JP3734041B2 - Polymerizable liquid crystal composition - Google Patents
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- JP3734041B2 JP3734041B2 JP22825094A JP22825094A JP3734041B2 JP 3734041 B2 JP3734041 B2 JP 3734041B2 JP 22825094 A JP22825094 A JP 22825094A JP 22825094 A JP22825094 A JP 22825094A JP 3734041 B2 JP3734041 B2 JP 3734041B2
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Description
【０００１】
【産業上の利用分野】
本発明は、光学、表示、記録材料等として利用される重合性液晶組成物に関する。
【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。
【０００３】
しかしながら、該発明の光学異方体は、内部の分子の配向構造の均一性や耐熱性には問題ないものの、屈折率の異方性の大きな重合性液晶組成物を用いて光学異方体を製造した際に、得られた光学異方体は、透明ではなく黄色に薄く着色してしまうという問題を有していた。
【０００４】
【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、屈折率の異方性の大きな重合性液晶組成物の光重合による光学異方体製造の際に、得られた光学異方体において、黄色の着色が低減・解消されるような重合性液晶組成物を提供することにある。
【０００５】
【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手段について鋭意検討した結果、かかる課題が重合性液晶組成物の構成成分として、特定の重合性化合物を含有することによって解決できることを見いだし本発明を提供するに到った。
【０００６】
即ち、本発明は、２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物を含有し、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。
【０００７】
即ち、本発明は屈折率の異方性が大きく、化学的に安定な２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物を重合性液晶組成物の構成成分として含有することにより、光重合によって得られる光学異方体の着色の低減・解消を図ったものである。
【０００８】
本発明の重合性液晶組成物で用いることができる２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物としては一般式（ＩＩＩ）
【０００９】
【化９】
（式中、Ｒ11は水素原子又はメチル基を表わし、ｔは０又は１を表わし、ｔが０のときｓは０〜１２の整数を表わし、ｔが１のときｓは１〜１２の整数を表わし、Ｒ12は炭素原子数１〜１２のアルキル基又はアルコキシ基を表わし、Ｙ6は−ＣＨ2ＣＨ2−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＣＨ2−又は−ＣＨ2ＣＯ−を表わし、環ｆ及び環ｇのうち一方は、
【００１１】
【化１０】
を表わし、他方は、
【００１３】
【化１１】
を表わす。）で表わされる化合物を挙げることができ、一般式（ＩＩＩ）で表わされる化合物において、Ｙ6は−ＯＣＯ−である化合物が好ましい。
本発明に係わる２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物の重合性液晶組成物中における好ましい含有量は、重合性液晶組成物の屈折率の異方性の大きさによって適宜調整されるが、５重量％以上が好ましい。
【００１５】
また、本発明は、一般式（Ｉ）
【００１６】
【化１２】
（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、
【００１８】
【化１３】
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。）で表わされる第１の単官能アクリレート化合物又は第１の単官能メタクリレート化合物及び前述の２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物含有することを特徴とする重合性液晶組成物を提供する。上記一般式（Ｉ）において、その中でも特に、６員環Ａ、Ｂ及びＣはそれぞれ独立的に、
【００２０】
【化１４】
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、Ｙ3はハロゲン原子、シアノ基、炭素原子数１〜２０のアルキル基又はアルコキシ基を表わす化合物が好ましい。
【００２２】
