JP4003244B2 - Liquid crystal compound having negative dielectric anisotropy value, liquid crystal composition containing the liquid crystal compound, and liquid crystal display device using the liquid crystal composition - Google Patents

Description

【００１４】
（式中、Ｒ^１及びＹ^１は各々独立して、直鎖の、炭素数１〜２０のアルキル基、炭素数１〜１９のアルコキシ基、炭素数２〜２０のアルケニル基、アルケニルオキシ基、アルキニル基、アルキニルオキシ基、炭素数２〜１９のアルコキシアルキル基、炭素数２〜１８のアルコキシアルコキシ基を表し、これらの基中の１個以上の水素原子はフッ素原子又は塩素原子で置換されていてもよく、又は各々独立して、水素原子、ハロゲン原子、−ＣＮ、−ＯＣＮ、−ＮＣ又は−ＮＣＳを表し、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は各々独立して単結合、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−ＣＨ＝ＣＨＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ＝ＣＨＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨＣＨ_２Ｏ−、−ＯＣＨ_２ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ_２ＣＦ_２−、−ＣＦ_２ＣＨ_２−、−（ＣＦ_２）_２−、−（ＣＦ_２）_４−、−（ＣＨ_２）_２ＣＯＯ−、−ＯＣＯ（ＣＨ_２）_２−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣ≡Ｃ−、−Ｃ≡ＣＣＨ＝ＣＨ−、又は−Ｏ（ＣＨ _２ ） _２ Ｏ−であり、環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４及び環Ａ^５は各々独立してトランス−シクロヘキシレン−１，４−ジイル、シクロヘキサ−１−エン−１，４−ジイル、１，４−フェニレン又はビシクロ〔１,１,１〕ペンタン−１，３−ジイルで表される環であり、
【００１６】
これらの環を構成する炭素原子は窒素原子、酸素原子又は硫黄原子で置換されていてもよく、環上の水素原子はハロゲン原子又はシアノ基で置換されていてもよく、ａ^１、ａ^２、ａ^３、ａ^４及びａ^５は各々独立して０又は１を表す。）
【００１７】
一般式（２）において、一般式（３）又は一般式（４）
【００１８】
【化１３】

【００１９】
で表される部分のどちらか一方が、一般式（５）
【００２０】
【化１４】

【００２１】
（式中Ｗ³、Ｗ⁴、Ｗ⁵及びＷ⁶は各々独立してフッ素原子又は塩素原子を表し、ｎは２を表す。）で表される液晶性化合物。
【００２２】
〔２〕第〔１〕項に記載の液晶性化合物を少なくとも１種類含有することを特徴とする、少なくとも２成分からなる液晶組成物。
〔３〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、一般式（６）、（７）及び（８）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
【００２３】
【化１５】

【００２４】
（式中、Ｒ²は炭素数１〜１０のアルキル基を表し、このアルキル基中の相隣接しない１個以上のメチレン基は酸素原子又は−ＣＨ＝ＣＨ−で置換されていてもよく、また、このアルキル基中の１個以上の水素原子はフッ素原子で置換されていてもよく、Ｙ²はフッ素原子、塩素原子、−ＯＣＦ₃、−ＯＣＦ₂Ｈ、−ＣＦ₃、−ＣＦ₂Ｈ、−ＣＦＨ₂、−ＯＣＦ₂ＣＦ₂Ｈ又は−ＯＣＦ₂ＣＦＨＣＦ₃を表し、Ｌ¹及びＬ²は各々独立して水素原子又はフッ素原子を表し、Ｚ¹及びＺ²は各々独立して−（ＣＨ₂）₂−、−（ＣＨ₂）₄−、−ＣＯＯ−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ＝ＣＨ−又は単結合を表し、環Ｑ¹はトランス−シクロヘキサン−１，４−ジイル、１，３−ジオキサン−２，５−ジイル、又は水素原子がフッ素原子で置換されていてもよい１，４−フェニレンを表し、環Ｑ²はトランス−シクロヘキサン−１，４−ジイル、又は水素原子がフッ素原子で置換されていてもよい１，４−フェニレンを表し、また、これらの化合物を構成する原子はその同位体で置換されていてもよい。）
【００２５】
〔４〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、一般式（９）及び（１０）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
【００２６】
【化１６】

【００２７】
（式中、Ｒ³及びＲ⁴は各々独立して炭素数１〜１０のアルキル基を表し、このアルキル基中の相隣接しない１個以上のメチレン基は酸素原子又は−ＣＨ＝ＣＨ−で置換されていてもよく、また、このアルキル基中の１個以上の水素原子はフッ素原子で置換されていてもよく、Ｙ³はシアノ基又は−Ｃ≡Ｃ−ＣＮを表し、環Ｑ³はトランス−シクロヘキサン−１，４−ジイル、１，４−フェニレン、１，３−ジオキサン−２，５−ジイル又はピリミジン−２，５−ジイルを表し、環Ｑ⁴はトランス−シクロヘキサン−１，４−ジイル、ピリミジン−２，５−ジイル、又は水素原子がフッ素原子で置換されていてもよい１，４−フェニレンを表し、環Ｑ⁵はトランス−シクロヘキサン−１，４−ジイル又は１，４−フェニレンを表し、Ｚ³は−（ＣＨ₂）₂−、−ＣＯＯ−又は単結合を表し、Ｌ³、Ｌ⁴及びＬ⁵は各々独立して水素原子又はフッ素原子を表し、ｂ、ｃ及びｄは各々独立して０又は１を表し、また、これらの化合物を構成する原子はその同位体で置換されていてもよい。）
【００２８】
〔５〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、前記一般式（６）、（７）及び（８）からなる化合物群から選択される化合物を少なくとも１種類含有し、第三成分として、一般式（１１）、（１２）及び（１３）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
【００２９】
【化１７】

【００３０】
（式中、Ｒ⁵及びＲ⁶は各々独立して炭素数１〜１０のアルキル基を表し、このアルキル基中の相隣接しない１個以上のメチレン基は酸素原子又は−ＣＨ＝ＣＨ−で置換されていてもよく、また、このアルキル基中の１個以上の水素原子はフッ素原子で置換されていてもよく、環Ｑ⁶、環Ｑ⁷及び環Ｑ⁸は各々独立して、トランス−シクロヘキサン−１，４−ジイル、ピリミジン−２，５−ジイル、又は水素原子がフッ素原子で置換されていてもよい１，４−フェニレンを表し、Ｚ⁴及びＺ⁵は各々独立して、−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ₂）₂−、−ＣＨ＝ＣＨ−又は単結合を表し、また、これらの化合物を構成する原子はその同位体で置換されていてもよい。）
【００３１】
〔６〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、前記一般式（１４）、（１５）及び（１６）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
【００３２】
【化１８】

