、熱重合を避ける意味からもできるだけ室温に近い温度が好ましい。
【００３５】
また、このような本発明の方法によって作製される光学異方体は、基板から剥離して用いても、また剥離せずに基板に担持させたまま用いてもよい。
【００３６】
【実施例】
以下、本発明の実施例を示し、本発明を更に詳細に説明する。しかしながら、本発明はこれらの実施例に限定されるものではない。
（参考例１）式（ａ）
【００３７】
【化１０】
の化合物５０重量部及び式（ｄ）
【００３９】
【化１１】
の化合物５０重量部及び光重合開始剤「ＩＲＧ−６５１」（チバガイギー社製）１．５重量部及び非イオン性界面活性剤「ＭＥＧＡＦＡＣ Ｆ−１７７」（大日本インキ化学工業株式会社製）０．５重量部からなる重合性液晶組成物（Ａ）を調製した。得られた組成物は室温でネマチック相を示し、ネマチック相から等方性液体相への相転移温度は４２℃であった。また、２５℃におけるｎe（異常光屈折率）は１．６４であり、ｎo（常光屈折率）は１．５２であった。
【００４１】
次に、重合性液晶組成物（Ａ）をスピンコーターを用いてガラス基板上に膜厚が１０ミクロンになるように塗布した。この重合性液晶組成物（Ａ）を塗布したガラス基板を、２枚の偏光フィルムの間において観察したところ、重合性液晶組成物（Ａ）は均一なホメオトロピック配向しており、且つ膜厚むらもなかった。
【００４２】
次に、重合性液晶組成物（Ａ）を塗布したガラス基板を窒素気流下において、室温で紫外線ランプ（ＵＶＰ社製、ＵＶＧＬ−２５）を用いて１６０ｍＪ／ｃｍ2の光量の紫外線を照射し、重合性液晶組成物を光重合させて光学異方体を作製した。得られた光学異方体には、均一なホメオトロピック配向が固定化されており、且つ膜厚むらもなかった。また耐熱性にも優れてい
た。
（参考比較例１）参考例１において非イオン性界面活性剤「ＭＥＧＡＦＡＣ Ｆ−１７７」を添加しなかった以外は、参考例１と同様にして光学異方体を作製した。得られた光学異方体は、配向方向は均一なものの、膜厚むらが観察された。
（実施例１）式（ａ）の化合物５０重量部及び式（ｄ）の化合物５０重量部及び光重合開始剤「ＩＲＧ−６５１」（チバガイギー社製）１．５重量部及び非イオン性界面活性剤ポリオキシエチレンソルビタンモノラウレート（商品名Ｔｗｅｅｎ＃２０）０．５重量部からなる重合性液晶組成物（Ｂ）を調製した。得られた組成物は室温でネマチック相を示し、ネマチック相から等方性液体相への相転移温度は４１℃であった。また、２５℃におけるｎe （異常光屈折率）は１．６４であり、ｎo （常光屈折率）は１．５２であった。
【００４３】
次に、重合性液晶組成物（Ｂ）をスピンコーターを用いてラビング処理を施したポリイミド配向膜を有するガラス基板上に膜厚が１０ミクロンになるように塗布した。この重合性液晶組成物（Ｂ）を塗布したガラス基板を、２枚の偏光フィルムの間において観察したところ、重合性液晶組成物は均一なホモジニアス配向しており、且つ膜厚むらもなかった。
【００４４】
次に、重合性液晶組成物（Ｂ）を塗布したガラス基板を窒素気流下において、室温で紫外線ランプ（ＵＶＰ社製、ＵＶＧＬ−２５）を用いて１６０ｍＪ／ｃｍ2の光量の紫外線を照射し、重合性液晶組成物を光重合して光学異方体を作製した。得られた光学異方体には、均一なホモジニアス配向が固定化されており、且つ膜厚むらもなかった。また耐熱性にも優れていた。
（比較例１）実施例１において非イオン性界面活性剤「Ｔｗｅｅｎ＃２０」を添加しなかった以外は、実施例１と同様にして光学異方体を作製した。得られた光学異方体は、配向方向は均一なものの、膜厚むらが観察された。
（参考例２）式（ａ）の化合物５０重量部と式（ｄ）の化合物５０重量部、及び光重合開始剤「ＩＲＧ−６５１」（チバガイギー社製）１．５重量部及び右巻きの螺旋構造を誘起するカイラル化合物「Ｒ−８１１」（メルク社製）０．４９重量部及び非イオン性界面活性剤「Ｔｗｅｅｎ＃２０」０．５重量部からなり、螺旋ピッチが１６．１ミクロンの重合性液晶組成物（Ｃ）を得た。
【００４５】
この重合性液晶組成物（Ｃ）をスピンコーターを用いてラビング処理を施したポリカーボネート基板上に膜厚が１０ミクロンになるように塗布した。この重合性液晶組成物を塗布したポリカーボネート基板を、２枚の偏光フィルムの間において観察したところ、重合性液晶組成物は２３０度右ねじれの螺旋配向をしており、且つ膜厚むらもなかった。
【００４６】
次に、重合性液晶組成物（Ｃ）を塗布したポリカーボネート基板を窒素気流下において、室温で紫外線ランプ（ＵＶＰ社製、ＵＶＧＬ−２５）を用いて１６０ｍＪ／ｃｍ2の光量の紫外線を照射して、重合性液晶組成物を光重合して光学異方体を作製した。得られた光学異方体には、均一な２３０度右ねじれの螺旋配向が固定化されており、且つ膜厚むらもなかった。
（参考比較例２）参考例２において非イオン性界面活性剤「Ｔｗｅｅｎ＃２０」を添加しなかった以外は、参考例２と同様にして光学異方体を作製した。得られた光学異方体は、膜厚むら及びピンホール状の欠陥が観察された。
【００４７】
【発明の効果】
本発明の重合性液晶組成物は、基板上に塗布する際のレベリング性が良いため、塗布後の光重合によって得られた光学異方体の膜厚むらを低減することが可能である。
【００４８】
従って、本発明の重合性液晶組成物を用いると、低コストで膜厚むらのない光学異方体を製造することができ、液晶表示素子の光学補償板や、偏光プリズム等の光学素子の材料として非常に有用である。[0001]
[Industrial application fields]
