JP3834857B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

（式中、Ｒ^１は炭素数１〜１０のアルキル基を示し、Ｑ^１はＨまたはＦを示し、ｍは０または１を示す。）
【化９】

（式中、Ｒ^２、Ｒ^３ およびＲ ^４ は各々独立して炭素数１〜１０のアルキル基または炭素数２〜１０のアルケニル基を示す。いずれにおいても基中の任意の１つまたは相隣接しない２つのメチレン基（−ＣＨ_２−）は酸素原子（−Ｏ−）によって置換されても良い。Ａ^１、Ａ^２、Ａ^３およびＡ^４は各々独立してトランス−１，４−シクロヘキシレンまたは１，４−フェニレンを示し、Ａ^５はトランス−１， ４−シクロヘキシレンまたは側位の１つのＨがＦで置換されても良い１，４−フェニレンを示す。Ｚ^１、Ｚ^２およびＺ^３は各々独立して、−ＣＨ_２ＣＨ_２−または単 結合を示す。Ｚ^４は−ＣＯＯ−、−ＣＨ_２ＣＨ_２−または単結合を示し、Ｑ ^１ はＨまたはＦを示し、ｉは０または１を示す。）
で表される化合物群から選択される化合物を少なくとも１種含有し、
第２成分として一般式（III）、（IV）および（Ｖ）
【化１０】

（式中、Ｒ^６およびＲ^７は各々独立して炭素数１〜１０のアルキル基または炭素数２〜８のアルケニル基を示す。いずれにおいても基中の任意の１つまたは相隣接しない２つ以上のメチレン基（−ＣＨ_２−）は酸素原子によって置換されても良い。Ｂはトランス−１，４−シクロヘキシレン、ピリミジン−２，５−ジイルまたは１，４−フェニレンを示し、Ｃはトランス−１，４−シクロヘキシレンまたは１，４−フェニレンを示し、Ｚ^５は−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または単結合を示す。）
【化１１】

（式中、Ｒ^８は炭素数１〜１０のアルキル基または炭素数２〜１０のアルケニル基を示す。いずれにおいても基中の任意の１つまたは相隣接しない２つ以上のメチレン基（−ＣＨ_２−）は酸素原子（−Ｏ−）によって置換されても良い。Ｒ^９は炭素数１〜１０のアルキル基、アルコキシ基またはアルコキシメチル基を示し、Ｄはトランス−１，４−シクロヘキシレンまたはピリミジン−２，５−ジイルを示し、Ｅはトランス−１，４−シクロヘキシレンまたは側位の１つのＨがＦで置換されても良い１，４−フェニレンを示し、Ｇはトランス−１，４−シクロヘキシレンまたは１，４−フェニレンを示し、Ｚ^６は−ＣＨ_２ＣＨ_２−または単結合を 示し、Ｚ^７は−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＨ＝ＣＨ−または単結合を示す。）
【化１２】

（式中、Ｒ^１０は炭素数１〜１０のアルキル基または炭素数２〜１０のアルケニル基を示す。いずれにおいても基中の任意の１つまたは相隣接しない２つ以上のメチレン基（−ＣＨ_２−）は酸素原子（−Ｏ−）によって置換されても良い。Ｒ^１１は炭素数１〜１０のアルキル基、アルコキシ基またはアルコキシメチル基を示し、Ｑ ^２ はＨまたはＦを示す。）
で表される化合物群から選択される少なくとも１種の化合物を含有し、
第３成分として２５℃におけるＨ．Ｔ．Ｐ．（Herical Twisting power：らせんねじり力）が０．１５（μｍ・ｗｔ％）^−１以上である光学活性化合物であって、下記式（ VI −ａ）、（ VI −ｂ）および（ VI −ｃ）
【化６】

（式中Ｒ ^１２ は炭素数１〜１０のアルキル基またはアルコキシ基を示し、Ｋはトランス−１，４−シクロヘキシレンまたは１，４−フェニレンを示し、Ｙは水素原子または炭素数１〜１０のアルキル基を示す。）で表される光学活性化合物群から選択される化合物を１種以上含有し、且つらせんのピッチが４μｍ以下に調整されていることを特徴とするカイラルネマチック液晶組成物に関する。
【００１２】
本発明の第２の発明は、液晶組成物の全重量に対して第１成分が１０〜６５重量％、第２成分が３５〜９０重量％であること特徴とする上記第１の発明に記載のカイラルネマチック液晶組成物に関する。
【００１３】
本発明の第３の発明は、さらに第４成分として、一般式（VII）
【化１４】

（式中、Ｒ^１３は炭素数１〜１０のアルキル基を示し、Ｊはトランス−１，４−シクロヘキシレンまたは側位の１つまたは２つのＨがＦで置換されていても良い１，４−フェニレンを示し、Ｑ^５はＦまたはＣｌを示し、Ｑ^４およびＱ^６は各々独立してはＨまたはＦを示し、Ｚ^８およびＺ^９は各々独立して−ＣＯＯ−、−Ｃ_２Ｈ_４−または単結合を示し、ｎは０、１または２を示す。）で表される化合物群から選択される化合物を少なくとも１種含有することを特徴とする上記第１および第２の発明のいずれかに記載のカイラルネマチック液晶組成物に関する。
【００１４】
本発明の第４の発明は、液晶組成物の全重量に対して、第４成分の含有量が０〜５０重量％であることを特徴とする上記第１〜第３の発明のいずれかに記載のカイラルネマチック液晶組成物に関する。
【００１５】
本発明の第５の発明は、第１〜４の発明のいずれかにおいて、一般式（II−ａ）、（II−ｂ）および（II−ｃ）におけるＲ ^２ 〜Ｒ ^４ が独立に炭素数１〜１０のアルキル基、アルコキシ基またはアルコキシメチル基を示すことを特徴とするカイラルネマチック液晶組成物に関する。
【００１６】
本発明の第６の発明は、第１〜５の発明のいずれかにおいて、一般式（III）におけるＲ^６およびＲ^７が各々独立して炭素数１〜１０のアルキル基、アルコキシ基またはアルコキシメチル基を示すことを特徴とするカイラルネマチック液晶組成物に関する。
【００１７】
本発明の第７の発明は、第１〜６の発明のいずれかにおいて、一般式（IV）におけるＲ^８が炭素数１〜１０のアルキル基を示し、Ｒ^９が炭素数１〜１０のアルキル基またはアルコキシ基を示すことを特徴とするカイラルネマチック液晶組成物に関する。
【００１８】
本発明の第８の発明は、上記第１〜第７の発明のいずれかに記載のカイラルネマチック液晶組成物を用いた液晶表示素子に関する。
【００１９】
以下、本発明の液晶組成物を構成する液晶化合物について説明する。
本発明の第１成分である、一般式（Ｉ）および／または（II−ａ）〜（II−ｃ）で表される化合物としては、好ましくは以下の化合物を挙げることができる。
【化１５】

【化１６】

（Ｒはアルキル基またはアルケニル基、Ｒ’はアルカンジイルまたはアルケンジイルを示す。）
【００２０】
これらの第１成分の化合物のなかでは、式（Ｉ−１）、（Ｉ−２）、（Ｉ−３）、（II−ａ−１）、（II−ａ−２）、（II−ａ−３）、（II−ｂ−１）、（II−ｃ−１）、（II−ｃ−５）、（II−ｃ−６）、（II−ｃ−１１）または（II−ｃ−１３）で表される化合物が本発明において特に好ましく用いられる。
【００２１】
これら第１成分の化合物は誘電率異方性が正の化合物で特にその値が大きく、主としてしきい値電圧を小さくする目的およびＳＴＮ特性として重要な急峻性を改善する目的で使用される。低電圧駆動を行うためには誘電率異方性の大きいこれらの化合物は不可欠な成分となる。
【００２２】
第２成分の、一般式（III）、（IV）および（Ｖ）で表される化合物として、好ましくは以下の化合物を挙げることができる。
【化１７】

【化１８】

【化１９】

【化２０】

（ＲおよびＲ’は各々独立してアルキル基またはアルケニル基を示す。）
【００２３】
これらの中で、式（III）で表される化合物としては、式（III−１）、（III−４）、（III−６）、（III−７）、（III−８）、（III−１０）、（III−１３）、（III−１４）、（III−１８）または（III−１９）で表される化合物が本発明において特に好ましく用いられる。また、式（IV）で表される化合物としては、式（IV−２）、（IV−５）、（IV−６）、（IV−８）、（IV−１１）、（IV−１２）または（IV−１４）で表される化合物が本発明において特に好ましく用いられる。式（Ｖ）で表される化合物としては（Ｖ−２）で表される化合物が本発明において特に好ましく用いられる。
【００２４】
第２成分の、一般式（III）、（IV）および（Ｖ）の化合物は、誘電率異方性が負かまたは弱い正の化合物である。一般式（III）の化合物は主として粘度低下および／またはΔｎ調整の目的で使用される。また、一般式（IV）の化合物は透明点を高くする等のネマチックレンジを広げる目的および／またはΔｎ調整、粘度調整の目的で使用される。
【００２５】
本発明の第３成分である、Ｈ．Ｔ．Ｐ．が０．１５０（μｍ・ｗｔ％）^-1以上の光学活性化合物の内、式（VI−ａ）、（VI−ｂ）または（VI−ｃ）で表される光学活性化合物として、好ましくは以下の光学活性化合物を挙げることができる。
【化２１】

【化２２】

（式中Ｒ、Ｒ’はそれぞれ炭素数１〜１０のアルキル基を示す。）
【００２６】
これらの化合物の中では、式（VI−ａ−１）、（VI−ａ−７）、（VI−ｂ−２）、（VI−ｂ−３）および（VI−ｃ−３）の化合物が本発明において特に好ましく用いられる。
第３成分である、一般式（VI−ａ）〜（VI−ｃ）の光学活性化合物は、カイラル成分としてらせんのピッチ長を調整するために用いられる。
【００２７】
本発明の第４成分である一般式（VII）で表される化合物として、好ましくは以下の化合物を挙げることができる。
【化２３】