【００３３】
（式中、Ｒ⁷及びＲ⁸は各々独立して炭素数１〜１０のアルキル基を表し、このアルキル基中の相隣接しない１個以上のメチレン基は酸素原子又は−ＣＨ＝ＣＨ−で置換されていてもよく、また、このアルキル基中の１個以上の水素原子はフッ素原子で置換されていてもよく、環Ｑ⁹及び環Ｑ¹⁰は各々独立して、トランス−シクロヘキサン−１，４−ジイル又は１，４−フェニレンを表し、Ｌ⁶及びＬ⁷は各々独立して水素原子又はフッ素原子を表すが同時に水素原子を表すことはなく、Ｚ⁶及びＺ⁷は各々独立して、−（ＣＨ₂）₂−、−ＣＯＯ−又は単結合を表し、また、これらの化合物を構成する原子はその同位体で置換されていてもよい。）
【００３４】
〔７〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、前記一般式（１１）、（１２）及び（１３）からなる化合物群から選択される化合物を少なくとも１種類含有し、第三成分として、前記一般式（１４）、（１５）及び（１６）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
〔８〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、前記一般式（９）及び（１０）からなる化合物群から選択される化合物を少なくとも１種類含有し、第三成分として、前記一般式（１１）、（１２）及び（１３）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
【００３５】
〔９〕第一成分として、第〔１〕項に記載の化合物を少なくとも１種類含有し、第二成分として、前記一般式（６）、（７）及び（８）からなる化合物群から選択される化合物を少なくとも１種類含有し、第三成分として、前記一般式（９）及び（１０）からなる化合物群から選択される化合物を少なくとも１種類含有し、第四成分として、前記一般式（１１）、（１２）及び（１３）からなる化合物群から選択される化合物を少なくとも１種類含有することを特徴とする液晶組成物。
〔１０〕第〔２〕〜〔９〕項の何れか１項に記載の液晶組成物に加えて、更に１種類以上の光学活性化合物を含有することを特徴とする液晶組成物。
〔１１〕第〔２〕〜〔１０〕項の何れか１項に記載の液晶組成物を用いて構成した液晶表示素子。
【００３６】
第〔６〕項及び第〔７〕項の発明は、Ｎ型（Δεが負）の液晶組成物に関する発明である。Ｎ型の液晶組成物は、例えば特開平２−１７６６２５号公報に記載されているような垂直配向方式や、ＩＰＳ等、種々の表示方式で駆動できる。また、第〔３〕、〔４〕、〔５〕、〔８〕及び〔９〕項の発明はＰ型（Δεが正）の液晶組成物に関する発明であるが、このようなＰ型液晶組成物の成分としてＮ型の化合物を使用することもできる。このことによって、誘電率異方性値を液晶組成物の使用目的に応じて自由に設定できるのみならず、その他の特性、例えば液晶組成物の屈折率異方性値や弾性定数のコントロール等も可能となる。
【００３９】
一般式（２）で表される本発明の化合物の好ましい態様を以下に示す。一般式（２）で表される化合物のＲ^１及びＹ^１は各々独立して、直鎖の、炭素数１〜２０のアルキル基、炭素数１〜１９のアルコキシ基、炭素数２〜２０のアルケニル基、アルケニルオキシ基、アルキニル基、アルキニルオキシ基、炭素数２〜１９のアルコキシアルキル基、炭素数２〜１８のアルコキシアルコキシ基を表し、これらの基中の１個以上の水素原子はフッ素原子又は塩素原子で置換されていてもよく、又は各々独立して、水素原子、ハロゲン原子、−ＣＮ、−ＯＣＮ、−ＮＣ又は−ＮＣＳを表す。
【００４０】
一般式（２）においてＲ¹及びＹ¹で表される基として、具体的には、炭素原子と水素原子のみから構成される飽和アルキル基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルケニル基、ハロアルケニル基、アルケニルオキシ基、ハロアルケニルオキシ基、アルキニル基、ハロアルキニル基、アルキニルオキシ基、ハロアルキニルオキシ基、アルコキシアルキル基、ハロアルコキシアルキル基、アルコキシアルコキシ基、及びハロアルコキシアルコキシ基が挙げられる。
【００４１】
Ｒ¹及びＹ¹の例としてより具体的には、以下の基又は原子を示すことができる。−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｃ₃Ｈ₇、−Ｃ₄Ｈ₉、−Ｃ₅Ｈ₁₁、−Ｃ₆Ｈ₁₃、−Ｃ₇Ｈ₁₅、−Ｃ₈Ｈ₁₇、−Ｃ₉Ｈ₁₉、−Ｃ₁₀Ｈ₂₁、−ＣＦＨ₂、−ＣＦ₂Ｈ、−ＣＦ₃、−ＣＨ₂ＣＨ₂Ｆ、−ＣＨ₂ＣＨＦ₂、−ＣＨ₂ＣＦ₃、−ＣＦ₂ＣＨ₃、−ＣＦ₂ＣＦ₂Ｈ、−ＣＦＨＣＦ₃、−ＣＦ₂ＣＦ₃、−（ＣＨ₂）₂ＣＨ₂Ｆ、−（ＣＨ₂）₂ＣＨＦ₂、−（ＣＨ₂）₂ＣＦ₃、−ＣＨ₂ＣＦ₂ＣＨ₃、−ＣＨ₂ＣＦ₂ＣＦ₃、−ＣＦ₂Ｃ₂Ｈ₅、−Ｃ₃Ｆ₇、−ＣＦ₂ＣＦＨＣＦ₃、−（ＣＨ₂）₃ＣＨ₂Ｆ、−（ＣＨ₂）₄ＣＨ₂Ｆ、−（ＣＨ₂）₅ＣＨ₂Ｆ、−ＣＦ₂Ｃ₃Ｈ₇、−ＣＨ₂ＣＦ₂Ｃ₂Ｈ₅、−（ＣＨ₂）₂ＣＦ₂ＣＨ₃、−ＣＦ₂Ｃ₄Ｈ₉、−ＣＨ₂ＣＦ₂ＣＨ₃、−（ＣＨ₂）₂ＣＦ₂Ｃ₂Ｈ₅、−（ＣＨ₂）₃ＣＦ₂ＣＨ₃、
【００４２】
−ＯＣＨ₃、−ＯＣ₂Ｈ₅、−ＯＣ₃Ｈ₇、−ＯＣ₄Ｈ₉、−ＯＣ₅Ｈ₁₁、−ＯＣ₆Ｈ₁₃、−ＯＣ₇Ｈ₁₅、−ＯＣ₈Ｈ₁₇、−ＯＣ₉Ｈ₁₉、−ＯＣ₁₀Ｈ₂₁、−ＯＣＦＨ₂、−ＯＣＦ₂Ｈ、−ＯＣＦ₃、−ＯＣＨ₂ＣＨ₂Ｆ、−ＯＣＨ₂ＣＨＦ₂、−ＯＣＨ₂ＣＦ₃、−ＯＣＦ₂ＣＨ₃、−ＯＣＦ₂ＣＦ₂Ｈ、−ＯＣＦＨＣＦ₃、−ＯＣＦ₂ＣＦ₃、−Ｏ（ＣＨ₂）₂ＣＨ₂Ｆ、−Ｏ（ＣＨ₂）₂ＣＨＦ₂、−Ｏ（ＣＨ₂）₂ＣＦ₃、−ＯＣＨ₂ＣＦ₂ＣＨ₃、−ＯＣＨ₂ＣＦ₂ＣＦ₃、−ＯＣＦ₂Ｃ₂Ｈ₅、−ＯＣ₃Ｆ₇、−ＯＣＦ₂ＣＦＨＣＦ₃、−Ｏ（ＣＨ₂）₃ＣＨ₂Ｆ、−Ｏ（ＣＨ₂）₄ＣＨ₂Ｆ、−Ｏ（ＣＨ₂）₅ＣＨ₂Ｆ、−ＯＣＦ₂Ｃ₃Ｈ₇、−ＯＣＨ₂ＣＦ₂Ｃ₂Ｈ₅、−Ｏ（ＣＨ₂）₂ＣＦ₂ＣＨ₃、−ＯＣＦ₂Ｃ₄Ｈ₉、−ＯＣＨ₂ＣＦ₂ＣＨ₃、−Ｏ（ＣＨ₂）₂ＣＦ₂Ｃ₂Ｈ₅、−Ｏ（ＣＨ₂）₃ＣＦ₂ＣＨ₃、
【００４３】
−ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨＣＨ₃、−ＣＨ＝ＣＨＣ₂Ｈ₅、−ＣＨ＝ＣＨＣ₃Ｈ₇、−ＣＨ＝ＣＨＣ₄Ｈ₉、−ＣＨ₂ＣＨ＝ＣＨＣＨ₃、−ＣＨ₂ＣＨ＝ＣＨＣ₂Ｈ₅、−ＣＨ₂ＣＨ＝ＣＨＣ₃Ｈ₇、−ＣＨ₂ＣＨ＝ＣＨＣ₄Ｈ₉、−（ＣＨ₂）₂ＣＨ＝ＣＨＣＨ₃、−（ＣＨ₂）₂ＣＨ＝ＣＨＣ₂Ｈ₅、−（ＣＨ₂）₂ＣＨ＝ＣＨＣ₃Ｈ₇、−（ＣＨ₂）₂ＣＨ＝ＣＨＣ₄Ｈ₉、−ＣＨ₂ＣＨ＝ＣＨ₂、−（ＣＨ₂）₂ＣＨ＝ＣＨ₂、−（ＣＨ₂）₃ＣＨ＝ＣＨ₂、−（ＣＨ₂）₄ＣＨ＝ＣＨ₂、−（ＣＨ₂）₅ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨＣＨ₂ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₃ＣＨ＝ＣＨ₂、−ＣＨ₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ＝ＣＨ₂、−（ＣＨ₂）₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ＝ＣＨ₂、
【００４４】