The present invention relates to a polymerizable liquid crystal composition useful as a material for an optical compensator or a polarizing prism of a liquid crystal display, an optical anisotropic body formed by polymerizing the polymerizable liquid crystal composition, and a method for producing the same.
[0002]
[Prior art]
In recent years, a polymer film in which the alignment structure of molecules inside is controlled as a compensator has been demanded from the demand for both improvement in display quality and weight reduction of liquid crystal display elements. As a technique for responding to this, a method using a liquid crystalline polymer (JP-A-3-28822, JP-A-4-3022, JP-A-4-55813, JP-A-5-27235, JP-A-5-27235). No. 61039) and a method using a bifunctional liquid crystalline acrylate compound or a composition (Japanese Patent Laid-Open No. 3-14029) are known. However, these techniques involve uniformity of molecular orientation structures in the film, There was a problem with the heat resistance of the film. In order to solve this problem, the present inventors have developed a polymerizable liquid crystal composition having liquid crystallinity at room temperature and a polymer film (optically anisotropic) with a controlled internal alignment structure obtained by photopolymerizing the composition. Body) was proposed first. In the invention, the polymerizable liquid crystal composition is supported on one substrate or sandwiched between two substrates, and then photopolymerization is performed to produce an optical anisotropic body. At this time, the manufacturing method using one substrate can reduce the manufacturing cost as compared with the manufacturing method using two substrates. However, since the manufacturing method using one substrate is difficult to control the film thickness of the optical anisotropic body as compared with the manufacturing method using two substrates, there is a disadvantage that the film thickness unevenness of the optical anisotropic body is likely to occur. It was.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is a polymerizable liquid crystal composition capable of reducing the occurrence of film thickness unevenness in the optical anisotropic body when producing the optical anisotropic body by polymerization of the polymerizable liquid crystal composition. Is to provide. Moreover, the optically anisotropic body obtained by photopolymerizing this, and its manufacturing method are also provided.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have made extensive studies focusing on the polymerizable liquid crystal composition, and as a result, have come to provide the present invention.