このような化合物の代表的なものの例と、その相転移温度を以下に示すが、本発明で使用することができる第１の単官能アクリレート又は第１の単官能メタクリレート化合物は、これらの化合物に限定されるものではない。
【００２３】
【化１５】
【化１６】
（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。）
また、これとは別に、本発明は、一般式（ＩＩ）
【００２６】
【化１７】
（式中、Ｒ1は水素原子又はメチル基を表わし、ｐは２〜１２の整数を表わし、ｑは０又は１を表わし、Ｙ4は単結合、−ＣＯＯ−又は−ＯＣＯ−を表わし、環Ｄ及びＥはそれぞれ独立的に、
【００２８】
【化１８】
を表わし、ｌは１から４の整数を表わし、ｋは０又は１を表わし、Ｒ2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、アルケニル基又はフェニル基を表わす。）で表わされる第２の単官能アクリレート化合物又は第２の単官能メタクリレート化合物及び、前述の２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物を含有し、室温でエナンチオトロピックなネマチック液晶相を示すことを特徴とする重合性液晶組成物をも提供する。
【００３０】
この一般式（ＩＩ）で表わされる化合物としては、例えば、
【００３１】
【化１９】
（式中、Ｒ3、Ｒ4及びＲ5はそれぞれ独立的に、水素原子又はメチル基を表わし、ｈ、ｉ及びｊはそれぞれ独立的に２〜１２の整数を表わし、Ｒ6はシアノ基、炭素原子数１〜６のアルキル基、アルコキシ基又はフェニル基を表わす）で表わされる化合物、あるいは、
【００３３】
【化２０】
（式中、Ｒ7及びＲ8はそれぞれ独立的に水素原子又はメチル基を表わし、Ｒ9及びＲ10はそれぞれ独立的に炭素原子数１〜６のアルキル基を表わす）で表わされる化合物を挙げることができる。
【００３５】
本発明の重合性液晶組成物において、２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物と併用できる化合物として、上記したような第１の単官能（メタ）アクリレート化合物、第２の単官能（メタ）アクリレート化合物が好ましい。また、第１の単官能（メタ）アクリレート化合物及び第２の単官能（メタ）アクリレートを共に含有するものであってもよく、第１及び第２の単官能（メタ）アクリレートを併用する場合は、第２の単官能（メタ）アクリレートの含有量は、第１の単官能（メタ）アクリレートに対して５０重量％以下であることが好ましい。これは第２の単官能（メタ）アクリレートの含有量が増えるに従って、得られる光学異方体の機械的強度及び耐熱性が劣る傾向があるからである。
【００３６】
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、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。しかしながら、その添加量が増えるに従い、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。
【００３７】
また、重合性官能基を有しているが、液晶性を示さない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。
【００３８】
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。
【００３９】
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、重合性液晶組成物に対して１０重量％以下が好ましく、５重量％以下が特に好ましい。
【００４０】
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０．０５重量％以下が好ましい。
【００４１】
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ねじれネマチック配向、又はコレステリック配向等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好ましい添加量は、製造される光学異方体の用途による。カイラルネマチック配向又はコレステリック配向の螺旋構造を導入し、例えば液晶表示素子の視角補償板として用いる場合には、コレステリック構造に由来する選択反射光の波長が可視光領域からはずれるように、螺旋構造のピッチ（Ｐ）を０．２５ミクロン以下もしくは０．５ミクロン以上になるように調整するのが好ましく、例えば特定波長の反射板として用いる場合には、選択反射光の波長が可視光領域にあるように螺旋構造のピッチ（Ｐ）を０．２５〜０．５ミクロンになるように調整するのが好ましい。また、特にスーパー・ツイステッド・ネマチック（ＳＴＮ）型液晶表示素子やツイステッド・ネマチック型液晶表示素子の光学補償に用いる場合には、得られる光学異方体の厚み（ｄ）を光学異方体中での螺旋ピッチ（Ｐ）で除した値（ｄ／Ｐ）が０．２５〜０．７５の範囲になるように添加量を調整することが特に好ましい。