【化２４】

【化２５】

【化２６】

【化２７】

（Ｒはアルキル基を示す。）
【００２８】
一般式（VII）で表される第４成分の化合物としては、式（VII−１）、（VII−５）、（VII−６）、（VII−７）、（VII−８）、（VII−９）、（VII−１０）、（VII−１１）、（VII−１２）、（VII−１５）、（VII−１６）、（VII−１７）、（VII−１８）、（VII−１９）、（VII−２０）、（VII−２２）、（VII−２９）、（VII−３４）、（VII−３５）、（VII−３７）、（VII−４１）、（VII−４５）、（VII−４６）、（VII−４７）または（VII−４８）で表される化合物が好ましく用いられ、さらにこれらの中で、（VII−１）、（VII−５）、（VII−７）、（VII−８）、（VII−９）、（VII−１１）、（VII−１２）、（VII−１５）、（VII−１９）、（VII−２０）または（VII−２９）で表される化合物が本発明において特に好ましく用いられる。
一般式（VII）の化合物は誘電率異方性が正の化合物であり、特にしきい値電圧を小さくする目的やその温度依存性を改善する目的で使用される。また、粘度調整、Δｎ調整、透明点を高くする等のネマチックレンジを広げる目的にも使用される。
【００２９】
本発明で使用される第１成分の混合割合は、液晶組成物の全重量に対して１０〜６５％が好ましい。より好ましくは１５〜６０％である。
第２成分の混合割合は３５〜９０％が好ましい。より好ましくは４０〜８５％である。
第４成分の混合割合は０〜５０％が好ましい。
【００３０】
本発明の液晶組成物は使用される液晶表示素子の目的に応じて、上記一般式（Ｉ）〜（VII）で表される化合物の他、しきい値電圧、ネマティックレンジ、Δｎ、誘電率異方性、粘度等を調整する目的で、他の化合物を本発明の目的を害さない範囲で適当量含有することができる。
【００３１】
本発明の液晶組成物は、それ自体慣用な方法で調整される。一般には、種々の成分を高い温度で互いに溶解させる方法がとられている。また、本発明の液晶材料は、適当な添加物によって意図する用途に応じた改良がなされ、最適化される。このような添加物は当業者によく知られており、文献等に詳細に記載されている。
また、本発明の液晶組成物は、メロシアニン系、スチリル系、アゾ系、アゾメチン系、アゾキシ系、キノフタロン系、アントラキノン系およびテトラジン系等の二色性色素を添加してゲストホスト（ＧＨ）モード用の液晶組成物としても使用できる。あるいは、ネマチック液晶をマイクロカプセル化して作製したＮＣＡＰや液晶中に三次元網目状高分子を作製したポリマーネットワーク液晶表示素子（ＰＮＬＣＤ）に代表されるポリマー分散型液晶表示素子（ＰＮＬＣＤ）用の液晶組成物としても使用できる。その他、複屈折制御（ＥＣＢ）モードや動的散乱（ＤＳ）モード用の液晶組成物としても使用できる。
【００３２】
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また、比較例、実施例に使用した液晶化合物は「表１」に基づいて記号で表し、光学活性化合物は「表２」に示した略号で表し、それらの組成比は液晶成分については全て重量％で示す。ただし、第３成分である光学活性化合物については、光学活性化合物以外の液晶組成物１００重量部に対する重量部で示す。
【表１】

【表２】

【００３３】
尚、透明点（ネマティック−アイソトロピック転移点）をＴ_NI［℃］、スメクティック−ネマティック転移点（またはネマチック相の下限）をＴ_SN［℃］（Ｔ_SNは、０℃、−１０℃、−２０℃、−３０℃の各々のフリーザー中に３０日間放置した後の液晶相で判断した）、２０℃における粘度をη₂₀［ｍＰａ・ｓ］、２５℃におけるらせんピッチ長をＰ₂₅［μｍ］、式▲１▼に基づきＰ₂₅と光学活性化合物の添加量から導かれるらせんねじり力をＨ．Ｔ．Ｐ．［μｍ^-1・ｗｔ％^-1］で示し、らせんピッチ長の温度依存性δＰを示すパラメーターとして、式▲２▼を定義する。
【数１】