−ＣＦ＝ＣＦ₂、−ＣＨ＝ＣＦ₂、−ＣＨ＝ＣＨＦ、−ＣＨ₂ＣＦ＝ＣＦ₂、−ＣＨ₂ＣＨ＝ＣＦＨ、−（ＣＨ₂）₂ＣＨ＝ＣＦ₂、−（ＣＨ₂）₂ＣＨ＝ＣＨＦ、−（ＣＨ₂）₃ＣＨ＝ＣＦ₂、−（ＣＨ₂）₃ＣＨ＝ＣＨＦ、−（ＣＨ₂）₄ＣＨ＝ＣＦ₂、−（ＣＨ₂）₄ＣＨ＝ＣＨＦ、−（ＣＨ₂）₅ＣＨ＝ＣＦ₂、−（ＣＨ₂）₅ＣＨ＝ＣＨＦ、−ＣＨ＝ＣＨＣＨ₂ＣＨ₂Ｆ、−ＣＨ＝ＣＨＣＨ₂ＣＨ₂Ｃｌ、−ＣＨ＝ＣＨＣＨ₂ＣＨＦ₂、−ＣＨ＝ＣＨＣＨ₂ＣＦ₃、−ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ₂Ｆ、−ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨＦ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＦ₃、−ＣＨ＝ＣＨ（ＣＨ₂）₃ＣＨ₂Ｆ、−ＣＨ＝ＣＨ（ＣＨ₂）₃ＣＨＦ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₃ＣＦ₃、−ＣＨ＝ＣＨ（ＣＨ₂）₄ＣＨ₂Ｆ、−ＣＨ＝ＣＨ（ＣＨ₂）₄ＣＨＦ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₄ＣＦ₃、−ＣＨ₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ₂Ｆ、−ＣＨ₂ＣＨ＝ＣＨＣＨ₂ＣＨ₂Ｆ、−（ＣＨ₂）₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ₂Ｆ、−（ＣＨ₂）₂ＣＨ＝ＣＨＣＨ₂ＣＨ₂Ｆ、−ＣＨ＝ＣＨＣＨ₂ＣＨ＝ＣＦ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ＝ＣＦ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＦ＝ＣＦ₂、−ＣＨ＝ＣＨ（ＣＨ₂）₃ＣＨＦＣＨ₃、
【００４５】
−ＯＣＨ₂ＣＨ＝ＣＨＣＨ₃、−ＯＣＨ₂ＣＨ＝ＣＨＣ₂Ｈ₅、−ＯＣＨ₂ＣＨ＝ＣＨＣ₃Ｈ₇、−ＯＣＨ₂ＣＨ＝ＣＨＣ₄Ｈ₉、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨＣＨ₃、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨＣ₂Ｈ₅、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨＣ₃Ｈ₇、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨＣ₄Ｈ₉、−ＯＣＨ₂ＣＨ＝ＣＨ₂、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨ₂、−Ｏ（ＣＨ₂）₃ＣＨ＝ＣＨ₂、−Ｏ（ＣＨ₂）₄ＣＨ＝ＣＨ₂、−Ｏ（ＣＨ₂）₅ＣＨ＝ＣＨ₂、−ＯＣＨ₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ＝ＣＨ₂、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ＝ＣＨ₂、
【００４６】
−ＯＣＨ₂ＣＦ＝ＣＦ₂、−ＯＣＨ₂ＣＨ＝ＣＦ₂、−ＯＣＨ₂ＣＦ＝ＣＨＦ、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＦ₂、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨＦ、−Ｏ（ＣＨ₂）₃ＣＨ＝ＣＦ₂、−Ｏ（ＣＨ₂）₃ＣＨ＝ＣＨＦ、−Ｏ（ＣＨ₂）₄ＣＨ＝ＣＦ₂、−Ｏ（ＣＨ₂）₄ＣＨ＝ＣＨＦ、−Ｏ（ＣＨ₂）₅ＣＨ＝ＣＦ₂、−Ｏ（ＣＨ₂）₅ＣＨ＝ＣＨＦ、−ＯＣＨ₂ＣＨ＝ＣＨＣＨ₂ＣＨ₂Ｆ、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨ（ＣＨ₂）₂ＣＨ₂Ｆ、−Ｏ（ＣＨ₂）₂ＣＨ＝ＣＨＣＨ₂ＣＨ₂Ｆ、
【００４７】
−Ｃ≡ＣＨ、−Ｃ≡ＣＣＨ₃、−Ｃ≡ＣＣ₂Ｈ₅、−Ｃ≡ＣＣ₃Ｈ₇、−Ｃ≡ＣＣ₄Ｈ₉、−ＣＨ₂Ｃ≡ＣＨ、−ＣＨ₂Ｃ≡ＣＣＨ₃、−ＣＨ₂Ｃ≡ＣＣ₂Ｈ₅、−ＣＨ₂Ｃ≡ＣＣ₃Ｈ₇、−ＣＨ₂Ｃ≡ＣＣ₄Ｈ₉、−（ＣＨ₂）₂Ｃ≡ＣＨ、−（ＣＨ₂）₂Ｃ≡ＣＣＨ₃、−（ＣＨ₂）₂Ｃ≡ＣＣ₂Ｈ₅、−（ＣＨ₂）₂Ｃ≡ＣＣ₃Ｈ₇、−（ＣＨ₂）₂Ｃ≡ＣＣ₄Ｈ₉、−（ＣＨ₂）₃Ｃ≡ＣＨ、−（ＣＨ₂）₃Ｃ≡ＣＣＨ₃、−（ＣＨ₂）₃Ｃ≡ＣＣ₂Ｈ₅、−（ＣＨ₂）₃Ｃ≡ＣＣ₃Ｈ₇、−（ＣＨ₂）₃Ｃ≡ＣＣ₄Ｈ₉、−Ｃ≡ＣＣＦ₃、−Ｃ≡ＣＣ₂Ｆ₅、−Ｃ≡ＣＣ₃Ｆ₇、−ＣＨ₂Ｃ≡ＣＣＦ₃、−（ＣＨ₂）₂Ｃ≡ＣＣＦ₃、
【００４８】
−ＯＣＨ₂Ｃ≡ＣＨ、−ＯＣＨ₂Ｃ≡ＣＣＨ₃、−ＯＣＨ₂Ｃ≡ＣＣ₂Ｈ₅、−ＯＣＨ₂Ｃ≡ＣＣ₃Ｈ₇、−ＯＣＨ₂Ｃ≡ＣＣ₄Ｈ₉、−Ｏ（ＣＨ₂）₂Ｃ≡ＣＨ、−Ｏ（ＣＨ₂）₂Ｃ≡ＣＣＨ₃、−Ｏ（ＣＨ₂）₂Ｃ≡ＣＣ₂Ｈ₅、−Ｏ（ＣＨ₂）₂Ｃ≡ＣＣ₃Ｈ₇、−Ｏ（ＣＨ₂）₂Ｃ≡ＣＣ₄Ｈ₉、−Ｏ（ＣＨ₂）₃Ｃ≡ＣＨ、−Ｏ（ＣＨ₂）₃Ｃ≡ＣＣＨ₃、−Ｏ（ＣＨ₂）₃Ｃ≡ＣＣ₂Ｈ₅、−Ｏ（ＣＨ₂）₃Ｃ≡ＣＣ₃Ｈ₇、−Ｏ（ＣＨ₂）₃Ｃ≡ＣＣ₄Ｈ₉、
【００４９】
−ＯＣＨ₂Ｃ≡ＣＣＦ₃、−Ｏ（ＣＨ₂）₂Ｃ≡ＣＣＦ₃、−ＣＨ₂ＯＣＨ₃、−ＣＨ₂ＯＣ₂Ｈ₅、−ＣＨ₂ＯＣ₃Ｈ₇、−ＣＨ₂ＯＣ₄Ｈ₉、−ＣＨ₂ＯＣ₅Ｈ₁₁、−（ＣＨ₂）₂ＯＣＨ₃、−（ＣＨ₂）₂ＯＣ₂Ｈ₅、−（ＣＨ₂）₂ＯＣ₃Ｈ₇、−（ＣＨ₂）₂ＯＣ₄Ｈ₉、−（ＣＨ₂）₂ＯＣ₅Ｈ₁₁、−（ＣＨ₂）₃ＯＣＨ₃、−（ＣＨ₂）₃ＯＣ₂Ｈ₅、−（ＣＨ₂）₃ＯＣ₃Ｈ₇、−（ＣＨ₂）₃ＯＣ₄Ｈ₉、−（ＣＨ₂）₃ＯＣ₅Ｈ₁₁、−（ＣＨ₂）₄ＯＣＨ₃、
【００５０】
−ＣＦ₂ＯＣＨ₃、−ＣＦ₂ＯＣ₂Ｈ₅、−ＣＦ₂ＯＣ₃Ｈ₇、−ＣＦ₂ＯＣ₄Ｈ₉、−ＣＦ₂ＯＣ₅Ｈ₁₁、−ＣＨ₂ＯＣＦ₃、−ＣＨ₂ＯＣ₂Ｆ₅、−ＯＣＨ₂ＯＣＨ₃、−ＯＣＨ₂ＯＣ₂Ｈ₅、−ＯＣＨ₂ＯＣ₃Ｈ₇、−ＯＣＨ₂ＯＣ₄Ｈ₉、−ＯＣＨ₂ＯＣ₅Ｈ₁₁、−Ｏ（ＣＨ₂）₂ＯＣＨ₃、−Ｏ（ＣＨ₂）₂ＯＣ₂Ｈ₅、−Ｏ（ＣＨ₂）₂ＯＣ₃Ｈ₇、−Ｏ（ＣＨ₂）₂ＯＣ₄Ｈ₉、−Ｏ（ＣＨ₂）₂ＯＣ₅Ｈ₁₁、−Ｏ（ＣＨ₂）₃ＯＣＨ₃、−Ｏ（ＣＨ₂）₃ＯＣ₂Ｈ₅、−Ｏ（ＣＨ₂）₃ＯＣ₃Ｈ₇、−Ｏ（ＣＨ₂）₃ＯＣ₄Ｈ₉、−Ｏ（ＣＨ₂）₃ＯＣ₅Ｈ₁₁、−Ｏ（ＣＨ₂）₄ＯＣＨ₃、
【００５１】
−ＯＣＨ₂ＯＣＦ₃、−ＯＣＨ₂ＯＣ₂Ｆ₅、
【００５２】
水素原子、ハロゲン原子、−ＣＮ、−ＯＣＮ、−ＮＣ及び−ＮＣＳ。
【００５３】
一般式（２）で表される化合物の化学的・物理的安定性に特に注目する場合、Ｒ¹及びＹ¹は、炭素原子と水素原子のみから構成される飽和アルキル基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルコキシアルキル基、ハロアルコキシアルキル基、アルコキシアルコキシ基、ハロアルコキシアルコキシ基、水素原子、ハロゲン原子、−ＣＮ、−ＯＣＮ、又は−ＮＣであることが好ましい。
【００５４】
一般式（２）で表される化合物の負の誘電率異方性値の絶対値をより大きくしたい場合、Ｒ¹及びＹ¹は、炭素原子と水素原子のみから構成される飽和アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基、アルキニル基、アルキニルオキシ基、アルコキシアルキル基、アルコキシアルコキシ基、又は水素原子等の極性の低い置換基であることが好ましい。
【００５５】
一般式（２）で表される化合物のＸ¹、Ｘ²、Ｘ³及びＸ⁴の内、最低限１個は−Ｏ（ＣＨ ₂ ） ₂ Ｏ−で表される基である。