【００４２】
また、本発明の重合性液晶組成物を用いた偏光板等の光学素子の作製を目的として、本発明の重合性液晶組成物に染料、顔料、色素等を添加することもできる。
【００４３】
以上のような本発明の重合性液晶組成物は、光学異方体を製造する際に、液晶状態での光重合において意図しない熱重合の誘起を避け、均一な配向状態の固定を可能にするために、室温において液晶相を示すように、特に室温においてエナンチオトロピックなネマチック相を示すように、各成分の添加量を調整するのが好ましい。
【００４４】
【実施例】
以下、本発明の実施例を示し、本発明を更に具体的に説明する。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。
（実施例１）
式（ａ）
【００４５】
【化２１】
の化合物５０重量部及び
式（ｃ）
【００４７】
【化２２】
の化合物５０重量部からなる重合性液晶組成物（Ａ）を調製した。得られた重合性液晶組成物（Ａ）は室温でネマチック液晶相を示し、２５℃における屈折率の異方性は０．０７５であった。この重合性液晶組成物（Ａ）８５重量部及び、式（ＩＸ）
【００４９】
【化２３】
の化合物１５重量部からなる重合性液晶組成物（Ｂ）を調製した。得られた重合性液晶組成物（Ｂ）は室温でネマチック液晶相を示し、２５℃における屈折率の異方性は０．０９０であり、式（ＩＸ）の化合物の添加により、屈折率の異方性の増大が認められた。
（応用例１）
実施例１で得られた重合性液晶組成物（Ｂ）９９重量部及び、光重合開始剤「ＩＲＧ−６５１」（チバガイギー社製）１重量部からなる重合性液晶組成物（Ｃ）を調製した。次に、ポリイミド配向膜を形成し、ラビング処理した２枚のガラス基板を、ポリイミド配向膜の面が内側になるように１０ミクロンの間隔をもって対向させ、この間に重合性液晶組成物（Ｃ）を挟持させた。この時の２枚のガラス基板のラビング方向は互いに左向きに８５度の角度をなすようにした。この２枚のガラス基板に挟持された重合性液晶組成物（Ｃ）を、透過軸が直交するように配置した２枚の偏光板の間において観察したところ、均一なツイステッドネマチック配向していることが確認できた。この重合性液晶組成物（Ｃ）にＵＶ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光重合を行い、２枚のガラス基板に挟持された光学異方体を得た。これを１５０℃に１０分間保った後、室温において冷却した。室温まで冷却後、光学異方体から、１枚のガラス基板を剥離して、１枚のガラス基板に担持された光学異方体を得た。この光学異方体を、２枚の偏光板の間に置いて観察したところ、光重合前の均一なツイステッドネマチック配向が光重合によって固定化されていることが確認できた。この光学異方体は１２０℃の温度に保っても、耐熱性には何ら問題はなく、また黄色の着色も観察されなかった。
（実施例２）
式（ａ）
【００５１】
【化２４】
の化合物５０重量部及び
式（ｌ）
【００５３】
【化２５】
の化合物２５重量部及び式（ｍ）
【００５５】
【化２６】
の化合物２５重量部からなる重合性液晶組成物（Ｄ）を調製した。得られた重合性液晶組成物（Ｄ）は室温でネマチック液晶相を示し、２５℃における屈折率の異方性は０．１１０であった。この重合性液晶組成物（Ｄ）６０重量部及び、式（ＩＸ）
【００５７】
【化２７】
の化合物４０重量部からなる重合性液晶組成物（Ｅ）を調製した。得られた重合性液晶組成物（Ｅ）は室温でネマチック液晶相を示し、２５℃における屈折率の異方性は０．１３５であり、式（ＩＸ）の化合物の添加により、屈折率の異方性の増大が認められた。
（応用例２）
実施例２で得られた重合性液晶組成物（Ｂ）９９重量部及び、光重合開始剤「ＩＲＧ−６５１」（チバガイギー社製）１重量部からなる重合性液晶組成物（Ｆ）を調製した。応用例１において、重合性液晶組成物（Ｃ）に代えて、上記で得られた重合性液晶組成物（Ｆ）を用いた以外は応用例１と同様にして光学異方体を作製した。この光学異方体を、２枚の偏光板の間に置いて観察したところ、光重合前の均一なツイステッドネマチック配向が光重合によって固定化されていることが確認できた。この光学異方体は１２０℃の温度に保っても、耐熱性には何ら問題はなく、また黄色の着色も観察されなかった。
【００５９】
【発明の効果】
本発明の重合性液晶組成物は、化学的に安定な２，６−置換ナフタレン骨格を有する単官能アクリレート化合物又は単官能メタクリレート化合物を含有しているので、重合性液晶組成物の屈折率の異方性を大きくすることが可能であり、また重合して得られる光学異方体の黄色の着色も低減・解消できる。従って、透明性に優れ、かつ複屈折率の大きな光学異方体を製造することが可能である。[0001]
[Industrial application fields]
The present invention relates to a polymerizable liquid crystal composition used as an optical, display, recording material or the like.