ここで、Ｐ₂₀およびＰ₅₀は各々２０℃、５０℃におけるらせんピッチ長［μｍ］を示し、δＰの値は０に近い程好ましい。
【００３４】
比較例１
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ ２４．０％
５−ＨＢ−Ｃ ３６．０％
７−ＨＢ−Ｃ ２５．０％
５−ＨＢＢ−Ｃ １５．０％
８ＯＢＢＥ１＊（Ｅｔ）Ｂ １．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝７０．５［℃］
Ｔ_SN≦−２０［℃］
η₂₀＝３６．４［ｍＰａ・ｓ］
Ｐ₂₅＝３．９［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２５６［μｍ^-1・ｗｔ％^-1］
δＰ＝０．０９
【００３５】
比較例２
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ ２４．０％
５−ＨＢ−Ｃ ３６．０％
７−ＨＢ−Ｃ ２５．０％
５−ＨＢＢ−Ｃ １５．０％
２１＊（Ｍｅ）１ＯＢＢＣ ２０．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝６３．１［℃］
Ｔ_SN≦０［℃］
η₂₀＝４０．２［ｍＰａ・ｓ］
Ｐ₂₅＝３．６［μｍ］
Ｈ．Ｔ．Ｐ．＝０．０１４［μｍ^-1・ｗｔ％^-1］
δＰ＝０．９２
【００３６】
比較例３
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ ２４．０％
５−ＨＢ−Ｃ ３６．０％
７−ＨＢ−Ｃ ２５．０％
５−ＨＢＢ−Ｃ １５．０％
６ＯＢＥＢＥ１＊（Ｍｅ）６ ２．２部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝６９．８［℃］
Ｔ_SN≦−１０［℃］
η₂₀＝４２．５［ｍＰａ・ｓ］
Ｐ₂₅＝３．９［μｍ］
Ｈ．Ｔ．Ｐ．＝０．１１７［μｍ^-1・ｗｔ％^-1］
δＰ＝０．３１
【００３７】
実施例１
次に示す組成の液晶組成物を調製した。
Ｖ２−ＨＢ−Ｃ １３．０％
１Ｖ２−ＨＢ−Ｃ １３．０％
３−ＨＢ−Ｃ ５．０％
１Ｏ１−ＨＨ−３ ２．０％
３−ＨＨ−４ １３．０％
２−ＢＴＢ−１ ７．０％
２−ＢＴＢ−３ ４．０％
２−Ｈ２ＢＴＢ−２ ４．０％
２−Ｈ２ＢＴＢ−３ ４．０％
２−Ｈ２ＢＴＢ−４ ４．０％
３−Ｈ２ＢＴＢ−２ ４．０％
３−Ｈ２ＢＴＢ−３ ４．０％
３−Ｈ２ＢＴＢ−４ ４．０％
３−ＨＢ（Ｆ）ＴＢ−２ ６．０％
２−ＰｙＢ−２ ３．３％
３−ＰｙＢ−２ ３．４％
４−ＰｙＢ−２ ３．３％
２−ＰｙＢＨ−３ ３．０％
８ＯＢＢＥ１＊（Ｍｅ）Ｂ ５．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝７８．９［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２６．８［ｍＰａ・ｓ］
Ｐ₂₅＝１．０［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２００［μｍ^-1・ｗｔ％^-1］
δＰ＝０．２１
上記の液晶組成物は、比較例に較べて、ＴNIが上昇する一方、ＴSNが低下してネマティック液晶範囲が顕著に拡大された。また、粘度も著しく低下し、比較例２、３に較べてδＰも優れている。
【００３８】
実施例２
次に示す組成の液晶組成物を調製した。
Ｖ２−ＨＢ−Ｃ １２．０％
１Ｖ２−ＨＢ−Ｃ １２．０％
３−ＨＢ−Ｃ ８．０％
２−ＨＨＢ−Ｃ ６．０％
３−ＨＨＢ−Ｃ ６．０％
４−ＨＨＢ−Ｃ ６．０％
５−ＨＨＢ−Ｃ ６．０％
３−ＨＢ−Ｏ２ １２．０％
３−ＨＨ−４ １１．０％
３−Ｈ２ＢＴＢ−２ ５．０％
３−Ｈ２ＢＴＢ−３ ４．０％
３−Ｈ２ＢＴＢ−４ ４．０％
３−ＨＢ（Ｆ）ＴＢ−２ ８．０％
６ＢＢＥ１＊（ｔ−Ｂｕ）Ｂ ２．５部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝１０８．８［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝３０．９［ｍＰａ・ｓ］
Ｐ₂₅＝１．２［μｍ］
Ｈ．Ｔ．Ｐ．＝０．３３３［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１８
上記の液晶組成物は、比較例に較べて、ＴNIが上昇する一方、ＴSNが低下してネマティック液晶範囲が顕著に拡大された。また、粘度も著しく低下し、比較例２、３に較べてδＰも優れている。
【００３９】
実施例３
次に示す組成の液晶組成物を調製した。
Ｖ２−ＨＢ−Ｃ １１．０％
１Ｖ２−ＨＢ−Ｃ １１．０％
３−ＨＢ−Ｃ １６．０％
５−ＨＢ−Ｃ ６．０％
１Ｏ１−ＨＢ−Ｃ ４．０％
２−ＨＨＢ−Ｃ ４．０％
３−ＨＨＢ−Ｃ ５．０％
４−ＨＨＢ−Ｃ ３．０％
３−ＨＨ−２Ｖ１ １０．０％
１Ｏ１−ＨＨ−５ ９．０％
２−ＢＴＢ−Ｏ１ １１．０％
３−ＨＢ（Ｆ）ＶＢ−２ ２．０％
３−ＨＢ（Ｆ）ＴＢ−２ ４．０％
３−ＨＢ（Ｆ）ＴＢ−３ ４．０％
６ＢＢＥ１＊（Ｍｅ）Ｂ２ １．５部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝７８．７［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２９．８［ｍＰａ・ｓ］
Ｐ₂₅＝２．９［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２３０［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１７
上記の液晶組成物は、比較例に較べて、ＴNIが上昇する一方、ＴSNが低下してネマティック液晶範囲が顕著に拡大された。また、粘度も著しく低下し、比較例２、３に較べてδＰも優れている。
【００４０】
実施例４
次に示す組成の液晶組成物を調製した。
Ｖ２−ＨＢ−Ｃ １３．０％
１Ｖ２−ＨＢ−Ｃ １３．０％
３−ＨＢ−Ｃ １２．０％
２−ＨＢ−Ｃ １０．０％
３−ＨＨ−４ ３．０％
２−ＢＴＢ−１ １０．０％
２−ＢＴＢ−３ ７．０％
２−Ｈ２ＢＴＢ−２ ４．０％
２−Ｈ２ＢＴＢ−３ ４．０％
３−Ｈ２ＢＴＢ−２ ４．０％
３−Ｈ２ＢＴＢ−３ ４．０％
３−Ｈ２ＢＴＢ−４ ４．０％
３−ＨＨＢ−１ ７．０％
３−ＨＨＢ−Ｏ１ ５．０％
６ＢＢＥ１＊（ｔ−Ｂｕ）Ｂ ０．８部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝７３．７［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２３．２［ｍＰａ・ｓ］
Ｐ₂₅＝３．７［μｍ］
Ｈ．Ｔ．Ｐ．＝０．３３８［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１５
【００４１】
実施例５
次に示す組成の液晶組成物を調製した。
３Ｏ１−ＢＥＢ（Ｆ）−Ｃ １２．０％
１Ｖ２−ＨＢ−Ｃ ７．０％
２−ＢＴＢ−Ｏ１ ８．０％
３−ＢＴＢ−Ｏ１ ８．０％
４−ＢＴＢ−Ｏ１ ８．０％
４−ＢＴＢ−Ｏ２ ８．０％
５−ＢＴＢ−Ｏ１ ９．０％
２−Ｈ２ＢＴＢ−２ ４．０％
２−Ｈ２ＢＴＢ−３ ３．０％
２−Ｈ２ＢＴＢ−４ ３．０％
３−Ｈ２ＢＴＢ−２ ４．０％
３−Ｈ２ＢＴＢ−３ ４．０％
３−Ｈ２ＢＴＢ−４ ４．０％
３−ＨＢ（Ｆ）ＴＢ−２ ６．０％
３−ＨＢ（Ｆ）ＴＢ−３ ６．０％
３−ＨＢ（Ｆ）ＴＢ−４ ６．０％
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８８．７［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝４０．８［ｍＰａ・ｓ］
Ｐ₂₅＝３．３［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２０２［μｍ^-1・ｗｔ％^-1］
δＰ＝−０．０８
【００４２】
実施例６
次に示す組成の液晶組成物を調製した。
３−ＰｙＢ（Ｆ）−Ｆ １２．０％
５−ＰｙＢ（Ｆ）−Ｆ ７．０％
３−ＰｙＢＢ−Ｆ １０．０％
４−ＰｙＢＢ−Ｆ １０．０％
５−ＰｙＢＢ−Ｆ １０．０％
２−ＰｙＢ−２ ２．６％
３−ＰｙＢ−２ ２．７％
４−ＰｙＢ−２ ２．７％
３−ＨＢ−Ｏ２ １５．０％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−Ｏ１ ５．０％
３−ＨＨＢ−３ １１．０％
３−ＨＨＢ−Ｆ ４．０％
８ＯＢＢＥ１＊（Ｅｔ）Ｂ １．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８４．９［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝４１．９［ｍＰａ・ｓ］
Ｐ₂₅＝３．９［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２５６［μｍ^-1・ｗｔ％^-1］
δＰ＝０．０９
上記の液晶組成物は、比較例１と同じ光学活性化合物を添加しているが、ＴNIが上昇する一方、ＴSNが低下してネマティック液晶範囲が顕著に拡大された。また、ＴNIが高い割には粘度も低く、δＰも優れている。
【００４３】
実施例７
次に示す組成の液晶組成物を調製した。
３−ＰｙＢ（Ｆ）−Ｆ １２．０％
５−ＰｙＢ（Ｆ）−Ｆ ７．０％
３−ＰｙＢＢ−Ｆ １０．０％
４−ＰｙＢＢ−Ｆ １０．０％
５−ＰｙＢＢ−Ｆ １０．０％
２−ＰｙＢ−２ ２．６％
３−ＰｙＢ−２ ２．７％
４−ＰｙＢ−２ ２．７％
３−ＨＢ−Ｏ２ １５．０％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−Ｏ１ ５．０％
３−ＨＨＢ−３ １１．０％
３−ＨＨＢ−Ｆ ４．０％
６ＢＢＥ１＊（Ｍｅ）Ｂ２ １．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８４．５［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝３４．６［ｍＰａ・ｓ］
Ｐ₂₅＝２．５［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２００［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１９
【００４４】
実施例８
次に示す組成の液晶組成物を調製した。
２−ＨＨＢ（Ｆ）−Ｃ ６．０％
３−ＨＨＢ（Ｆ）−Ｃ ６．０％
２−ＨＢ−Ｃ ８．０％
３−ＨＢ−Ｃ ８．０％
２−ＰｙＢ−Ｆ １４．０％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−３ ５．５％
２−ＰｙＢＨ−３ ５．０％
３−ＰｙＢＨ−３ ５．０％
４−ＰｙＢＨ−３ ５．０％
２−ＰｙＢ−２ ２．５％
３−ＰｙＢ−２ ２．５％
４−ＰｙＢ−２ ２．５％
２−ＨＨＢ（Ｆ）−Ｆ １１．０％
３−ＨＨＢ（Ｆ）−Ｆ １１．０％
８ＯＢＢＥ１＊（Ｅｔ）Ｂ １．５部
ＣＮ ０．５部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８３．３［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２８．３［ｍＰａ・ｓ］
Ｐ₂₅＝３．８［μｍ］
δＰ＝０．１４
【００４５】
実施例９
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ １６．０％
１Ｏ１−ＨＢ−Ｃ １０．０％
３−ＨＢ（Ｆ）−Ｃ ５．０％
３−ＰｙＢＢ−Ｆ ５．０％
２−ＢＴＢ−１ ３．０％
３−ＨＨ−４ ５．０％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−Ｏ１ ２．０％
３−ＨＢ（Ｆ）ＴＢ−２ ３．０％
３−ＨＢ（Ｆ）ＴＢ−３ ３．０％
２−ＨＨＢ（Ｆ）−Ｆ １２．０％
３−ＨＨＢ（Ｆ）−Ｆ １２．０％
５−ＨＨＢ（Ｆ）−Ｆ １２．０％
３−ＨＨＢ−Ｆ ４．０％
６ＢＢＥ１＊（Ｍｅ）Ｂ２ ３．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８９．３［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２７．８［ｍＰａ・ｓ］
Ｐ₂₅＝１．５［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２２２［μｍ^-1・ｗｔ％^-1］
δＰ＝０．２１
【００４６】
実施例１０
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ １０．０％
５−ＨＢ−Ｃ ２０．０％
３−ＨＨＢ−Ｏ１ ５．０％
３−ＨＨＢ−１ １０．０％
３−ＨＨＢ−３ １６．０％
１Ｏ１ＨＢＢＨ−３ ２．０％
５−ＨＥＢ−Ｆ １３．０％
７−ＨＥＢ−Ｆ １３．０％
３−ＨＨＥＢ−Ｆ ３．０％
５−ＨＨＥＢ−Ｆ ３．０％
３−ＨＨＢ−Ｆ ５．０％
８ＯＢＢＥ１＊（Ｍｅ）Ｂ ２．５部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８４．１［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２９．７［ｍＰａ・ｓ］
Ｐ₂₅＝２．０［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２００［μｍ^-1・ｗｔ％^-1］
δＰ＝−０．１２
【００４７】
実施例１１
次に示す組成の液晶組成物を調製した。
２−ＢＢ−Ｃ １２．０％
４−ＢＢ−Ｃ ８．０％
５−ＢＢ−Ｃ ４．０％
２−ＨＨＢ−Ｃ ４．０％
３−ＨＨＢ−Ｃ ８．０％
２−ＨＢ−Ｃ １０．０％
５−ＰｙＢ−Ｆ ８．０％
１Ｏ１−ＨＨ−３ ８．０％
１Ｏ１−ＨＨ−５ ８．０％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−３ １０．０％
３−ＨＨＢ−Ｏ１ ４．０％
３−ＨＨＢ−Ｆ ４．０％
３−ＨＢＥＢ−Ｆ ４．０％
５ＨＢＥ１＊（Ｅｔ）Ｂ １．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８０．５［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２８．８［ｍＰａ・ｓ］
Ｐ₂₅＝３．０［μｍ］
Ｈ．Ｔ．Ｐ．＝０．３３３［μｍ^-1・ｗｔ％^-1］
δＰ＝０．２５
【００４８】
実施例１２
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ ２２．０％
２−ＨＢ−Ｃ １０．０％
３−ＨＨＢ−１ ６．０％
３−ＨＨＢ−Ｏ１ ４．０％
３−ＨＨＢ−３ １２．０％
２−ＨＢＢ（Ｆ）−Ｆ ６．０％
３−ＨＢＢ（Ｆ）−Ｆ ６．０％
５−ＨＢＢ（Ｆ）−Ｆ １２．０％
３−ＨＨＥＢ（Ｆ，Ｆ）−Ｆ １０．０％
４−ＨＨＥＢ（Ｆ，Ｆ）−Ｆ ３．０％
５−ＨＨ２Ｂ（Ｆ，Ｆ）−Ｆ ３．０％
３−ＨＨＢ（Ｆ，Ｆ）−Ｆ ６．０％
６ＢＢＥ１＊（ｔ−Ｂｕ）Ｂ ２．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８５．５［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２８．９［ｍＰａ・ｓ］
Ｐ₂₅＝１．５［μｍ］
Ｈ．Ｔ．Ｐ．＝０．３３３［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１６
【００４９】
実施例１３
次に示す組成の液晶組成物を調製した。
２Ｏ１−ＢＥＢ（Ｆ）−Ｃ ４．０％
３Ｏ１−ＢＥＢ（Ｆ）−Ｃ １５．０％
１Ｖ２−ＢＥＢ（Ｆ，Ｆ）−Ｃ ９．０％
Ｖ２−ＨＢ−Ｃ ９．０％
３−ＨＢ−Ｏ２ ７．０％
３−ＨＨ−４ ９．０％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−Ｏ１ ５．０％
３−ＨＨＢ−３ ６．０％
３−Ｈ２ＢＴＢ−２ ４．０％
３−Ｈ２ＢＴＢ−３ ４．０％
３−Ｈ２ＢＴＢ−４ ４．０％
２−Ｈ２ＢＴＢ−２ ２．０％
３−ＨＨＥＢ−Ｆ ５．０％
５−ＨＨＥＢ−Ｆ ５．０％
３−ＨＨＢ−Ｆ ４．０％
５ＨＢＥ１＊（Ｅｔ）Ｂ ０．８部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８９．７［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝３３．８［ｍＰａ・ｓ］
Ｐ₂₅＝３．６［μｍ］
Ｈ．Ｔ．Ｐ．＝０．３４７［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１９
【００５０】
実施例１４
次に示す組成の液晶組成物を調製した。
３−ＨＢ（Ｆ）ＥＢ（Ｆ）−Ｃ ７．０％
３−ＨＢ（Ｆ）−Ｃ ３．０％
２−ＨＨＢ（Ｆ）−Ｃ ５．０％
３−ＨＢ−Ｏ２ １０．０％
３−ＨＨ−４ １０．０％
３−ＨＨＢ−１ ５．０％
３−ＨＨＢ−Ｏ１ ５．０％
３−ＨＨＢ−３ ５．０％
５−ＨＢ−ＣＬ ４．０％
７−ＨＢ−ＣＬ ３．０％
２−ＨＨＢ（Ｆ）−Ｆ ５．０％
３−ＨＨＢ（Ｆ）−Ｆ ５．０％
５−ＨＨＢ（Ｆ）−Ｆ ５．０％
３−ＨＨ２Ｂ（Ｆ，Ｆ）−Ｆ １０．０％
５−ＨＨ２Ｂ（Ｆ，Ｆ）−Ｆ ５．０％
３−ＨＨＢ（Ｆ，Ｆ）−Ｆ １０．０％
３−ＨＨＢ−ＣＬ ３．０％
８ＯＢＢＥ１＊（Ｅｔ）Ｂ ２．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８３．１［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２１．３［ｍＰａ・ｓ］
Ｐ₂₅＝１．９［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２６３［μｍ^-1・ｗｔ％^-1］
δＰ＝０．１４
【００５１】
実施例１５
次に示す組成の液晶組成物を調製した。
２−ＨＢ−Ｃ ８．０％
３−ＨＢ−Ｃ １４．０％
３−ＰｙＢ（Ｆ）−Ｆ １２．０％
５−ＰｙＢ（Ｆ）−Ｆ ８．０％
２−ＨＨＢ−Ｃ ４．０％
３−ＨＨＢ−Ｃ ５．０％
３−ＰｙＢＨ−２ ３．０％
２−ＰｙＢＨ−３ ６．０％
３−ＰｙＢＨ−３ ６．０％
４−ＰｙＢＨ−３ ６．０％