【００５６】
上記以外で好ましい基としては、単結合、−（ＣＨ₂）₂−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−（ＣＨ₂）₄−、−（ＣＨ₂）₃Ｏ−、−Ｏ（ＣＨ₂）₃−、−ＣＨ＝ＣＨＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ＝ＣＨＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ＝ＣＨ−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ＝ＣＨＣＨ₂Ｏ−、−ＯＣＨ₂ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ₂ＣＦ₂−、−ＣＦ₂ＣＨ₂−、−（ＣＦ₂）₂−、−（ＣＦ₂）₄−、−（ＣＨ₂）₂ＣＯＯ−、−ＯＣＯ（ＣＨ₂）₂−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣ≡Ｃ−、及び−Ｃ≡ＣＣＨ＝ＣＨ−である。
【００５７】
一般式（２）で表される化合物の化学的・物理的安定性に特に注目する場合、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴に好ましい基は、−Ｏ（ＣＨ ₂ ） ₂ Ｏ−で表される基であるが、それら以外の基で、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴に好ましいものとして以下に示す基が挙げられる。単結合、−（ＣＨ₂）₂−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−（ＣＨ₂）₄−、−（ＣＨ₂）₃Ｏ−、−Ｏ（ＣＨ₂）₃−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ₂ＣＦ₂−、−ＣＦ₂ＣＨ₂−、−（ＣＦ₂）₂−、−（ＣＦ₂）₄−、−（ＣＨ₂）₂ＣＯＯ−、及び−ＯＣＯ（ＣＨ₂）₂−。一般式（２）で表される化合物の負の誘電率異方性値の絶対値をより大きくしたい場合、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴に好ましい基は、−Ｏ（ＣＨ ₂ ） _２ Ｏ−で表される基であるが、それら以外の基で、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴に好ましいものとして以下に示す基が挙げられる。単結合、−（ＣＨ₂）₂−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−（ＣＨ₂）₄−、−（ＣＨ₂）₃Ｏ−、−Ｏ（ＣＨ₂）₃−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ₂ＣＦ₂−、−ＣＦ₂ＣＨ₂−、−（ＣＦ₂）₂−、−（ＣＦ₂）₄−、−（ＣＨ₂）₂ＣＯＯ−、及び−ＯＣＯ（ＣＨ₂）₂−。
【００５８】
一般式（２）で表される化合物の環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴及び環Ａ⁵の内、最低限１個は２，３−ジフルオロベンゼン−１，４−ジイル、２，３−ジクロロベンゼン−１，４−ジイル、及び２−クロロ−３−フルオロベンゼン−１，４−ジイル。
【００５９】
上記以外の環で好ましい環としては、ビシクロ〔１．１．１〕ペンタン−１，３−ジイル、トランス−シクロヘキサン−１，４−ジイル、シクロヘキサ−１−エン−１，４−ジイル、及び１，４−フェニレンが挙げられ、これらの環を構成する炭素原子は窒素原子、酸素原子又は硫黄原子で置換されていてもよく、環上の水素原子はハロゲン原子又はシアノ基で置換されていてもよい。
【００６０】
具体的には、１−シアノ−トランス−シクロヘキサン−１，４−ジイル、２，２−ジフルオロ−トランス−シクロヘキサン−１，４−ジイル、２−フルオロシクロヘキサ−１−エン−１，４−ジイル、及び２，２−ジクロロビシクロ〔１．１．１〕ペンタン−１，３−ジイルが挙げられる。更に、環上の水素原子がフッ素原子、塩素原子又はシアノ基で置換されていてもよい環として、以下に示す環も挙げられる。ビシクロ〔１．１．１〕ペンタン−１，３−ジイル、トランス−シクロヘキサン−１，４−ジイル、シクロヘキサ−１−エン−１，４−ジイル、１，４−フェニレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ピラジン−２，５−ジイル、ピリダジン−３，６−ジイル、１，３−ジチアン−２，５−ジイル、１，３−オキサチアン−２，５−ジイル、及びビシクロ〔２．２．２〕オクタン−１，４−ジイル）。
【００６１】
一般式（２）で表される化合物の化学的・物理的安定性に特に注目する場合、環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴及び環Ａ⁵に好ましい環は、例えば２，３−ジフルオロベンゼン−１，４−ジイルであるが、それ以外のもので、環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴及び環Ａ⁵に好ましい環として以下に示す環が挙げられる。１−シアノ−トランス−シクロヘキサン−１，４−ジイル、２，２−ジフルオロ−トランス−シクロヘキサン−１，４−ジイル、２−フルオロシクロヘキサ−１−エン−１，４−ジイル、又は２，２−ジクロロビシクロ〔１．１．１〕ペンタン−１，３−ジイル等、環上の水素原子がフッ素原子、塩素原子又はシアノ基で置換されていてもよい環として以下に示す環が挙げられる。ビシクロ〔１．１．１〕ペンタン−１，３−ジイル、トランス−シクロヘキサン−１，４−ジイル、シクロヘキサ−１−エン−１，４−ジイル、１，４−フェニレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ピリダジン−３，６−ジイル、１、３−ジチアン−２，５−ジイル、２，３−ジフルオロベンゼン−１，４−ジイル、及び１，３−オキサチアン−２，５−ジイル。
【００６２】
一般式（２）で表される化合物の負の誘電率異方性値の絶対値をより大きくしたい場合、環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴及び環Ａ⁵に好ましい環は、例えば２，３−ジフルオロベンゼン−１，４−ジイルであるが、それ以外のもので、環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴及び環Ａ⁵に好ましい環として以下に示す環が挙げられる。１−シアノ−トランス−シクロヘキサン−１，４−ジイル、２，２−ジフルオロ−トランス−シクロヘキサン−１，４−ジイル、２−フルオロシクロヘキサ−１−エン−１，４−ジイル、及び２，２−ジクロロビシクロ〔１．１．１〕ペンタン−１，３−ジイル。環上の水素原子がフッ素原子、塩素原子又はシアノ基で置換されていてもよい環として以下に示す環が挙げられる。トランス−シクロヘキサン−１，４−ジイル、シクロヘキサ−１−エン−１，４−ジイル、及びピリダジン−３，６−ジイル。
【００６３】
一般式（２）において、一般式（３）又は一般式（４）で表される部分の少なくとも一方が、一般式（５）で表される基であることが好ましい。具体的には、以下の基を示すことができる。
【００６４】
【化１９】