[0005]
That is, the present invention relates to a monofunctional acrylate or monofunctional methacrylate which is a cyclic alcohol, phenol or aromatic hydroxy compound acrylic acid or methacrylic acid ester having a liquid crystalline skeleton having at least two 6-membered rings as a partial structure, and a surfactant. And a polymerizable liquid crystal composition characterized by exhibiting a liquid crystal phase.
[0006]
In addition, (1) a first step of performing an alignment treatment on the substrate using the polymerizable liquid crystal composition of the present invention (2) a second step of applying the polymerizable liquid crystal composition to the surface subjected to the alignment treatment of the substrate. (3) The manufacturing method of the optical anisotropic body which has the 3rd process of polymerizing the said polymeric liquid crystal composition and forming an optical anisotropic body, and the optical anisotropic body obtained from this are also provided.
[0007]
Hereinafter, the polymerizable liquid crystal composition of the present invention will be described in more detail.
The polymerizable liquid crystal composition of the present invention is obtained by lowering the surface tension of the polymerizable liquid crystal composition by containing a surfactant. Therefore, the polymerizable liquid crystal composition of the present invention has the characteristics that the leveling property when applied to a substrate is improved and the occurrence of film thickness unevenness can be reduced. In addition, it contains a monofunctional acrylate or monofunctional methacrylate which is an acrylic acid or methacrylic ester of a cyclic alcohol, phenol or aromatic hydroxy compound having a liquid crystalline skeleton having at least two 6-membered rings as a partial structure. The phase can be developed at around room temperature, and therefore, in the photopolymerization with the polymerizable liquid crystal composition aligned, it is possible to avoid unintentional thermal polymerization and to fix the uniform alignment state. It also has the feature.
[0008]
The surfactant contained in the polymerizable liquid crystal composition of the present invention is not distinguished between an ionic surfactant and a nonionic surfactant, but components other than the surfactant contained in the polymerizable liquid crystal composition. Must be compatible with each other. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, silicone derivatives and the like. More specifically, “MEGAFAC F-110”, “MEGAFAC F-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F” -150 "," MEGAFAC F-171 "," MEGAFAC F-173 "," MEGAFAC F-177 "," MEGAFAC F-183 "," MEGAFAC F-195 "," MEGAFAC F-824 "," MEGAFAC F- 833 "(manufactured by Dainippon Ink and Chemicals, Inc.)," L-77 "," L-720 "," L-722 "," L-7001 "," L-7002 "," L-7602 " , “L-7604”, “L-7605”, “L-7607N”, “Y-7006”, “F -2104 "," FZ-2110 "," FZ-2120 "," FZ-2161 "," FZ-2162 "," FZ-2163 "," FZ-2164 "," FZ-2165 "," FZ-2166 ""," FZ-2171 "(Nippon Unicar Co., Ltd.) and the like.
[0009]
The preferred addition amount of the surfactant in the polymerizable liquid crystal composition of the present invention varies depending on components other than the surfactant contained in the polymerizable liquid crystal composition, the use temperature, etc., but in the polymerizable liquid crystal composition Is preferably in the range of 0.01 to 10% by weight, and particularly preferably in the range of 0.03 to 5% by weight. When the content is lower than 0.01% by weight, it is difficult to obtain the intended effect, and when it is higher than 10% by weight, the liquid crystal properties of the polymerizable liquid crystal composition are remarkably impaired.
[0010]
The acrylate or methacrylate compound (hereinafter referred to as the polymerizable compound according to the present invention) contained in the polymerizable liquid crystal composition of the present invention is represented by the general formula (I) in detail.