４−ＰｙＢＢ−２ ３．０％
３−ＨＢ（Ｆ）ＴＢ−２ ５．０％
３−ＨＢ（Ｆ）ＴＢ−３ ４．０％
３−ＨＨＢ−１ ６．０％
３−ＨＨＢ−Ｏ１ ４．０％
３−ＨＨＢ−３ ６．０％
５ＨＢＥ１＊（Ｅｔ）Ｂ ２．０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝９７．８［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝３７．７［ｍＰａ・ｓ］
Ｐ₂₅＝１．５［μｍ］
Ｈ．Ｔ．Ｐ．＝０．３３３［μｍ^-1・ｗｔ％^-1］
δＰ＝０．３０
【００５２】
実施例１６
次に示す組成の液晶組成物を調製した。
３−ＨＢ−Ｃ ７．０％
１Ｏ１−ＨＢ−Ｃ ７．０％
２Ｏ１−ＨＢ−Ｃ ７．０％
２−ＨＨＢ−Ｃ ６．０％
３−ＨＨＢ−Ｃ ６．０％
１Ｏ−ＢＥＢ−２ １１．０％
３−ＨＥＢ−Ｏ４ ８．３％
４−ＨＥＢ−Ｏ２ ６．３％
５−ＨＥＢ−Ｏ１ ６．３％
３−ＨＥＢ−Ｏ２ ４．９％
５−ＨＥＢ−Ｏ２ ３．９％
４−ＨＥＢ−Ｏ４ ８．３％
３−ＨＨＢ−１ ８．０％
３−ＨＨＢ−Ｏ１ ４．０％
３−ＨＨＢ−３ ６．０％
６ＢＢＥ１＊（Ｍｅ）Ｂ２ １．８部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝８２．６［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝３６．２［ｍＰａ・ｓ］
Ｐ₂₅＝２．５［μｍ］
Ｈ．Ｔ．Ｐ．＝０．２２２［μｍ^-1・ｗｔ％^-1］
δＰ＝０．２３
【００５３】
実施例１７
次に示す組成の液晶組成物を調製した。
Ｖ２−ＨＢ−Ｃ １１．０％
１Ｖ２−ＨＢ−Ｃ １１．０％
３−ＨＢ−Ｃ １６．０％
５−ＨＢ−Ｃ ６．０％
１Ｏ１−ＨＢ−Ｃ ４．０％
２−ＨＨＢ−Ｃ ４．０％
３−ＨＨＢ−Ｃ ５．０％
４−ＨＨＢ−Ｃ ３．０％
３−ＨＨ−２Ｖ１ １０．０％
１Ｏ１−ＨＨ−５ ９．０％
２−ＢＴＢ−Ｏ１ １１．０％
３−ＨＢ（Ｆ）ＶＢ−２ ２．０％
３−ＨＢ（Ｆ）ＴＢ−２ ４．０％
３−ＨＢ（Ｆ）ＴＢ−３ ４．０％
８ＯＢＢＥ１＊（Ｅｔ）Ｂ ０．０５部
２１＊（Ｍｅ）１ＯＢＢＣ ０．５０部
この液晶組成物の諸物性値は次の通りであった。
Ｔ_NI＝７８．５［℃］
Ｔ_SN≦−３０［℃］
η₂₀＝２６．８［ｍＰａ・ｓ］
Ｐ₂₅＝２．２［μｍ］
δＰ＝０．１９
以上の比較例および実施例の透明点と粘度の関係を「図１」のグラフで表した。比較例１〜３に較べて実施例１〜１７の液晶組成物が透明点が高い割には粘度が低いことが、顕著に表れている。
【００５４】
【発明の効果】
実施例に示したように、双安定スイッチング液晶表示素子に求められる種々の特性を満たしながら、高速応答性に対応するために低粘度であり、さらに低温相溶性に優れ、電圧駆動可能な温度範囲を大きくし、またピッチの温度依存性の小さいカイラル−ネマチック液晶組成物を提供することができる。
【図面の簡単な説明】
【図１】本発明の実施例および比較例の液晶組成物の透明点と粘度の関係を示すグラフ。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a nematic liquid crystal composition containing at least one chiral additive used in a sealed liquid crystal display cell formed of two substrates having transparent electrodes, and a liquid crystal display using the liquid crystal composition It relates to an element. More specifically, the present invention relates to a liquid crystal composition suitable for a simple matrix liquid crystal display element utilizing two metastable state switching (bistable switching), and a liquid crystal display element using the liquid crystal composition.
[0002]
[Prior art]
As a liquid crystal display element (LCD) display method, a twisted nematic (TN) method, a super twisted nematic (STN) method, an active matrix (AM-LCD) method, and the like have been proposed and put into practical use one after another. For example, proposed by M. Schadt and W. Helfrich (Appl. Phys. Lett. 18 (1971) 127), proposed by the TN system in which the orientation of liquid crystal molecules in the upper and lower substrates is twisted by 90 °, TJScheffer, etc. (Appl. Phy. Lett., 45 (10), 1021 (1984)) Since the STN method in which the orientation of liquid crystal molecules on the upper and lower substrates is twisted to 180 to 270 ° has no memory effect, the voltage averaging method is used. Are driven by a simple matrix driving method based on the above or an active matrix driving method in which an active element such as a transistor is provided in each pixel.
[0003]
In addition, methods using bistable switching have been proposed in Japanese Patent Laid-Open Nos. 6-230751 and 6-235920. These sandwich a chiral nematic liquid crystal between a pair of transparent electrode substrates provided with an alignment film, and the chiral nematic liquid crystal has a twisted structure with a twist angle φ in the initial state, causing a Fredericks transition in the initial state. In a liquid crystal display device having two metastable states (for example, φ ± 180 °) different from the initial state as a relaxed state after applying the voltage to be applied, the voltage applied to cause the Fredericks transition is changed to the initial state and Select a voltage pulse above the threshold in two metastable states and then select the voltage applied to select one of the two metastable states with reference to the critical value that produces the two metastable states It is a liquid crystal display element which makes the voltage pulse performed. Multiplex driving can be performed by using a voltage applied during a period in which the state selected in any metastable state is maintained as a pulse equal to or lower than a threshold value in two metastable states.
[0004]
The liquid crystal composition used in these bistable switching liquid crystal display elements is required to have the following characteristics.
(1) To exhibit a nematic liquid crystal phase in a wide temperature range including room temperature.
(2) Appropriate dielectric anisotropy (Δε) can be taken to achieve both bistability and steep threshold characteristics.
(3) The viscosity (η) is small in order to minimize the response time (τ). Or spray elastic constant (K₁₁) Is large.
(4) Appropriate refractive index anisotropy (Δn) can be taken to achieve both high contrast ratio and high transmittance.
(5) The temperature dependence of the pitch (P) is small in order to widen the temperature range in which voltage driving is possible.
And so on.
[0005]
With the recent development of portable LCDs, development on the premise of outdoor use has also been considered. In order to withstand outdoor use, it is required to exhibit a nematic phase over a region exceeding the temperature range of the use environment. Usually, nematic-isotropic phase transition temperature (clearing point: T_NI) Is 60 ° C. or higher, smectic-nematic phase transition temperature (T_SN) Is required to be −20 ° C. or lower.
[0006]
A method for maintaining display quality by adding a trace amount of an optically active substance to a liquid crystal composition to suppress the reverse twist of the liquid crystal molecules to give the liquid crystal molecules a clockwise or counterclockwise spiral structure and maintaining display quality is already well known. It is. H. Torsional force of optically active substance added as chiral component T. T. et al. P. (Μm · wt%)^-1Is defined by the following formula (1) using the additive concentration “c (wt%)” and the pitch “P (μm)”.
P = 1 / (HTP P × c) …………………… Formula (1)
[0007]
The pitch required for the bistable switching liquid crystal display element is characterized by a short P <4 μm. Therefore, this H.P. T. T. et al. P. If it is small, it is necessary to add the chiral component at a considerably high concentration in order to obtain a necessary pitch of 4 μm or less, which adversely affects other material parameters. For example, smectic-nematic phase transition point T_SNBecomes extremely high, and the temperature range in which voltage driving is possible becomes narrow. Further, since the concentration of the chiral component is high, the viscosity of the chiral-nematic liquid crystal composition increases, and as a result, the response speed increases. Further H. T. T. et al. P. When a chiral component having a small value is used, the temperature dependence of the pitch tends to increase as the temperature rises, and the temperature range in which voltage driving is possible becomes narrow, which is not preferable.
As described above, although the liquid crystal composition has been intensively studied for various purposes, the current situation is that a new improvement is always required.
[0008]
[Problems to be solved by the invention]
The object of the present invention is to achieve a high temperature response range while satisfying various characteristics required for the above-described bistable switching liquid crystal display device, and to have a low viscosity, excellent low-temperature compatibility, and a voltage-driven temperature range. An object of the present invention is to provide a chiral-nematic liquid crystal composition having a large pitch and a small temperature dependency of the pitch.
[0009]
[Means for Solving the Problems]
As a result of intensive investigations on compositions using various liquid crystal compounds in order to solve these problems, the present inventors have found this purpose when the liquid crystal composition of the present invention is used in a bistable switching liquid crystal display device. I found what I could achieve.
The present invention will be described in detail below.
[0010]
  In the first invention of the present invention, the general formula (I), (II-a), (II-b) is used as the first component.and(II-c)
[Chemical 8]