【００６５】
請求項１に記載の本発明の化合物は絶対値の大きな負の誘電率異方性値を有する。このため、本発明の化合物を主として用いることにより、誘電率異方性値が負の液晶組成物を調整することができる。この液晶組成物は、とりわけ特開平２−１７６６２５号公報に記載されているような垂直配向方式や、ＩＰＳ等をはじめとする、誘電率異方性値が負の液晶組成物を使用する素子の作成に有用なものである。また、他の液晶化合物や組成物に本発明の化合物を混合使用することで、誘電率異方性値の適切な設定を行うことができるため、他の液晶性化合物や組成物の適用範囲を広げることができる。請求項１〜４に記載の本発明の化合物は小さい弾性定数を有し、また、該定数の温度依存性も小さい。従って、本発明の化合物を使用することで駆動電圧の低い新規液晶組成物を調整することができる。
【００６６】
請求項１に記載の本発明の化合物は他の液晶性化合物との良好な相溶性を有している。このため、本発明の化合物を液晶組成物に配合したとき、化合物の析出などの問題が起こり難い。また本発明の化合物を液晶組成物に多量に配合することができ、その結果本発明の化合物の有する優れた特性を液晶組成物に強く反映させることができる。
【００６７】
請求項１に記載の本発明の化合物は、その構造を適切に設計することで所望の大きさの屈折率異方性値を得ることができる。即ち、特に高い屈折率異方性値を必要とする場合は、芳香族環等の共鳴構造を持つ部位を多く含む環を選択すればよい。低い屈折率異方性値を必要とする場合はトランス−シクロヘキサン−１，４−ジイル環等の共鳴構造を持たない部位を多く含む環を選択すればよい。より詳しく説明すれば、一般式（２）で表される本発明の化合物は、Ｒ¹、Ｙ¹、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴、環Ａ⁵、ａ¹、ａ²、ａ³、ａ⁴及びａ⁵を適切に選択することで所望の大きさの屈折率異方性値を得ることができる。更に詳しく説明すれば、環Ａ¹、環Ａ²、環Ａ³、環Ａ⁴及び環Ａ⁵ を適切に選択することで屈折率異方性値を調整することができる。即ち、特に高い屈折率異方性値を必要とする場合は、芳香族環等の共鳴構造を持つ部位を多く含む環を選択すればよい。低い屈折率異方性値を必要とする場合はトランス−シクロヘキサン−１，４−ジイル環等の共鳴構造を持たない部位を多く含む環を選択すればよい。屈折率異方性値を自由に選択することで、液晶パネルの設計の自由度が大きくなる。
【００６８】
請求項１に記載の本発明の化合物は何れも低い粘性を有し、液晶組成物に多量に使用しても、液晶組成物全体の粘度を著しく上昇させることはない。また、粘度の温度依存性、特に低温での温度依存性が極めて小さい。この優れた粘性を有する液晶性化合物を使用することで高速応答性を有する液晶組成物を調整することができる。請求項１に記載の本発明の化合物は何れも化学的・物理的に安定で、これを使用した液晶組成物の比抵抗値、電圧保持率は高い。紫外線、加熱といった外的要因に対する安定性が高く実用液晶組成物の構成要素として十分な化学的・物理的安定性を持つ。
【００６９】
請求項１に記載の本発明の化合物は環の数を適切に選択することでその相転移温度を調整することができる。即ち、特に高い透明点を必要とする場合には４環以上の化合物を、中庸な透明点を必要とする場合は３環の化合物を、特に低い透明点を必要とするときは２環の化合物を選択すればよい。更に詳しく説明すれば、一般式（２）で表される本発明の化合物は、ａ¹、ａ²、ａ³、ａ⁴及びａ⁵を適切に選択することでその相転移温度を調整することができる。即ち、特に高い透明点を必要とする場合にはａ¹＋ａ²＋ａ³＋ａ⁴＋ａ⁵≧４である４環以上の化合物を、中庸な透明点を必要とする場合はａ¹＋ａ²＋ａ³＋ａ⁴＋ａ⁵＝３である３環の化合物を、特に低い透明点を必要とするときはａ¹＋ａ²＋ａ³＋ａ⁴＋ａ⁵＝２である２環の化合物を選択すればよい。
【００７０】
このように、請求項１に記載の本発明の化合物は、電気光学表示材料として好適な諸物性を有する。本発明の化合物を使用することで良好な特性を持つ新規液晶組成物を調整することができる。また、用途に応じてその構造を適切に設計することにより、目的の特性を持つ液晶性化合物、それを用いた液晶組成物や液晶表示素子を得ることもできる。例えば、本発明の化合物は大きな負の誘電率異方性値を表すことを特徴とするが、誘電率異方性値が負の液晶組成物のみに使用することができるにとどまらず、正の誘電率異方性値を持つ組成物に添加してその誘電率異方性値や、その他の特性を調整することもできる。より詳しく説明すれば、本発明の化合物やこれを用いた液晶組成物は誘電率異方性値が負である化合物や組成物を用いる各種表示方式（例えば、特開平２−１７６６２５号公報に記載されているような垂直配向方式、ＩＰＳ、ＥＣＢ（ＨＡＮ又はＤＡＰ等）、ＤＳ、ＧＨ又はＰＣ等）、とりわけ特開平２−１７６６２５号公報に記載されているような垂直配向方式や、ＩＰＳに使用できる。しかし、それらの方式に使用できるのみならず、誘電率異方性値が正である化合物や組成物を用いる各種表示方式（例えば、ＴＮ、ＳＴＮ、又はＴＮをベースにしたＡＭ（ＴＦＴ又はＭＩＭ）等）用の液晶組成物の諸特性（例えば、誘電率異方性値、弾性定数、屈折率異方性値、粘度、又は化学的・物理的安定性）の改善や調整にも使用することができる。
【００７１】
以下、本発明の液晶組成物に関して説明する。本発明に係る液晶組成物は、請求項１に記載の化合物の少なくとも１種類を０．１〜９９．９重量％の割合で含有することが、優良な特性を発現せしめるために好ましい。更に詳しくは、本発明で提供される液晶組成物は、請求項１の何れかに記載の化合物を少なくとも１種類含有する第一成分に加え、液晶組成物の目的に応じて一般式（６）〜（１６）で表される化合物群から選択される化合物を適当な割合で混合することにより完成する。本発明の液晶組成物に用いられる一般式（６）〜（８）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。（Ｒ²及びＹ²は前記と同一の意味を表す。）
【００７２】
【化２０】