[0011]
[Formula 4]
(In the formula, X represents a hydrogen atom or a methyl group, and the 6-membered rings A, B and C are each independently,
[0013]
[Chemical formula 5]
N represents an integer of 0 or 1, m represents an integer of 1 to 4, Y 1 and Y 2 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C—, —CH═CH—, —CF═CF—, — (CH 2 ) 4 —, —CH 2 CH 2 CH 2 O—, — OCH 2 CH 2 CH 2 —, —CH 2 ═CHCH 2 CH 2 — or —CH 2 CH 2 CH═CH—, Y 3 represents a single bond, —COO—, —OCO—, and R represents a hydrogen atom. , A halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group or an alkenyloxy group. ).
[0015]
In the above general formula (I), the 6-membered rings A, B and C are each independently
[Chemical 6]
M represents an integer of 1 or 2, Y 1 and Y 2 each independently represent a single bond or —C≡C—, R represents a halogen atom, a cyano group, or a carbon atom number of 1 to 20 It preferably represents an alkyl group, an alkoxyl group or an alkenyl group.
[0018]
Although the example of the typical thing of the polymeric compound concerning this invention and its phase transition temperature are shown, the polymeric compound which can be used by this invention is not limited to these compounds.
[0019]
[Chemical 7]
[Chemical 8]
[Chemical 9]
(In the above, the cyclohexane ring represents a transcyclohexane ring, and C in the phase transition temperature scheme represents a crystalline phase, N represents a nematic phase, S represents a smectic phase, I represents an isotropic liquid phase, and the number represents the phase transition temperature. Represents.)
The polymerizable compound according to the present invention may be used alone or as a mixture of two or more compounds.
[0023]
Moreover, you may add the liquid crystal compound which does not have a polymerizable functional group to the polymeric liquid crystal composition of this invention in the range in which the total amount in a polymeric liquid crystal composition does not exceed 10 weight%. As a liquid crystal compound having no polymerizable functional group, a nematic liquid crystal compound, a smectic liquid crystal compound, a cholesteric liquid crystal compound and the like can be used without particular limitation as long as they are normally recognized as liquid crystals in this technical field. As the addition amount increases, the mechanical strength of the optical anisotropic body obtained by photopolymerization of the polymerizable liquid crystal composition tends to decrease, so the addition amount needs to be appropriately adjusted.
[0024]
A polymerizable compound that does not exhibit liquid crystallinity can also be added. Such a compound is not particularly limited as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field, but an acrylate compound is particularly preferable.
[0025]
These liquid crystal compounds or polymerizable compounds may be appropriately selected and combined and added, but the addition amount of each component may be adjusted so that at least the liquid crystal properties of the obtained polymerizable liquid crystal composition are not lost. is necessary.
[0026]
Moreover, you may add a photoinitiator and a sensitizer to the polymeric liquid crystal composition of this invention for the purpose of improving the polymerization reactivity. Here, examples of the photopolymerization initiator that can be used include known benzoin ethers, benzophenones, acetophenones, and benzyl ketals. The addition amount is preferably in the range of 10% by weight or less, particularly preferably 5% by weight or less, in the polymerizable liquid crystal composition.
[0027]
In addition, a stabilizer may be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used here include known hydroquinones, hydroquinone monoalkyl ethers, and tert-butylcatechol. The added amount of the stabilizer is preferably in the range of 0.05% by weight or less based on the total amount in the polymerizable liquid crystal composition.