(Wherein R¹Represents an alkyl group having 1 to 10 carbon atoms, and Q¹Represents H or F, and m represents 0 or 1. )
[Chemical 9]

(Wherein R², R³ And R ⁴ IsEach independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any one of the groups or two non-adjacent methylene groups (-CH₂-) May be substituted by an oxygen atom (-O-). A¹, A², A³And A⁴Each independently represents trans-1,4-cyclohexylene or 1,4-phenylene;⁵Represents trans-1,4-cyclohexylene or 1,4-phenylene in which one H in the side position may be substituted with F. Z¹, Z²And Z³Each independently represents —CH₂CH₂-Or a single bond. Z⁴Is —COO—, —CH₂CH₂-Or a single bond,Q ¹ Represents H or F, and i represents 0 or 1. )
Containing at least one compound selected from the group of compounds represented by:
  General formulas (III), (IV) and (V) as the second component
[Chemical Formula 10]

(Wherein R⁶And R⁷Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. In any case, any one of the groups or two or more methylene groups (-CH₂-) May be substituted by an oxygen atom. B represents trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene, C represents trans-1,4-cyclohexylene or 1,4-phenylene, Z⁵Is —C≡C—, —COO—, —CH₂CH₂-, -CH = CH-, -CF = CF- or a single bond. )
Embedded image

(Wherein R⁸Represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any one of the groups or two or more methylene groups (-CH₂-) May be substituted by an oxygen atom (-O-). R⁹Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkoxymethyl group, D represents trans-1,4-cyclohexylene or pyrimidine-2,5-diyl, and E represents trans-1,4-cyclohexylene. Alternatively, one H in the side position represents 1,4-phenylene which may be substituted with F, G represents trans-1,4-cyclohexylene or 1,4-phenylene, and Z⁶Is -CH₂CH₂-Or a single bond, Z⁷Is —C≡C—, —COO—, —CH═CH— or a single bond.Show. )
Embedded image

(Wherein R¹⁰Represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any one of the groups or two or more methylene groups (-CH₂-) May be substituted by an oxygen atom (-O-). R¹¹Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkoxymethyl group;Q ² Represents H or F. )
Containing at least one compound selected from the group of compounds represented by:
  As a third component, H.P. T. T. et al. P. (Herical Twisting power) is 0.15 (μm · wt%)^-1Optically active compoundAnd the following formula ( VI -A), ( VI -B) and ( VI -C)
[Chemical 6]

(Where R ¹² Represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group, K represents trans-1,4-cyclohexylene or 1,4-phenylene, and Y represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Compound selected from the group of optically active compounds represented byFurther, the present invention relates to a chiral nematic liquid crystal composition characterized by containing at least one of the above and having a helical pitch adjusted to 4 μm or less.
[0012]
  First of the present invention2According to the present invention, the first component is 10 to 65% by weight and the second component is 35 to 90% by weight with respect to the total weight of the liquid crystal composition.1'sThe present invention relates to a chiral nematic liquid crystal composition described in the invention.
[0013]
  First of the present invention3The present invention further comprises, as a fourth component, the general formula (VII)
Embedded image

(Wherein R¹³Represents an alkyl group having 1 to 10 carbon atoms, J represents trans-1,4-cyclohexylene or 1,4-phenylene in which one or two H atoms on the side positions may be substituted with F;⁵Represents F or Cl, Q⁴And Q⁶Each independently represents H or F;⁸And Z⁹Are each independently -COO-, -C₂H₄-Represents a single bond, and n represents 0, 1 or 2. 1), containing at least one compound selected from the group of compounds represented byandFirst2The chiral nematic liquid crystal composition according to any one of the inventions.
[0014]
  First of the present invention4According to the present invention, the content of the fourth component is 0 to 50% by weight with respect to the total weight of the liquid crystal composition.3The chiral nematic liquid crystal composition according to any one of the inventions.
[0015]
  First of the present invention5The inventions 1 to 14In any of the inventions in general formulas (II-a), (II-b) and (II-c)R ² ~R ⁴ The present invention relates to a chiral nematic liquid crystal composition, wherein each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkoxymethyl group.
[0016]
  First of the present invention6The inventions 1 to 15In any of the inventions, R in the general formula (III)⁶And R⁷The present invention relates to a chiral nematic liquid crystal composition, wherein each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or an alkoxymethyl group.
[0017]
  First of the present invention7The inventions 1 to 16In any of the inventions, R in the general formula (IV)⁸Represents an alkyl group having 1 to 10 carbon atoms, R⁹The present invention relates to a chiral nematic liquid crystal composition characterized in that represents an alkyl group or alkoxy group having 1 to 10 carbon atoms.
[0018]
  First of the present invention8The invention of the first to first7The present invention relates to a liquid crystal display device using the chiral nematic liquid crystal composition described in any of the inventions.
[0019]
Hereinafter, the liquid crystal compound constituting the liquid crystal composition of the present invention will be described.
Preferred examples of the compound represented by the general formula (I) and / or (II-a) to (II-c), which are the first component of the present invention, include the following compounds.
Embedded image

Embedded image

(R represents an alkyl group or alkenyl group, and R 'represents alkanediyl or alkenediyl.)
[0020]
Among these compounds of the first component, formulas (I-1), (I-2), (I-3), (II-a-1), (II-a-2), (II-a -3), (II-b-1), (II-c-1), (II-c-5), (II-c-6), (II-c-11) or (II-c-13) ) Is particularly preferably used in the present invention.
[0021]
These compounds of the first component are compounds having a positive dielectric anisotropy and are particularly large in value, and are used mainly for the purpose of reducing the threshold voltage and the purpose of improving the steepness important as STN characteristics. In order to perform low-voltage driving, these compounds having a large dielectric anisotropy are indispensable components.
[0022]
As the compounds represented by the general formulas (III), (IV) and (V) of the second component, the following compounds are preferably exemplified.
Embedded image