【００７３】
【化２１】

【００７４】
【化２２】

【００７５】
一般式（６）〜（８）で表される化合物は誘電率異方性値が正の化合物であり、熱的安定性や化学的安定性が非常に優れており、電圧保持率の高い、あるいは比抵抗値の大きいといった高信頼性が要求されるＴＦＴ用の液晶組成物を調製する場合には、特に好ましい化合物である。ＴＦＴ用の液晶組成物を調整する場合、一般式（６）〜（８）で表される化合物の使用量は、液晶組成物の全重量に対して０．１〜９９．９重量％の範囲で使用できるが、好ましくは１０〜９７重量％、より好ましくは４０〜９５重量％である。また、一般式（１１）〜（１３）で表される化合物を、粘度調整の目的で更に含有してもよい。ＳＴＮ又はＴＮ用の液晶組成物を調製する場合も一般式（６）〜（８）で表される化合物を使用することができる。その場合５０重量％以下の使用量が好ましい。
【００７６】
本発明の液晶組成物に用いられる一般式（９）〜（１０）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。（Ｒ³、Ｙ³及びＲ⁴は前記と同一の意味を表す。）
【００７７】
【化２３】

【００７８】
【化２４】

【００７９】
一般式（９）〜（１０）で表される化合物は誘電率異方性値が正でその値が大きく、特に液晶組成物のしきい値電圧を小さくする目的で使用される。また、屈折率異方性値の調整、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。更に、ＳＴＮ又はＴＮ用の液晶組成物のＶ−Ｔ曲線の急峻性を改良する目的にも使用される。
【００８０】
一般式（９）〜（１０）で表される化合物は、特にＳＴＮ及びＴＮ用の液晶組成物を調製する場合には、好ましい化合物である。一般式（９）〜（１０）で表される化合物の使用量を増加させると、液晶組成物のしきい値電圧が小さくなり、粘度が上昇する。従って、液晶組成物の粘度が要求特性を満足する限り、多量に使用した方が低電圧駆動できるので有利である。一般式（９）〜（１０）で表される化合物の使用量は、ＳＴＮ又はＴＮ用の液晶組成物を調整する場合には０．１〜９９．９重量％の範囲で使用できるが、好ましくは１０〜９７重量％、より好ましくは４０〜９５重量％である。
【００８１】
本発明の液晶組成物に用いられる一般式（１１）〜（１３）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。（Ｒ⁵及びＲ⁶は前記と同一の意味を表す。）
【００８２】
【化２５】

【００８３】
一般式（１１）〜（１３）で表される化合物は、誘電率異方性の絶対値が小さく、中性に近い化合物である。一般式（１１）で表される化合物は主として粘度調整又は屈折率異方性値の調整の目的で使用される。また、一般式（１２）及び（１３）で表される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又は屈折率異方性値の調整の目的で使用される。一般式（１１）〜（１３）で表される化合物の使用量を増加させると液晶組成物のしきい値電圧が大きくなり、粘度が小さくなる。従って、液晶組成物のしきい値電圧の要求値を満足している限り、多量に使用することができる。一般式（１１）〜（１３）で表される化合物の使用量は、ＴＦＴ用の液晶組成物を調製する場合には、好ましくは４０重量％、より好ましくは３５重量％以下である。また、ＳＴＮ又はＴＮ用の液晶組成物を調整する場合には、好ましくは７０重量％以下、より好ましくは６０重量％以下である。
【００８４】
本発明の液晶組成物で用いられる一般式（１４）〜（１６）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。（Ｒ⁷及びＲ⁸は前記と同一の意味を表す。）
【００８５】
【化２６】

【００８６】
一般式（１４）〜（１６）で表される化合物は、本発明の請求項１に記載の化合物と同様、誘電率異方性の値が負の化合物であり、Ｎ型の液晶組成物のベース化合物として、あるいはＰ型の液晶組成物の誘電率異方性の制御に用いられる。その他の用途として、一般式（１４）で表される化合物は２環化合物であり、主としてしきい値電圧の調整、粘度調整又は屈折率異方性値の調整の目的で使用される。一般式（１５）で表される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又は屈折率異方性値の調整の目的で使用される。一般式（１６）で表される化合物はネマチックレンジを広げる目的の他、しきい値電圧を小さくする目的及び屈折率異方性値を大きくする目的で使用される。
【００８７】
一般式（１４）〜（１６）で表される化合物は主としてＮ型の液晶組成物に使用され、その使用量を増加させると液晶組成物のしきい値電圧が小さくなるが、粘度が大きくなる。従って、液晶組成物のしきい値電圧の要求値を満足している限り、少量使用することが望ましい。しかしながら負の誘電率異方性の絶対値が５以下であるので、４０重量％より少なくなると低電圧駆動が出来なくなる場合がある。一般式（１４）〜（１６）で表される化合物の使用量は、Ｎ型のＴＦＴ用の液晶組成物を調製する場合には４０重量％以上が好ましく、より好ましくは５０〜９５重量％である。また、弾性定数をコントロールし、液晶組成物の電圧−透過率曲線（Ｖ−Ｔカーブ）を制御する目的で、一般式（１４）〜（１６）で表される化合物をＰ型の組成物に混合する場合もある。この場合の一般式（１４）〜（１６）で表される化合物使用量は３０重量％以下が好ましい。
【００８８】
また、本発明の液晶組成物には、ＯＣＢ（Ｏｐｔｉｃａｌｌｙ Ｃｏｍｐｅｎｓａｔｅｄ Ｂｉｒｅｆｒｉｎｇｅｎｃｅ）用液晶組成物等の特別な場合を除き、通常、液晶組成物のらせん構造を誘起して必要なねじれ角を調整し、逆ねじれ（ｒｅｖｅｒｓｅ ｔｗｉｓｔ）を防ぐ目的で、光学活性化合物を添加する。本発明は、このような目的で使用される公知の光学活性化合物が何れも使用できるが、好ましい化合物として以下の光学活性化合物を挙げることができる。
【００８９】
【化２７】

【００９０】
本発明の液晶組成物では、通常、これらの光学活性化合物を添加して、ねじれのピッチを調整する。ねじれのピッチは、ＴＦＴ用及びＴＮ用の液晶組成物であれば４０〜２００μｍの範囲に調整するのが好ましい。ＳＴＮ用の液晶組成物であれば６〜２０μｍの範囲に調整するのが好ましい。また、双安定ＴＮ（Ｂｉｓｔａｂｌｅ ＴＮ）用の場合は、１．５〜４μｍの範囲に調整するのが好ましい。また、ピッチの温度依存性を調整する目的で、２種類以上の光学活性化合物を添加してもよい。
【００９１】
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、又はテトラジン系等の二色性色素を添加してＧＨ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（ＰＤＬＣＤ）用の液晶組成物としても使用できる。その他、ＤＳ用の液晶組成物としても使用できる。
【００９２】
本発明の液晶組成物は、慣用な方法で調製される。一般には、種々の成分を高い温度で各々溶解させる方法がとられている。
【００９３】
請求項１に記載の本発明の化合物は公知の有機合成化学的手法により容易に製造できる。その製造方法の一例を反応式１に示す。
【００９４】
【化２８】

【００９５】
以下に、上記の合成経路について説明する。式１で表される化合物は、sec-ブチルリチウムのような塩基によりリチオ化され、次いで沃素と反応させて式２で表される化合物へと誘導される。得られた式２の化合物は、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）とＴＨＦ（テトラヒドロフラン）の混合溶媒中で水素化ナトリウムのような塩基の存在下、エチレングリコールと反応させて式３で表される目的の化合物へと誘導される。
【００９６】
【実施例】
以下、実施例により本発明の化合物の製造法及び使用例について更に詳細に説明する。なお、本発明は実施例により何等制限を受けるものではない。実施例の説明において、Ｎは規定濃度（グラム当量／ｌ）、Ｍはモル濃度（ｍｏｌ／ｌ）を表し、液晶性化合物のΔε（誘電率異方性値）は、下記の母液晶Ａ８５ｗｔ％と当該化合物１５ｗｔ％とからなる組成物からの外挿値（２５℃において測定）を表し、Δｎ（屈折率異方性値）は、下記の化合物を母液晶Ｂ８５ｗｔ％と当該化合物１５ｗｔ％とからなる組成物の実測値（２５℃において測定）を表す。母液晶Ａの組成
【００９７】
【化２９】