[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.
[0003]
However, although the optical anisotropic body of the present invention has no problem with the uniformity of the alignment structure of the internal molecules and the heat resistance, the optical anisotropic body is formed using a polymerizable liquid crystal composition having a large refractive index anisotropy. When manufactured, the obtained optical anisotropic body had a problem that it was not transparent but colored pale yellow.
[0004]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to reduce yellow coloring in the obtained optical anisotropic body during the production of the optical anisotropic body by photopolymerization of a polymerizable liquid crystal composition having a large refractive index anisotropy. It is to provide a polymerizable liquid crystal composition that can be eliminated.
[0005]
[Means for Solving the Problems]
As a result of intensive studies on means for solving the above problems, the present inventors have found that such problems can be solved by containing a specific polymerizable compound as a constituent component of the polymerizable liquid crystal composition, and provide the present invention. Arrived.
[0006]
That is, the present invention provides a polymerizable liquid crystal composition containing a monofunctional acrylate compound or monofunctional methacrylate compound having a 2,6-substituted naphthalene skeleton and exhibiting a liquid crystal phase.
[0007]
That is, the present invention contains a monofunctional acrylate compound or a monofunctional methacrylate compound having a chemically stable 2,6-substituted naphthalene skeleton having a large refractive index anisotropy as a constituent component of the polymerizable liquid crystal composition. Thus, the coloring of the optical anisotropic body obtained by photopolymerization is reduced or eliminated.
[0008]
The monofunctional acrylate compound or monofunctional methacrylate compound having a 2,6-substituted naphthalene skeleton that can be used in the polymerizable liquid crystal composition of the present invention is represented by the general formula (III).
[0009]
[Chemical 9]
(Wherein R 11 represents a hydrogen atom or a methyl group, t represents 0 or 1, s represents an integer of 0 to 12 when t is 0, and s represents an integer of 1 to 12 when t is 1) R 12 represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and Y 6 represents —CH 2 CH 2 —, —COO—, —OCO—, —COCH 2 — or —CH 2 CO—. One of ring f and ring g is
[0011]
[Chemical Formula 10]
And the other is
[0013]
Embedded image
Represents. In the compound represented by the general formula (III), a compound in which Y 6 is —OCO— is preferable.
The preferred content in the polymerizable liquid crystal composition of the monofunctional acrylate compound or monofunctional methacrylate compound having a 2,6-substituted naphthalene skeleton according to the present invention is the magnitude of the refractive index anisotropy of the polymerizable liquid crystal composition. The amount is appropriately adjusted depending on the amount, but is preferably 5% by weight or more.
[0015]
The present invention also relates to a compound of the general formula (I)
[0016]
Embedded image
(In the formula, X represents a hydrogen atom or a methyl group, and the 6-membered rings A, B and C are each independently,
[0018]
Embedded image
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— represents Y 3 is a hydrogen atom, a halogen atom, a cyano group, or an alkyl having 1 to 20 carbon atoms. Represents a group, an alkoxy group, an alkenyl group or an alkenyloxy group. 1) a monofunctional acrylate compound or a monofunctional methacrylate compound having the first monofunctional acrylate compound or the first monofunctional methacrylate compound represented by formula (1) and the aforementioned 2,6-substituted naphthalene skeleton. A composition is provided. In the above general formula (I), in particular, the 6-membered rings A, B and C are each independently
[0020]
Embedded image
M represents an integer of 1 or 2, Y 1 and Y 2 each independently represents a single bond or —C≡C—, and Y 3 represents a halogen atom, a cyano group, or a carbon atom number of 1 to 20. A compound representing an alkyl group or an alkoxy group is preferred.