Embedded image

Embedded image

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(R and R 'each independently represents an alkyl group or an alkenyl group.)
[0023]
Among these, the compounds represented by the formula (III) include the formulas (III-1), (III-4), (III-6), (III-7), (III-8), (III −10), (III-13), (III-14), (III-18) or (III-19) are particularly preferably used in the present invention. Moreover, as a compound represented by Formula (IV), Formula (IV-2), (IV-5), (IV-6), (IV-8), (IV-11), (IV-12) Alternatively, the compound represented by (IV-14) is particularly preferably used in the present invention. As the compound represented by the formula (V), the compound represented by (V-2) is particularly preferably used in the present invention.
[0024]
The compounds of the general formulas (III), (IV) and (V) as the second component are positive compounds having a negative or weak dielectric anisotropy. The compound of the general formula (III) is mainly used for the purpose of viscosity reduction and / or Δn adjustment. The compound of the general formula (IV) is used for the purpose of widening the nematic range such as increasing the clearing point and / or for the purpose of adjusting Δn and viscosity.
[0025]
H., which is the third component of the present invention. T. T. et al. P. Is 0.150 (μm · wt%)^-1Of the above optically active compounds, the optically active compounds represented by the formula (VI-a), (VI-b) or (VI-c) are preferably the following optically active compounds.
Embedded image

Embedded image

(In the formula, R and R 'each represents an alkyl group having 1 to 10 carbon atoms.)
[0026]
Among these compounds, compounds of formula (VI-a-1), (VI-a-7), (VI-b-2), (VI-b-3) and (VI-c-3) are It is particularly preferably used in the present invention.
The optically active compounds of general formulas (VI-a) to (VI-c), which are the third component, are used as chiral components to adjust the pitch length of the helix.
[0027]
Preferred examples of the compound represented by the general formula (VII) as the fourth component of the present invention include the following compounds.
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(R represents an alkyl group.)
[0028]
The compounds of the fourth component represented by the general formula (VII) include the formulas (VII-1), (VII-5), (VII-6), (VII-7), (VII-8), (VII -9), (VII-10), (VII-11), (VII-12), (VII-15), (VII-16), (VII-17), (VII-18), (VII-19) ), (VII-20), (VII-22), (VII-29), (VII-34), (VII-35), (VII-37), (VII-41), (VII-45), The compounds represented by (VII-46), (VII-47) or (VII-48) are preferably used, and among these, (VII-1), (VII-5), (VII-7) , (VII-8), (VII-9), (VII-11), (VII-12), (VII-15), (VII-19), (VII-20) or (VII-29) Are particularly preferably used in the present invention.
The compound of the general formula (VII) is a compound having a positive dielectric anisotropy, and is used particularly for the purpose of reducing the threshold voltage and improving its temperature dependency. It is also used for the purpose of widening the nematic range such as viscosity adjustment, Δn adjustment, and clearing point increase.
[0029]
The mixing ratio of the first component used in the present invention is preferably 10 to 65% with respect to the total weight of the liquid crystal composition. More preferably, it is 15 to 60%.
The mixing ratio of the second component is preferably 35 to 90%. More preferably, it is 40 to 85%.
The mixing ratio of the fourth component is preferably 0 to 50%.
[0030]
Depending on the purpose of the liquid crystal display element to be used, the liquid crystal composition of the present invention may have a threshold voltage, a nematic range, Δn, a different dielectric constant in addition to the compounds represented by the general formulas (I) to (VII). For the purpose of adjusting the isotropic property, viscosity, etc., other compounds can be contained in appropriate amounts within a range that does not impair the purpose of the present invention.
[0031]
The liquid crystal composition of the present invention is prepared by a conventional method. In general, a method is used in which various components are dissolved together at a high temperature. Further, the liquid crystal material of the present invention is optimized and optimized in accordance with the intended use by appropriate additives. Such additives are well known to those skilled in the art and are described in detail in the literature.
In addition, the liquid crystal composition of the present invention is for guest host (GH) mode by adding a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. It can also be used as a liquid crystal composition. Alternatively, a liquid crystal composition for a polymer dispersed liquid crystal display element (PNLCD) represented by NCAP produced by encapsulating nematic liquid crystal or a polymer network liquid crystal display element (PNLCD) in which a three-dimensional network polymer is produced in the liquid crystal. It can also be used as a product. In addition, it can be used as a liquid crystal composition for birefringence control (ECB) mode and dynamic scattering (DS) mode.
[0032]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the liquid crystal compounds used in Comparative Examples and Examples are represented by symbols based on “Table 1”, the optically active compounds are represented by abbreviations shown in “Table 2”, and their composition ratios are all weights for the liquid crystal components. Shown in%. However, the optically active compound as the third component is shown in parts by weight with respect to 100 parts by weight of the liquid crystal composition other than the optically active compound.
[Table 1]

[Table 2]

[0033]
The clearing point (nematic-isotropic transition point) is T_NI[° C], the smectic-nematic transition point (or the lower limit of the nematic phase) as T_SN[℃] (T_SNIs determined by the liquid crystal phase after being left in each freezer at 0 ° C., −10 ° C., −20 ° C., and −30 ° C. for 30 days), and the viscosity at 20 ° C. is η₂₀[MPa · s], the helical pitch length at 25 ° C is P_{twenty five}[Μm], P based on formula (1)_{twenty five}And the helical torsional force derived from the amount of the optically active compound added. T. T. et al. P. [Μm^-1・ Wt%^-1The equation (2) is defined as a parameter indicating the temperature dependence δP of the helical pitch length.
[Expression 1]