【００９８】
上記の一般式で表され、両末端のアルキル基（Ｒ⁹、Ｒ¹⁰）が異なる５種類のエステル化合物を、下記の割合で混合し母液晶Ａとした。

【００９９】
母液晶Ｂの組成
【０１００】
【化３０】

【０１０１】
上記の一般式で表され、末端のアルキル基（Ｒ¹¹、Ｒ¹²）が異なる４種類の化合物を、下記の割合で混合し母液晶Ｂとした。

【０１０２】
実施例１
１，２−ビス−（（２，３−ジフルオロ−４−ｎ−プロピルオキシ）フェニルオキシ）エタン（３）の合成
第１段
２，３−ジフルオロ−４−ｎ−プロピルオキシヨードベンゼン（２）の合成２，３−ジフルオロ−ｎ−プロピルオキシベンゼン（１）（８６．０９ｇ、０．５００ｍｏｌ）のＴＨＦ（１０００ｍｌ）溶液に、−７８℃で１．５６Ｍのsec-ブチルリチウムのヘキサン溶液（３８５ｍｌ、０．６００ｍｏｌ）を３０分で滴下し、そのまま３０分撹拌して２、３−ジフルオロ−４−エトキシフェニルリチウムの溶液を得た。この溶液に同温度で沃素（３０４．６ｇ、１．２０ｍｏｌ）のＴＨＦ（５００ｍｌ）溶液を滴下した後、−１０℃で２時間反応させた。反応終了後、反応液に水（１０００ｍｌ）を加えた後、トルエン（２２００ｍｌ）で抽出した。得られた有機層を水（８００ｍｌ）で洗浄した後、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー（溶出溶媒：ヘキサン）で精製して、２，３−ジフルオロ−４−ｎ−プロピルオキシヨードベンゼン（２）（９８．３５ｇ、０．３３０ｍｏｌ；収率６６％）を得た。
ＭＳ／２９８（Ｍ⁺）。
【０１０３】
第２段
１，２−ビス−（（２，３−ジフルオロ−４−ｎ−プロピルオキシ）フェニルオキシ）エタン（３）の合成
エチレングリコール（８．０７ｇ、０．１３０ｍｏｌ）、ＤＭＦ（２００ｍｌ）及びＴＨＦ（２００ｍｌ）の混合物を−１０℃に冷却し、同温度で水素化ナトリウム（９．６０ｇ、０．４００ｍｏｌ）を３０分かけて添加した。同温度で２時間反応させた後、第１段で得られた２，３−ジフルオロ−４−ｎ−プロピルオキシヨードベンゼン（２）（９８．３０ｇ、０．３３０ｍｏｌ）のＴＨＦ（３００ｍｌ）溶液を３０分かけて滴下した。反応液を徐々に室温まで昇温させ、室温で１０時間反応させた。反応終了後、氷冷下、反応液に水（１００ｍｌ）を加え、次いで溶媒を減圧留去した。残渣に水（５００ｍｌ）を加え、次いでトルエン（１２００ｍｌ）で抽出した。得られた有機層を水（５００ｍｌ）で洗浄した後、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー（溶出溶媒：トルエン）、次いで再結晶（ヘキサン：トルエン＝１：１）で精製して、１，２−ビス−（（２，３−ジフルオロ−４−ｎ−プロピルオキシ）フェニルオキシ）エタン（３）（２２．５２ｇ、０．０５６０ｍｏｌ；収率４３％）を得た。
ＭＳ／４０２（Ｍ⁺）、Δε＝−１１．３、Δｎ＝０．１３８。
【０１０４】
実施例１の方法に準じて、以下の化合物の合成ができる。
【０１０５】
【化３１】