[0022]
Examples of typical examples of such compounds and their phase transition temperatures are shown below. The first monofunctional acrylate or the first monofunctional methacrylate compound that can be used in the present invention is included in these compounds. It is not limited.
[0023]
Embedded image
Embedded image
(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.)
Apart from this, the present invention provides a compound of the general formula (II)
[0026]
Embedded image
(In the formula, R 1 represents a hydrogen atom or a methyl group, p represents an integer of 2 to 12, q represents 0 or 1, Y 4 represents a single bond, —COO— or —OCO—, D and E are each independently
[0028]
Embedded image
1 represents an integer of 1 to 4, k represents 0 or 1, R 2 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 phenyl. Represents a group. And a monofunctional acrylate compound or a monofunctional methacrylate compound having a 2,6-substituted naphthalene skeleton, which is enantiotropic at room temperature. Also provided is a polymerizable liquid crystal composition characterized by exhibiting a nematic liquid crystal phase.
[0030]
As the compound represented by the general formula (II), for example,
[0031]
Embedded image
(Wherein R 3 , R 4 and R 5 each independently represents a hydrogen atom or a methyl group, h, i and j each independently represents an integer of 2 to 12, R 6 represents a cyano group, A compound represented by an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a phenyl group, or
[0033]
Embedded image
(Wherein R 7 and R 8 each independently represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represents an alkyl group having 1 to 6 carbon atoms). be able to.
[0035]
In the polymerizable liquid crystal composition of the present invention, as the compound that can be used in combination with the monofunctional acrylate compound or monofunctional methacrylate compound having a 2,6-substituted naphthalene skeleton, the first monofunctional (meth) acrylate compound as described above, Two monofunctional (meth) acrylate compounds are preferred. Further, it may contain both the first monofunctional (meth) acrylate compound and the second monofunctional (meth) acrylate, and when the first and second monofunctional (meth) acrylates are used in combination. The content of the second monofunctional (meth) acrylate is preferably 50% by weight or less with respect to the first monofunctional (meth) acrylate. This is because the mechanical strength and heat resistance of the obtained optical anisotropic body tend to be inferior as the content of the second monofunctional (meth) acrylate increases.
[0036]
Moreover, you may add to the polymeric liquid crystal composition of this invention the liquid crystal compound which does not have a polymerizable functional group in the range whose total amount in a polymeric liquid crystal composition does not exceed 10 weight%. As the liquid crystal compound having no polymerizable functional group, a nematic liquid crystal compound, a smectic liquid crystal compound, a cholesteric liquid crystal compound, or the like can be used without particular limitation as long as it is generally recognized as a liquid crystal in this technical field. However, since the mechanical strength of the obtained optical anisotropic body tends to decrease as the amount added increases, it is necessary to adjust the amount added appropriately.
[0037]
A compound having a polymerizable functional group but not exhibiting 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 preferred.
[0038]
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.
[0039]
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. Examples of the photopolymerization initiator that can be used here include known benzoin ethers, benzophenones, acetophenones, and benzyl ketals. The amount added is preferably 10% by weight or less, particularly preferably 5% by weight or less, based on the polymerizable liquid crystal composition.
[0040]
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 amount of the stabilizer added is preferably 0.05% by weight or less.