Where P₂₀And P₅₀Indicates the helical pitch length [μm] at 20 ° C. and 50 ° C., respectively, and the value of δP is preferably closer to 0.
[0034]
Comparative Example 1
A liquid crystal composition having the following composition was prepared.
3-HB-C 24.0%
5-HB-C 36.0%
7-HB-C 25.0%
5-HBB-C 15.0%
8OBBE1 * (Et) B 1.0 part
Various physical properties of this liquid crystal composition were as follows.
T_NI= 70.5 [° C]
T_SN≦ −20 [° C.]
η₂₀= 36.4 [mPa · s]
P_{twenty five}= 3.9 [μm]
H. T. T. et al. P. = 0.256 [μm^-1・ Wt%^-1]
δP = 0.09
[0035]
Comparative Example 2
A liquid crystal composition having the following composition was prepared.
3-HB-C 24.0%
5-HB-C 36.0%
7-HB-C 25.0%
5-HBB-C 15.0%
21 * (Me) 1OBBC 20.0 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 63.1 [° C]
T_SN≦ 0 [℃]
η₂₀= 40.2 [mPa · s]
P_{twenty five}= 3.6 [μm]
H. T. T. et al. P. = 0.014 [μm^-1・ Wt%^-1]
δP = 0.92
[0036]
Comparative Example 3
A liquid crystal composition having the following composition was prepared.
3-HB-C 24.0%
5-HB-C 36.0%
7-HB-C 25.0%
5-HBB-C 15.0%
6 OBEBE 1 * (Me) 6 2.2 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 69.8 [° C]
T_SN≦ −10 [℃]
η₂₀= 42.5 [mPa · s]
P_{twenty five}= 3.9 [μm]
H. T. T. et al. P. = 0.117 [μm^-1・ Wt%^-1]
δP = 0.31
[0037]
Example 1
A liquid crystal composition having the following composition was prepared.
V2-HB-C 13.0%
1V2-HB-C 13.0%
3-HB-C 5.0%
1O1-HH-3 2.0%
3-HH-4 13.0%
2-BTB-1 7.0%
2-BTB-3 4.0%
2-H2BTB-2 4.0%
2-H2BTB-3 4.0%
2-H2BTB-4 4.0%
3-H2BTB-2 4.0%
3-H2BTB-3 4.0%
3-H2BTB-4 4.0%
3-HB (F) TB-2 6.0%
2-PyB-2 3.3%
3-PyB-2 3.4%
4-PyB-2 3.3%
2-PyBH-3 3.0%
8OBBE1 * (Me) B 5.0 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 78.9 [° C]
T_SN≦ −30 [℃]
η₂₀= 26.8 [mPa · s]
P_{twenty five}= 1.0 [μm]
H. T. T. et al. P. = 0.200 [μm^-1・ Wt%^-1]
δP = 0.21
In the above liquid crystal composition, the TNI increased while the TSN decreased and the nematic liquid crystal range was remarkably expanded as compared with the comparative example. In addition, the viscosity is remarkably lowered, and δP is superior to Comparative Examples 2 and 3.
[0038]
Example 2
A liquid crystal composition having the following composition was prepared.
V2-HB-C 12.0%
1V2-HB-C 12.0%
3-HB-C 8.0%
2-HHB-C 6.0%
3-HHB-C 6.0%
4-HHB-C 6.0%
5-HHB-C 6.0%
3-HB-O2 12.0%
3-HH-4 11.0%
3-H2BTB-2 5.0%
3-H2BTB-3 4.0%
3-H2BTB-4 4.0%
3-HB (F) TB-2 8.0%
2.5 parts of 6BBE1 * (t-Bu) B
Various physical properties of this liquid crystal composition were as follows.
T_NI= 108.8 [° C]
T_SN≦ −30 [℃]
η₂₀= 30.9 [mPa · s]
P_{twenty five}= 1.2 [μm]
H. T. T. et al. P. = 0.333 [μm^-1・ Wt%^-1]
δP = 0.18
In the above liquid crystal composition, the TNI increased while the TSN decreased and the nematic liquid crystal range was remarkably expanded as compared with the comparative example. In addition, the viscosity is remarkably lowered, and δP is superior to Comparative Examples 2 and 3.
[0039]
Example 3
A liquid crystal composition having the following composition was prepared.
V2-HB-C 11.0%
1V2-HB-C 11.0%
3-HB-C 16.0%
5-HB-C 6.0%
1O1-HB-C 4.0%
2-HHB-C 4.0%
3-HHB-C 5.0%
4-HHB-C 3.0%
3-HH-2V1 10.0%
1O1-HH-5 9.0%
2-BTB-O1 11.0%
3-HB (F) VB-2 2.0%
3-HB (F) TB-2 4.0%
3-HB (F) TB-3 4.0%
1.5 parts of 6BBE1 * (Me) B2
Various physical properties of this liquid crystal composition were as follows.
T_NI= 78.7 [° C]
T_SN≦ −30 [℃]
η₂₀= 29.8 [mPa · s]
P_{twenty five}= 2.9 [μm]
H. T. T. et al. P. = 0.230 [μm^-1・ Wt%^-1]
δP = 0.17
In the above liquid crystal composition, the TNI increased while the TSN decreased and the nematic liquid crystal range was remarkably expanded as compared with the comparative example. In addition, the viscosity is remarkably lowered, and δP is superior to Comparative Examples 2 and 3.
[0040]
Example 4
A liquid crystal composition having the following composition was prepared.
V2-HB-C 13.0%
1V2-HB-C 13.0%
3-HB-C 12.0%
2-HB-C 10.0%
3-HH-4 3.0%
2-BTB-1 10.0%
2-BTB-3 7.0%
2-H2BTB-2 4.0%
2-H2BTB-3 4.0%
3-H2BTB-2 4.0%
3-H2BTB-3 4.0%
3-H2BTB-4 4.0%
3-HHB-1 7.0%
3-HHB-O1 5.0%
6BBE1 * (t-Bu) B 0.8 part
Various physical properties of this liquid crystal composition were as follows.
T_NI= 73.7 [° C.]
T_SN≦ −30 [℃]
η₂₀= 23.2 [mPa · s]
P_{twenty five}= 3.7 [μm]
H. T. T. et al. P. = 0.338 [μm^-1・ Wt%^-1]
δP = 0.15
[0041]
Example 5
A liquid crystal composition having the following composition was prepared.
3O1-BEB (F) -C 12.0%
1V2-HB-C 7.0%
2-BTB-O1 8.0%
3-BTB-O1 8.0%
4-BTB-O1 8.0%
4-BTB-O2 8.0%
5-BTB-O1 9.0%
2-H2BTB-2 4.0%
2-H2BTB-3 3.0%
2-H2BTB-4 3.0%
3-H2BTB-2 4.0%
3-H2BTB-3 4.0%
3-H2BTB-4 4.0%
3-HB (F) TB-2 6.0%
3-HB (F) TB-3 6.0%
3-HB (F) TB-4 6.0%
Various physical properties of this liquid crystal composition were as follows.
T_NI= 88.7 [° C]
T_SN≦ −30 [℃]
η₂₀= 40.8 [mPa · s]
P_{twenty five}= 3.3 [μm]
H. T. T. et al. P. = 0.202 [μm^-1・ Wt%^-1]
δP = −0.08
[0042]
Example 6
A liquid crystal composition having the following composition was prepared.
3-PyB (F) -F 12.0%
5-PyB (F) -F 7.0%
3-PyBB-F 10.0%
4-PyBB-F 10.0%
5-PyBB-F 10.0%
2-PyB-2 2.6%
3-PyB-2 2.7%
4-PyB-2 2.7%
3-HB-O2 15.0%
3-HHB-1 8.0%
3-HHB-O1 5.0%
3-HHB-3 11.0%
3-HHB-F 4.0%
8OBBE1 * (Et) B 1.0 part
Various physical properties of this liquid crystal composition were as follows.
T_NI= 84.9 [° C]
T_SN≦ −30 [℃]
η₂₀= 41.9 [mPa · s]
P_{twenty five}= 3.9 [μm]
H. T. T. et al. P. = 0.256 [μm^-1・ Wt%^-1]
δP = 0.09
In the above liquid crystal composition, the same optically active compound as in Comparative Example 1 was added. However, while TNI increased, TSN decreased and the nematic liquid crystal range was remarkably expanded. Moreover, although the TNI is high, the viscosity is low and the δP is also excellent.
[0043]
Example 7
A liquid crystal composition having the following composition was prepared.
3-PyB (F) -F 12.0%
5-PyB (F) -F 7.0%
3-PyBB-F 10.0%
4-PyBB-F 10.0%
5-PyBB-F 10.0%
2-PyB-2 2.6%
3-PyB-2 2.7%
4-PyB-2 2.7%
3-HB-O2 15.0%
3-HHB-1 8.0%
3-HHB-O1 5.0%
3-HHB-3 11.0%
3-HHB-F 4.0%
1.0 part of 6BBE1 * (Me) B2
Various physical properties of this liquid crystal composition were as follows.
T_NI= 84.5 [° C]
T_SN≦ −30 [℃]
η₂₀= 34.6 [mPa · s]
P_{twenty five}= 2.5 [μm]
H. T. T. et al. P. = 0.200 [μm^-1・ Wt%^-1]
δP = 0.19
[0044]
Example 8
A liquid crystal composition having the following composition was prepared.
2-HHB (F) -C 6.0%
3-HHB (F) -C 6.0%
2-HB-C 8.0%
3-HB-C 8.0%
2-PyB-F 14.0%
3-HHB-1 8.0%
3-HHB-3 5.5%
2-PyBH-3 5.0%
3-PyBH-3 5.0%
4-PyBH-3 5.0%
2-PyB-2 2.5%
3-PyB-2 2.5%
4-PyB-2 2.5%
2-HHB (F) -F 11.0%
3-HHB (F) -F 11.0%
1.5 parts of 8OBBE1 * (Et) B
CN 0.5 part
Various physical properties of this liquid crystal composition were as follows.
T_NI= 83.3 [° C]
T_SN≦ −30 [℃]
η₂₀= 28.3 [mPa · s]
P_{twenty five}= 3.8 [μm]
δP = 0.14
[0045]
Example 9
A liquid crystal composition having the following composition was prepared.
3-HB-C 16.0%
1O1-HB-C 10.0%
3-HB (F) -C 5.0%
3-PyBB-F 5.0%
2-BTB-1 3.0%
3-HH-4 5.0%
3-HHB-1 8.0%
3-HHB-O1 2.0%
3-HB (F) TB-2 3.0%
3-HB (F) TB-3 3.0%
2-HHB (F) -F 12.0%
3-HHB (F) -F 12.0%
5-HHB (F) -F 12.0%
3-HHB-F 4.0%
6BBE1 * (Me) B2 3.0 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 89.3 [° C]
T_SN≦ −30 [℃]
η₂₀= 27.8 [mPa · s]
P_{twenty five}= 1.5 [μm]
H. T. T. et al. P. = 0.222 [μm^-1・ Wt%^-1]
δP = 0.21
[0046]
Example 10
A liquid crystal composition having the following composition was prepared.
3-HB-C 10.0%
5-HB-C 20.0%
3-HHB-O1 5.0%
3-HHB-1 10.0%
3-HHB-3 16.0%
1O1HBBH-3 2.0%
5-HEB-F 13.0%
7-HEB-F 13.0%
3-HHEB-F 3.0%
5-HHEB-F 3.0%
3-HHB-F 5.0%
2.5 parts of 8OBBE1 * (Me) B
Various physical properties of this liquid crystal composition were as follows.
T_NI= 84.1 [° C.]
T_SN≦ −30 [℃]
η₂₀= 29.7 [mPa · s]
P_{twenty five}= 2.0 [μm]
H. T. T. et al. P. = 0.200 [μm^-1・ Wt%^-1]
δP = −0.12
[0047]
Example 11
A liquid crystal composition having the following composition was prepared.
2-BB-C 12.0%
4-BB-C 8.0%
5-BB-C 4.0%
2-HHB-C 4.0%
3-HHB-C 8.0%
2-HB-C 10.0%
5-PyB-F 8.0%
1O1-HH-3 8.0%
1O1-HH-5 8.0%
3-HHB-1 8.0%
3-HHB-3 10.0%
3-HHB-O1 4.0%
3-HHB-F 4.0%
3-HBEB-F 4.0%
1.0 part of 5HBE1 * (Et) B
Various physical properties of this liquid crystal composition were as follows.
T_NI= 80.5 [° C]
T_SN≦ −30 [℃]
η₂₀= 28.8 [mPa · s]
P_{twenty five}= 3.0 [μm]
H. T. T. et al. P. = 0.333 [μm^-1・ Wt%^-1]
δP = 0.25
[0048]
Example 12
A liquid crystal composition having the following composition was prepared.
3-HB-C 22.0%
2-HB-C 10.0%
3-HHB-1 6.0%
3-HHB-O1 4.0%
3-HHB-3 12.0%
2-HBB (F) -F 6.0%
3-HBB (F) -F 6.0%
5-HBB (F) -F 12.0%
3-HHEB (F, F) -F 10.0%
4-HHEB (F, F) -F 3.0%
5-HH2B (F, F) -F 3.0%
3-HHB (F, F) -F 6.0%
6BBE1 * (t-Bu) B 2.0 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 85.5 [° C.]
T_SN≦ −30 [℃]
η₂₀= 28.9 [mPa · s]
P_{twenty five}= 1.5 [μm]
H. T. T. et al. P. = 0.333 [μm^-1・ Wt%^-1]
δP = 0.16
[0049]
Example 13
A liquid crystal composition having the following composition was prepared.
2O1-BEB (F) -C 4.0%
3O1-BEB (F) -C 15.0%
1V2-BEB (F, F) -C 9.0%
V2-HB-C 9.0%
3-HB-O2 7.0%
3-HH-4 9.0%
3-HHB-1 8.0%
3-HHB-O1 5.0%
3-HHB-3 6.0%
3-H2BTB-2 4.0%
3-H2BTB-3 4.0%
3-H2BTB-4 4.0%
2-H2BTB-2 2.0%
3-HHEB-F 5.0%
5-HHEB-F 5.0%
3-HHB-F 4.0%
5HBE1 * (Et) B 0.8 part
Various physical properties of this liquid crystal composition were as follows.
T_NI= 89.7 [° C]
T_SN≦ −30 [℃]
η₂₀= 33.8 [mPa · s]
P_{twenty five}= 3.6 [μm]
H. T. T. et al. P. = 0.347 [μm^-1・ Wt%^-1]
δP = 0.19
[0050]
Example 14
A liquid crystal composition having the following composition was prepared.
3-HB (F) EB (F) -C 7.0%
3-HB (F) -C 3.0%
2-HHB (F) -C 5.0%
3-HB-O2 10.0%
3-HH-4 10.0%
3-HHB-1 5.0%
3-HHB-O1 5.0%
3-HHB-3 5.0%
5-HB-CL 4.0%
7-HB-CL 3.0%
2-HHB (F) -F 5.0%
3-HHB (F) -F 5.0%
5-HHB (F) -F 5.0%
3-HH2B (F, F) -F 10.0%
5-HH2B (F, F) -F 5.0%
3-HHB (F, F) -F 10.0%
3-HHB-CL 3.0%
8OBBE1 * (Et) B 2.0 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 83.1 [° C]
T_SN≦ −30 [℃]
η₂₀= 21.3 [mPa · s]
P_{twenty five}= 1.9 [μm]
H. T. T. et al. P. = 0.263 [μm^-1・ Wt%^-1]
δP = 0.14
[0051]
Example 15
A liquid crystal composition having the following composition was prepared.
2-HB-C 8.0%
3-HB-C 14.0%
3-PyB (F) -F 12.0%
5-PyB (F) -F 8.0%
2-HHB-C 4.0%
3-HHB-C 5.0%
3-PyBH-2 3.0%
2-PyBH-3 6.0%
3-PyBH-3 6.0%
4-PyBH-3 6.0%
4-PyBB-2 3.0%
3-HB (F) TB-2 5.0%
3-HB (F) TB-3 4.0%
3-HHB-1 6.0%
3-HHB-O1 4.0%
3-HHB-3 6.0%
5 parts of 5HBE1 * (Et) B
Various physical properties of this liquid crystal composition were as follows.
T_NI= 97.8 [° C]
T_SN≦ −30 [℃]
η₂₀= 37.7 [mPa · s]
P_{twenty five}= 1.5 [μm]
H. T. T. et al. P. = 0.333 [μm^-1・ Wt%^-1]
δP = 0.30
[0052]
Example 16
A liquid crystal composition having the following composition was prepared.
3-HB-C 7.0%
1O1-HB-C 7.0%
2O1-HB-C 7.0%
2-HHB-C 6.0%
3-HHB-C 6.0%
1O-BEB-2 11.0%
3-HEB-O4 8.3%
4-HEB-O2 6.3%
5-HEB-O1 6.3%
3-HEB-O2 4.9%
5-HEB-O2 3.9%
4-HEB-O4 8.3%
3-HHB-1 8.0%
3-HHB-O1 4.0%
3-HHB-3 6.0%
6BBE1 * (Me) B2 1.8 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 82.6 [° C]
T_SN≦ −30 [℃]
η₂₀= 36.2 [mPa · s]
P_{twenty five}= 2.5 [μm]
H. T. T. et al. P. = 0.222 [μm^-1・ Wt%^-1]
δP = 0.23
[0053]
Example 17
A liquid crystal composition having the following composition was prepared.
V2-HB-C 11.0%
1V2-HB-C 11.0%
3-HB-C 16.0%
5-HB-C 6.0%
1O1-HB-C 4.0%
2-HHB-C 4.0%
3-HHB-C 5.0%
4-HHB-C 3.0%
3-HH-2V1 10.0%
1O1-HH-5 9.0%
2-BTB-O1 11.0%
3-HB (F) VB-2 2.0%
3-HB (F) TB-2 4.0%
3-HB (F) TB-3 4.0%
8OBBE1 * (Et) B 0.05 part
21 * (Me) 1OBBC 0.50 parts
Various physical properties of this liquid crystal composition were as follows.
T_NI= 78.5 [° C.]
T_SN≦ −30 [℃]
η₂₀= 26.8 [mPa · s]
P_{twenty five}= 2.2 [μm]
δP = 0.19
The relationship between the clearing point and the viscosity in the comparative examples and examples described above is represented by the graph in FIG. Compared to Comparative Examples 1 to 3, the liquid crystal compositions of Examples 1 to 17 have a markedly low viscosity for a high clearing point.
[0054]
【The invention's effect】
As shown in the examples, while satisfying various characteristics required for a bistable switching liquid crystal display element, it has a low viscosity in order to respond to high-speed response, has excellent low-temperature compatibility, and can be driven by voltage. And a chiral-nematic liquid crystal composition having a small temperature dependency of pitch can be provided.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between clearing point and viscosity of liquid crystal compositions of Examples and Comparative Examples of the present invention.