[0028]
In addition, a dichroic dye may be added to the polymerizable liquid crystal composition of the present invention in order to impart dichroism to the optical anisotropic body. Dichroic dyes that can be used include azo, azoxy, anthraquinone, and perylene, and these dyes can be used alone or in combination. Examples of such dichroic dyes include “LSY-116”, “LSR-401”, “LSR-406”, “LSR-426”, “LSB-278”, “LSB-350” (above, Manufactured by Mitsubishi Chemical Corporation), “SI-209”, “M-710”, “M-361”, “M-86”, “M-618”, “SI-252”, “M-777”, “ “M-370”, “M-137”, “M-141”, “M-438”, “M-412”, “M-34”, “M-430”, “M-406”, “S-” 301 "," S-304 "," M-676 "(Mitsui Toatsu Co., Ltd.). The amount of addition of these dichroic dyes depends on the use of the optical anisotropic body to be produced, but is adjusted so that the total amount in the polymerizable liquid crystal composition is in the range of 0.1 to 10% by weight. Is preferable, and the range of 0.2 to 2% by weight is particularly preferable.
[0029]
Furthermore, an optically active compound is added to the polymerizable liquid crystal composition of the present invention for the purpose of introducing a helical structure of a liquid crystal molecular skeleton into an optical anisotropic body produced by photopolymerizing the polymerizable liquid crystal composition. May be. The optically active compound that can be used here does not need to exhibit liquid crystal properties per se, and may or may not have a polymerizable functional group. Further, the direction of the twist can be appropriately selected depending on the purpose of use. Examples of such an optically active compound include cholesterol pelargonate having a cholesteryl group as an optically active group, cholesterol stearate, and “CB-15” and “C-15” having a 2-methylbutyl group as an optically active group (above) BDH), “S1082” (manufactured by Merck), “CM-19”, “CM-20”, “CM” (manufactured by Chisso), “S- having 1-methylheptyl group as an optically active group” 811 "(manufactured by Merck)," CM-21 ", and" CM-22 "(manufactured by Chisso). The amount of the optically active compound added is preferably adjusted as appropriate depending on the use of the optically anisotropic body to be produced.
[0030]
Next, the manufacturing method of the optical anisotropic body obtained by superposition | polymerization of the said polymeric liquid crystal composition is demonstrated still in detail. The production method of the present invention comprises:
(1) First step of applying an alignment treatment to the substrate (2) Second step of applying a polymerizable liquid crystal composition to the surface of the substrate subjected to the alignment treatment (3) Polymerizing the polymerizable liquid crystal composition It has the 3rd process of forming an optical anisotropic body.
[0031]
The alignment of the polymerizable liquid crystal composition in a certain direction is, for example, a substrate on which the polymerizable liquid crystal composition is applied, such as a substrate surface that is rubbed with a cloth or the like, or SiO 2 is obliquely deposited on the substrate surface. This can be achieved if something is used. Moreover, when not using the board | substrate which performed such an orientation process, the method of utilizing an electric field or a magnetic field can be mentioned. These orientation means may be used alone or in combination. Among them, the method using a substrate whose substrate surface is rubbed with a cloth or the like is particularly preferable because of its simplicity.
[0032]
The substrate which can be used at this time can be used regardless of an organic material or an inorganic material. Specific examples of the organic material include polyethylene terephthalate, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, Examples of cellulose, polyetheretherketone, and inorganic materials include silicon and glass. When a polarizing film is used as a substrate, an optical anisotropic body can be directly formed on the polarizing film. The optical anisotropic body thus obtained is suitable as an elliptically polarizing film as a component of a liquid crystal display. Can be used.
[0033]
When appropriate orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. May be. Further, it is particularly preferable to positively use a polyimide thin film that gives a pretilt angle as used in a normal TN or STN cell because the internal structure of the optical anisotropic body can be controlled more precisely. When the orientation state is controlled by an electric field, a substrate having an electrode layer can be used. In this case, it is preferable to form an organic thin film such as the aforementioned polyimide thin film on the electrode. In the polymerizable liquid crystal composition of the present invention, depending on the surfactant contained, some liquid crystal molecules may be aligned. Therefore, when such a liquid crystal material is used, the substrate may not be subjected to an alignment treatment. Good.