[0041]
Furthermore, in the polymerizable liquid crystal composition of the present invention, an optical anisotropic liquid is produced for the purpose of introducing a helical structure such as twisted nematic alignment or cholesteric alignment into an optical anisotropic body produced by photopolymerizing the polymerizable liquid crystal composition. Active compounds may be added. 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 preferable addition amount of this optically active compound depends on the use of the optically anisotropic body to be produced. When a spiral structure of chiral nematic orientation or cholesteric orientation is introduced and used, for example, as a viewing angle compensator for a liquid crystal display device, the pitch of the spiral structure is set so that the wavelength of selectively reflected light derived from the cholesteric structure deviates from the visible light region. (P) is preferably adjusted to be 0.25 microns or less or 0.5 microns or more. For example, when used as a reflector having a specific wavelength, the wavelength of the selectively reflected light is in the visible light region. The pitch (P) of the spiral structure is preferably adjusted to be 0.25 to 0.5 microns. In particular, when used for optical compensation of a super twisted nematic (STN) type liquid crystal display element or a twisted nematic type liquid crystal display element, the thickness (d) of the obtained optical anisotropic body is determined in the optical anisotropic body. It is particularly preferable to adjust the addition amount so that the value (d / P) divided by the helical pitch (P) is in the range of 0.25 to 0.75.
[0042]
In addition, for the purpose of producing an optical element such as a polarizing plate using the polymerizable liquid crystal composition of the present invention, a dye, a pigment, a pigment, or the like can be added to the polymerizable liquid crystal composition of the present invention.
[0043]
The polymerizable liquid crystal composition of the present invention as described above avoids unintentional induction of thermal polymerization in photopolymerization in a liquid crystal state and enables a uniform alignment state to be fixed when producing an optical anisotropic body. Therefore, it is preferable to adjust the addition amount of each component so as to exhibit a liquid crystal phase at room temperature, and in particular, to exhibit an entropy nematic phase at room temperature.
[0044]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Example 1
Formula (a)
[0045]
Embedded image
50 parts by weight of the compound of formula (c)
[0047]
Embedded image
A polymerizable liquid crystal composition (A) comprising 50 parts by weight of the above compound was prepared. The obtained polymerizable liquid crystal composition (A) exhibited a nematic liquid crystal phase at room temperature, and the anisotropy of the refractive index at 25 ° C. was 0.075. 85 parts by weight of this polymerizable liquid crystal composition (A) and formula (IX)
[0049]
Embedded image
A polymerizable liquid crystal composition (B) comprising 15 parts by weight of the above compound was prepared. The resulting polymerizable liquid crystal composition (B) exhibits a nematic liquid crystal phase at room temperature, and the anisotropy of the refractive index at 25 ° C. is 0.090. The addition of the compound of formula (IX) results in a difference in refractive index. An increase in directionality was observed.
(Application 1)
A polymerizable liquid crystal composition (C) comprising 99 parts by weight of the polymerizable liquid crystal composition (B) obtained in Example 1 and 1 part by weight of a photopolymerization initiator “IRG-651” (manufactured by Ciba Geigy) was prepared. . Next, two glass substrates on which a polyimide alignment film was formed and rubbed were opposed to each other with an interval of 10 microns so that the surface of the polyimide alignment film was on the inside, and the polymerizable liquid crystal composition (C) was interposed therebetween. I was pinched. The rubbing directions of the two glass substrates at this time were set to make an angle of 85 degrees to the left. When the polymerizable liquid crystal composition (C) sandwiched between the two glass substrates was observed between two polarizing plates arranged so that the transmission axes were orthogonal, it was confirmed that the twisted nematic alignment was uniform. did it. This polymerizable liquid crystal composition (C) was subjected to photopolymerization by irradiating it with UV light of 160 mJ / cm 2 using a UV lamp (manufactured by UVP, UVGL-25), and was sandwiched between two glass substrates. An optical anisotropic body was obtained. This was kept at 150 ° C. for 10 minutes and then cooled at room temperature. After cooling to room temperature, one glass substrate was peeled from the optical anisotropic body to obtain an optical anisotropic body carried on one glass substrate. When this optical anisotropic body was observed between two polarizing plates, it was confirmed that the uniform twisted nematic orientation before photopolymerization was fixed by photopolymerization. Even when this optical anisotropic body was kept at a temperature of 120 ° C., there was no problem in heat resistance, and yellow coloring was not observed.