Claims (8)

(1) As the first component, general formulas (I), (II-a), (II-b) and (II-c)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, Q ¹ represents H or F, and m represents 0 or 1.)

^(Wherein, R 2, ^{R 3} and ^{R 4} represents an alkenyl group of alkyl or 2 to 10 carbon atoms having 1 to 10 carbon atoms each independently. Also any one or adjacent to each other in the group in either Two methylene groups (—CH ₂ —) may be substituted by an oxygen atom (—O—), A ¹ , A ² , A ³ and A ⁴ are each independently trans-1,4-cyclohexylene Alternatively, it represents 1,4-phenylene, and A ⁵ represents trans-1,4-cyclohexylene or 1,4-phenylene in which one H in the side position may be substituted with F. Z ¹ , Z ² and Z ³ each independently represents —CH ₂ CH ₂ — or a single bond, Z ⁴ represents —COO—, —CH ₂ CH ₂ — or a single bond, Q ¹ represents H or F, and i represents 0 Or 1 is shown.)
Containing at least one compound selected from the group of compounds represented by:
(2) General formulas (III), (IV) and (V) as the second component

(In the formula, R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. In any case, any one of the groups or two not adjacent to each other) The above methylene group (—CH ₂ —) may be substituted with an oxygen atom, B represents trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene, and C represents trans -1,4-cyclohexylene or 1,4-phenylene, Z ⁵ is —C≡C—, —COO—, —CH ₂ CH ₂ —, —CH═CH—, —CF═CF— or a single bond Is shown.)

(Wherein R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any one of the groups or two or more methylene groups (—CH _2- ) may be substituted by an oxygen atom (—O—), R ⁹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkoxymethyl group, and D represents trans-1,4-cyclohexylene or P represents pyrimidine-2,5-diyl, E represents trans-1,4-cyclohexylene or 1,4-phenylene in which one H in the side position may be substituted with F, and G represents trans-1,4 - indicates cyclohexylene or 1,4-phenylene, ^{Z 6} are _-CH 2 CH ₂ - or a single bond, ^{Z 7} is -C≡C -, - COO -, - shows a CH = CH- or a single bond .)

(In the formula, R ¹⁰ represents an alkyl group having 1 to ¹⁰ carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any one of the groups or two or more methylene groups (—CH _2- ) may be substituted by an oxygen atom (-O-), R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkoxymethyl group, and Q ² represents H or F.)
Containing at least one compound selected from the group of compounds represented by:
(3) H.P. at 25 ° C. as the third component. T.A. P. An optically active compound having a (Herical Twisting power) of 0.15 (μm · wt%) ⁻¹ or more , which has the following formulas ( VI- a), ( VI- b) and ( VI- c)

(Wherein R ¹² represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group, K represents trans-1,4-cyclohexylene or 1,4-phenylene, and Y represents a hydrogen atom or 1 to 10 carbon atoms. Represents an alkyl group.)
Containing one or more compounds selected from the group of optically active compounds represented by:
A chiral nematic liquid crystal composition, wherein the spiral pitch is adjusted to 4 μm or less. (1) 10 to 65% by weight of the first component with respect to the total weight of the liquid crystal composition,
(2) 35 to 90% by weight of the second component
The chiral nematic liquid crystal composition according to claim 1, wherein In addition to the liquid crystal composition according to claim 1 or 2 , (4) as a fourth component, a compound represented by the general formula (VII)

(In the formula, R ¹³ represents an alkyl group having 1 to 10 carbon atoms, J represents trans-1,4-cyclohexylene, or one or two H atoms on the side positions may be substituted with F. 1,4 - indicates phenylene, ^{Q 5} represents F or Cl, ^{Q 4} and ^{Q 6} are each independently denote H or F, ^{Z 8} and ^{Z 9} are each independently -COO -, _- C 2 _{H 4} -Represents a single bond, and n represents 0, 1 or 2.)
A chiral nematic liquid crystal composition comprising at least one compound selected from the group of compounds represented by: The chiral nematic liquid crystal composition according to claim 3 , wherein the content of the fourth component is 50% by weight or less based on the total weight of the liquid crystal composition. In any one of claims 1-4, the general formula (II-a), (II -b) and (II-c) in R ² ~ R ⁴ are independently an alkyl group having 1 to 10 carbon atoms, alkoxy A chiral nematic liquid crystal composition characterized by showing a group or an alkoxymethyl group. In any one of claims. 1 to 5, R ⁶ and R ⁷ in the general formula (III) are each independently characterized by an alkyl group, an alkoxy group or an alkoxymethyl group having 1 to 10 carbon atoms Chiral nematic liquid crystal composition. In any one of claims. 1 to 6, ^{R 8} in the general formula (IV) represents an alkyl group having 1 to 10 carbon atoms, ^{R 9} is to indicate an alkyl group or an alkoxy group having 1 to 10 carbon atoms A chiral nematic liquid crystal composition. The liquid crystal display device using chiral nematic liquid crystal composition according to any one of claims 1-7.

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