[0034]
As a polymerization method, since rapid progress of polymerization is desirable, a method of photopolymerization by irradiating the substrate with energy rays such as ultraviolet rays or electron beams is preferable. The energy rays may be irradiated from either the substrate surface coated with the polymerizable liquid crystal composition of the present invention or the substrate surface not coated. However, when the substrate surface not coated is irradiated, the substrate used is transparent. Must have. The temperature during polymerization must be such that the liquid crystal state of the polymerizable liquid crystal composition used in the present invention is maintained, but is preferably as close to room temperature as possible to avoid thermal polymerization.
[0035]
Moreover, the optical anisotropic body produced by such a method of the present invention may be used after being peeled from the substrate, or may be used while being carried on the substrate without being peeled off.
[0036]
【Example】
Hereinafter, the present invention will be described in further detail with reference to examples. However, the present invention is not limited to these examples.
Reference Example 1 Formula (a)
[0037]
[Chemical Formula 10]
50 parts by weight of the compound of formula (d)
[0039]
Embedded image
50 parts by weight of the above compound and 1.5 parts by weight of photopolymerization initiator “IRG-651” (manufactured by Ciba Geigy) and nonionic surfactant “MEGAFAC F-177” (manufactured by Dainippon Ink & Chemicals, Inc.) A polymerizable liquid crystal composition (A) consisting of 5 parts by weight was prepared. The obtained composition showed a nematic phase at room temperature, and the phase transition temperature from the nematic phase to the isotropic liquid phase was 42 ° C. Further, n e at 25 ° C. (extraordinary index) is 1.64, n o (ordinary refractive index) was 1.52.
[0041]
Next, the polymerizable liquid crystal composition (A) was applied on a glass substrate using a spin coater so that the film thickness was 10 microns. When the glass substrate coated with the polymerizable liquid crystal composition (A) was observed between two polarizing films, the polymerizable liquid crystal composition (A) was uniformly homeotropically aligned and the film thickness was uneven. There was not.
[0042]
Next, the glass substrate coated with the polymerizable liquid crystal composition (A) was irradiated with ultraviolet rays having a light amount of 160 mJ / cm 2 at room temperature using an ultraviolet lamp (UVGL-25, manufactured by UVP) under a nitrogen stream, The polymerizable liquid crystal composition was photopolymerized to produce an optical anisotropic body. In the obtained optical anisotropic body, uniform homeotropic alignment was fixed, and there was no film thickness unevenness. It was also excellent in heat resistance.
Reference Comparative Example 1 An optical anisotropic body was prepared in the same manner as in Reference Example 1 except that the nonionic surfactant “MEGAFAC F-177” was not added in Reference Example 1 . The obtained optical anisotropic body was uniform in the orientation direction, but uneven film thickness was observed.
(Example 1) 50 parts by weight of the compound of the formula (a), 50 parts by weight of the compound of the formula (d), 1.5 parts by weight of a photopolymerization initiator “IRG-651” (manufactured by Ciba Geigy) and nonionic surface activity A polymerizable liquid crystal composition (B) comprising 0.5 part by weight of a polyoxyethylene sorbitan monolaurate (trade name Tween # 20) was prepared. The obtained composition showed a nematic phase at room temperature, and the phase transition temperature from the nematic phase to the isotropic liquid phase was 41 ° C. Further, ne (abnormal light refractive index) at 25 ° C. was 1.64, and no (normal light refractive index) was 1.52.
[0043]
Next, the polymerizable liquid crystal composition (B) was applied on a glass substrate having a polyimide alignment film which was rubbed using a spin coater so as to have a film thickness of 10 microns. When the glass substrate coated with the polymerizable liquid crystal composition (B) was observed between two polarizing films, the polymerizable liquid crystal composition was uniformly homogeneously aligned and there was no film thickness unevenness.
[0044]
Next, the glass substrate coated with the polymerizable liquid crystal composition (B) was irradiated with ultraviolet rays having a light amount of 160 mJ / cm 2 at room temperature using an ultraviolet lamp (UVGL-25, manufactured by UVP) under a nitrogen stream, The polymerizable liquid crystal composition was photopolymerized to produce an optical anisotropic body. In the obtained optical anisotropic body, uniform homogeneous orientation was fixed, and there was no film thickness unevenness. It was also excellent in heat resistance.