(Example 2)
Formula (a)
[0051]
Embedded image
50 parts by weight of the compound of formula (1)
[0053]
Embedded image
25 parts by weight of the compound of formula (m)
[0055]
Embedded image
A polymerizable liquid crystal composition (D) comprising 25 parts by weight of the above compound was prepared. The obtained polymerizable liquid crystal composition (D) exhibited a nematic liquid crystal phase at room temperature, and the anisotropy of the refractive index at 25 ° C. was 0.110. 60 parts by weight of this polymerizable liquid crystal composition (D) and formula (IX)
[0057]
Embedded image
A polymerizable liquid crystal composition (E) comprising 40 parts by weight of the above compound was prepared. The obtained polymerizable liquid crystal composition (E) exhibits a nematic liquid crystal phase at room temperature, and the anisotropy of the refractive index at 25 ° C. is 0.135, and the refractive index varies with the addition of the compound of formula (IX). An increase in directionality was observed.
(Application example 2)
A polymerizable liquid crystal composition (F) comprising 99 parts by weight of the polymerizable liquid crystal composition (B) obtained in Example 2 and 1 part by weight of a photopolymerization initiator “IRG-651” (manufactured by Ciba Geigy) was prepared. . In Application Example 1, an optical anisotropic body was produced in the same manner as Application Example 1 except that the polymerizable liquid crystal composition (F) obtained above was used instead of the polymerizable liquid crystal composition (C). When this optical anisotropic body was observed between two polarizing plates, it was confirmed that the uniform twisted nematic orientation before photopolymerization was fixed by photopolymerization. Even when this optical anisotropic body was kept at a temperature of 120 ° C., there was no problem in heat resistance, and yellow coloring was not observed.
[0059]
【The invention's effect】
Since the polymerizable liquid crystal composition of the present invention contains a monofunctional acrylate compound or monofunctional methacrylate compound having a chemically stable 2,6-substituted naphthalene skeleton, the refractive index of the polymerizable liquid crystal composition is different. It is possible to increase the isotropic property, and it is possible to reduce or eliminate the yellow coloring of the optically anisotropic body obtained by polymerization. Therefore, it is possible to produce an optical anisotropic body having excellent transparency and a large birefringence.
Claims (7)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22825094A JP3734041B2 (en) | 1994-09-22 | 1994-09-22 | Polymerizable liquid crystal composition |
| DE69419120T DE69419120T2 (en) | 1993-12-24 | 1994-12-23 | Polymerizable liquid crystal composition and optically anisotropic film containing such a composition |
| EP94120614A EP0659865B1 (en) | 1993-12-24 | 1994-12-23 | Polymerizable liquid crystal composition and optically anisotropic film comprising the same |
| US08/657,526 US5863457A (en) | 1993-12-24 | 1996-06-04 | Polymerizable liquid crystal composition and optically anisotropic film comprising the same |
| HK98109469A HK1008679A1 (en) | 1993-12-24 | 1998-07-28 | Polymerizable liquid crystal composition and optically anisotropic film comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22825094A JP3734041B2 (en) | 1994-09-22 | 1994-09-22 | Polymerizable liquid crystal composition |
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| Publication Number | Publication Date |
|---|---|
| JPH0892556A JPH0892556A (en) | 1996-04-09 |
| JP3734041B2 true JP3734041B2 (en) | 2006-01-11 |
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| JP22825094A Expired - Lifetime JP3734041B2 (en) | 1993-12-24 | 1994-09-22 | Polymerizable liquid crystal composition |
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| JP4182452B2 (en) * | 1997-11-18 | 2008-11-19 | Ｄｉｃ株式会社 | Liquid crystal composition and optical anisotropic body using the same |
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