Comparative Example 1 An optical anisotropic body was prepared in the same manner as in Example 1 except that the nonionic surfactant “Tween # 20” was not added in Example 1 . The obtained optical anisotropic body was uniform in the orientation direction, but uneven film thickness was observed.
Reference Example 2 50 parts by weight of the compound of the formula (a), 50 parts by weight of the compound of the formula (d), 1.5 parts by weight of a photopolymerization initiator “IRG-651” (manufactured by Ciba Geigy) and a right-handed spiral Polymer comprising 0.49 parts by weight of the chiral compound “R-811” (manufactured by Merck & Co., Inc.) and 0.5 parts by weight of the nonionic surfactant “Tween # 20” with a helical pitch of 16.1 microns. Liquid crystal composition (C) was obtained.
[0045]
This polymerizable liquid crystal composition (C) was applied on a polycarbonate substrate subjected to rubbing treatment using a spin coater so as to have a film thickness of 10 microns. When the polycarbonate substrate coated with this polymerizable liquid crystal composition was observed between two polarizing films, the polymerizable liquid crystal composition had a right-handed spiral orientation of 230 degrees and no film thickness unevenness. .
[0046]
Next, the polycarbonate substrate coated with the polymerizable liquid crystal composition (C) was irradiated with ultraviolet rays having a light amount of 160 mJ / cm 2 at room temperature using an ultraviolet lamp (UVGL-25, manufactured by UVP) under a nitrogen stream. The polymerizable liquid crystal composition was photopolymerized to prepare an optical anisotropic body. In the obtained optical anisotropic body, a uniform 230 ° right-handed helical orientation was fixed, and the film thickness was not uneven.
Reference Comparative Example 2 An optical anisotropic body was prepared in the same manner as in Reference Example 2 except that the nonionic surfactant “Tween # 20” was not added in Reference Example 2 . The obtained optical anisotropic body was observed to have film thickness unevenness and pinhole-like defects.
[0047]
【The invention's effect】
Since the polymerizable liquid crystal composition of the present invention has good leveling properties when applied on a substrate, it is possible to reduce the film thickness unevenness of the optical anisotropic body obtained by photopolymerization after application.
[0048]
Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to produce an optical anisotropic body that is low in cost and has no film thickness unevenness, and is a material for optical compensators for liquid crystal display elements and optical elements such as polarizing prisms. As very useful.
Claims (6)
（１）基板に配向処理を施す第１工程
（２）前記基板の配向処理を施した面に、重合性液晶組成物を塗布する第２工程
（３）前記重合性液晶組成物を重合させて光学異方体を形成する第３工程を有することを特徴とする製造方法。In the manufacturing method of the homogeneous alignment optical anisotropic body using the polymerizable liquid crystal composition according to claim 1, 2, or 3,
(1) First step of applying an alignment treatment to the substrate (2) Second step of applying a polymerizable liquid crystal composition to the surface of the substrate subjected to the alignment treatment (3) Polymerizing the polymerizable liquid crystal composition A manufacturing method comprising a third step of forming an optical anisotropic body.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03820095A JP3783787B2 (en) | 1995-02-27 | 1995-02-27 | Polymerizable liquid crystal composition and method for producing optical anisotropic body |
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| JP03820095A JP3783787B2 (en) | 1995-02-27 | 1995-02-27 | Polymerizable liquid crystal composition and method for producing optical anisotropic body |
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| JP2005015433A Division JP3783871B2 (en) | 2005-01-24 | 2005-01-24 | Polymerizable liquid crystal composition and method for producing optical anisotropic body |
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| JPH08231958A JPH08231958A (en) | 1996-09-10 |
| JP3783787B2 true JP3783787B2 (en) | 2006-06-07 |
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1995
- 1995-02-27 JP JP03820095A patent/JP3783787B2/en not_active Expired - Lifetime
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