【０１０６】
【化３２】

【０１０７】
【発明の効果】
以上説明したように、本発明により、絶対値の大きな負の誘電率異方性値を持ち、かつ低粘性で、制御された光学異方性値、高い比抵抗値及び高い電圧保持率を有し、熱や紫外線照射に対しても安定である液晶性化合物、これを含有する液晶組成物及び該液晶組成物を用いて作成した液晶表示素子を提供することが可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention mainly relates to various display systems such as liquid crystal display elements, for example, vertical alignment system, IPS = in-plane switching, TFT = thin film transistor, TN = twisted nematic, or STN = supertwisted nematic, especially liquid crystal composition for vertical alignment system and IPS. The present invention relates to a novel liquid crystal compound that exhibits various physical properties suitable for a material, a liquid crystal composition having suitable physical properties using the compound, and a liquid crystal display device using the liquid crystal composition. In the present application, the term “liquid crystalline compound” is used as a general term for a compound that exhibits a liquid crystal phase and a compound that does not exhibit a liquid crystal phase but is useful as a component of a liquid crystal composition.
[0002]
[Background]
Conventionally, various liquid crystal display methods have been proposed. As an example of these, the following display method can be cited (the latest technology of liquid crystal, edited by the Industrial Research Committee (1983)). As a method using a liquid crystal composition having a positive dielectric anisotropy value, there is a method such as AM = active matrix (TFT or MIM = metal / insulating film / metal, etc.) based on TN, STN, or TN. . Further, as a method using a liquid crystal composition having a negative dielectric anisotropy value, ECB = electric field control birefringence effect (HAN = hybrid molecular arrangement or DAP = vertical molecular arrangement, etc.), DS = dynamic scattering, GH = There are methods such as guest host or PC = phase transition. Among these methods, the one that is currently in practical use is a method that uses a liquid crystal composition having a positive dielectric anisotropy value. Compared with this, the method of using a liquid crystal composition having a negative dielectric anisotropy value is delayed in practical use. In this connection, the development of liquid crystal compositions having negative dielectric anisotropy values and the compounds themselves are also compared with the development of liquid crystal compositions having positive dielectric anisotropy values and compounds used therefor. Then, the situation is not enough.
[0003]
Under such circumstances, particularly, attempts to improve the narrowness of the viewing angle, which is one of the drawbacks of the liquid crystal display, have recently been actively made. One of the methods is IPS (R. Kiefer et al., JAPAN DISPLAY '92, 547 (1992), M. Oh-e et al., ASIA DISPLAY '95, 577 (1995), JP-T 5-505247, JP 7 -128647 etc.). One of the features of IPS is that, in the conventional liquid crystal panel, electrodes are provided on the upper and lower substrates, respectively, whereas in the liquid crystal panel of this method, comb-shaped electrodes are provided on one substrate. It is. Another feature of this method is that the liquid crystal composition can be used regardless of whether the dielectric anisotropy value is positive or negative. As another example of an attempt to improve the narrowness of the viewing angle, there is a method in which the viewing angle is improved by utilizing the vertical alignment of liquid crystal molecules (JP-A-2-176625, etc.). One of the features of this method is that a liquid crystal composition having a negative dielectric anisotropy is used. Against this background, liquid crystal compounds and liquid crystal compositions having a negative dielectric anisotropy value have been strongly demanded.
[0004]
By the way, in all the display systems, the liquid crystal composition used is not only an appropriate dielectric anisotropy value but also other characteristics such as a refractive index anisotropy value (Δn), an elastic constant ratio K₃₃/ K₁₁(K₃₃: Bend elastic constant, K₁₁: Properties of physical properties such as spray elastic constants) must be adjusted to optimum values, and the liquid crystal phase must be in an appropriate temperature range and low viscosity even at low temperatures. Is done. None of the conventionally known liquid crystal compounds alone satisfy all of these conditions. Therefore, in order to obtain a composition that can be used as a normal liquid crystal phase, it is prepared by mixing a compound having several to twenty or more liquid crystal phases and, if necessary, a compound not having several liquid crystal phases. . Therefore, the individual liquid crystalline compounds are required to have good compatibility with other liquid crystalline compounds, and characteristics such as good compatibility in the low temperature range from the requirement for use in a low temperature environment. Yes.
[0005]
However, as described above, since the conventional display method mainly uses a liquid crystal composition containing a liquid crystal compound having a positive dielectric anisotropy value, the compound having a negative dielectric anisotropy value is used. As for the composition and the composition, the development cannot be said to be sufficient. Therefore, the conventional liquid crystal compounds and compositions have not been able to cope with such diversified methods and various characteristics associated therewith. For example,
・ Even if the dielectric anisotropy value is negative, its absolute value is small,
・ The driving voltage cannot be lowered due to the large elastic constant.
・ Cannot be used in large quantities due to poor compatibility.
・ It is difficult to freely set the refractive index anisotropy value.
・ Viscosity is large,
・ Poor chemical and physical stability
There was a problem that said.
[0006]
An example of a liquid crystal compound having a negative dielectric anisotropy value known before the present invention is a liquid crystal compound having a 2,3-difluorophenylene skeleton (Japanese Patent Laid-Open No. 57-114532). . However, the absolute value of the negative dielectric anisotropy value of these compounds is not necessarily large enough, and the small elastic constant, compatibility, freedom of refractive index anisotropy value, low viscosity, chemical / physical properties The characteristics such as mechanical stability are not always satisfactory, and further improvement has been demanded. In addition, here, in order to improve the above-described characteristics of the compound having a 2,3-difluorophenylene skeleton, for example, attempts to increase the absolute value of the negative dielectric anisotropy have not been sufficiently performed. It was. In particular, a compound having a 2,3-difluorophenylene skeleton includes, for example, —O (CH₂)₂There has never been an idea to introduce an O-skeleton. Thus, the compounds of the present invention are not easily conceivable from the prior art.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to have a negative dielectric anisotropy value such as a vertical alignment method, IPS, ECB (HAN, DAP, etc.), DS, GH, PC, etc. as described in JP-A-2-176625. Not only can it be used for various display methods using a certain compound or composition, but also a compound or composition having a positive dielectric anisotropy value such as AM (TFT or MIM) based on TN, STN, or TN. A novel liquid crystalline compound which can be used for adjusting various properties of liquid crystal compositions for various display systems to be used, which solves the above-mentioned problems, a liquid crystal composition containing the same, and the liquid crystal composition An object of the present invention is to provide a prepared liquid crystal display element.
[0008]
[Means for solving the problems]
As a result of diligent research to solve the above problems, the inventors of the present invention not only have a negative dielectric anisotropy value having a large absolute value but also an appropriate refractive index anisotropy value. The elastic constant is small, the compatibility is good, the viscosity is low, the chemical / physical stability is high, and the compound according to claim 1 is used in the liquid crystal composition. A liquid crystal composition that is small, has a suitable dielectric anisotropy value and refractive index anisotropy value, has a low viscosity, and excellent chemical and physical stability, especially a negative dielectric constant with a large absolute value. The inventors have found that a liquid crystal composition having an isotropic value can be obtained, and that a liquid crystal display element can be obtained using the composition, and the present invention has been completed.
[0009]
That is, the present invention provides the following [1] to [11].
[0012]
[1] General formula (2)
[0013]
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[0014]
(Wherein R¹And Y¹Are each independentlyLinear,An alkyl group having 1 to 20 carbon atoms,Represents an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkoxyalkyl group having 2 to 19 carbon atoms, and an alkoxyalkoxy group having 2 to 18 carbon atoms. ,One or more hydrogen atoms in these groups may be substituted with fluorine atoms or chlorine atoms,Or each independently,Hydrogen atom, halogen atom,-CN,-OCN,-NCOr-NCSX¹, X², X³And X⁴Are each independently a single bond, — (CH₂)₂-, -CH = CH-, -C≡C-, -COO-, -OCO-, -CH₂O-, -OCH₂-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -CH = CHCH₂CH₂-, -CH₂CH = CHCH₂-, -CH₂CH₂CH = CH-, -CH = CHCH = CH-, -CF₂O-, -OCF₂-, -CH = CHCH₂O-, -OCH₂CH = CH-, -CF = CF-, -CH₂CF₂-, -CF₂CH₂-,-(CF₂)₂-,-(CF₂)₄-,-(CH₂)₂COO-, -OCO (CH₂)₂-, -CH = CHCOO-, -OCOCH = CH-, -CH = CHC≡C-, -C≡CCH = CH-, or-O (CH ₂ ) ₂ O-And ring A¹, Ring A², Ring A³, Ring A⁴And ring A⁵Are each independently trans-cyclohexylene-1,4-diyl, cyclohex-1-ene-1,4-diyl, 1,4-phenylene or bicyclo [1,1,1] pentane-1,3-diyl. A ring represented,
[0016]
The carbon atoms constituting these rings may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom, the hydrogen atom on the ring may be substituted with a halogen atom or a cyano group, and a¹, A², A³, A⁴And a⁵Each independently represents 0 or 1. )
[0017]
In general formula (2), general formula (3) or general formula (4)
[0018]
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[0019]
Either one of the parts represented by general formula (5)
[0020]
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[0021]
(W^Three, W^Four, W^FiveAnd W⁶Each independently represents a fluorine atom or a chlorine atom, and n is2Represents. ) A liquid crystal compound represented by
[0022]
[2] A liquid crystal composition comprising at least two components, comprising at least one liquid crystalline compound according to item [1].
[3] A compound selected from the group consisting of general formulas (6), (7) and (8) as the second component, containing at least one compound according to item [1] as the first component A liquid crystal composition containing at least one kind.
[0023]
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[0024]
(Wherein R²Represents an alkyl group having 1 to 10 carbon atoms, and one or more methylene groups that are not adjacent to each other in the alkyl group may be substituted with an oxygen atom or —CH═CH—, One or more hydrogen atoms may be substituted with fluorine atoms, Y²Is a fluorine atom, a chlorine atom, -OCF_Three, -OCF₂H, -CF_Three, -CF₂H, -CFH₂, -OCF₂CF₂H or -OCF₂CFHCF_ThreeRepresents L¹And L²Each independently represents a hydrogen atom or a fluorine atom;¹And Z²Are each independently-(CH₂)₂-,-(CH₂)_Four-, -COO-, -CF₂O-, -OCF₂-, -CH = CH- or a single bond, ring Q¹Represents trans-cyclohexane-1,4-diyl, 1,3-dioxane-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom;²Represents trans-cyclohexane-1,4-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and the atoms constituting these compounds are substituted with the isotope thereof. Also good. )
[0025]
[4] The first component contains at least one compound according to item [1], and the second component contains at least one compound selected from the compound group consisting of general formulas (9) and (10). A liquid crystal composition characterized by comprising:
[0026]
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[0027]
(Wherein R^ThreeAnd R^FourEach independently represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or —CH═CH—, One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and Y^ThreeRepresents a cyano group or —C≡C—CN, and the ring Q^ThreeRepresents trans-cyclohexane-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;^FourRepresents trans-cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and ring Q^FiveRepresents trans-cyclohexane-1,4-diyl or 1,4-phenylene;^ThreeIs-(CH₂)₂-, -COO- or a single bond, L^Three, L^FourAnd L^FiveEach independently represents a hydrogen atom or a fluorine atom, b, c and d each independently represent 0 or 1, and the atoms constituting these compounds may be substituted with the isotopes thereof. )
[0028]
[5] A compound selected from the group consisting of the general formulas (6), (7) and (8) as the second component, containing at least one compound according to item [1] as the first component A liquid crystal composition comprising at least one compound selected from the group consisting of general formulas (11), (12) and (13) as a third component.
[0029]
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[0030]
(Wherein R^FiveAnd R⁶Each independently represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or —CH═CH—, One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and the ring Q⁶, Ring Q⁷And ring Q⁸Each independently represents trans-cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom;^FourAnd Z^FiveEach independently represents —C≡C—, —COO—, — (CH₂)₂It represents-, -CH = CH- or a single bond, and atoms constituting these compounds may be substituted with the isotope thereof. )
[0031]
[6] A compound selected from the group consisting of the general formulas (14), (15) and (16) as the second component, containing at least one compound according to item [1] as the first component A liquid crystal composition containing at least one of the above.
[0032]
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[0033]
(Wherein R⁷And R⁸Each independently represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or —CH═CH—, One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and the ring Q⁹And ring Q^TenEach independently represents trans-cyclohexane-1,4-diyl or 1,4-phenylene;⁶And L⁷Each independently represents a hydrogen atom or a fluorine atom, but does not represent a hydrogen atom at the same time.⁶And Z⁷Are each independently-(CH₂)₂It represents-, -COO- or a single bond, and atoms constituting these compounds may be substituted with the isotope thereof. )
[0034]
[7] A compound selected from the group consisting of the general formulas (11), (12) and (13) as the second component, containing at least one compound according to item [1] as the first component A liquid crystal composition comprising at least one compound selected from the group consisting of the general formulas (14), (15) and (16) as a third component.
[8] As a first component, at least one compound according to item [1] is contained, and as a second component, at least one compound selected from the compound group consisting of the general formulas (9) and (10) is used. A liquid crystal composition comprising at least one compound selected from the group consisting of the general formulas (11), (12) and (13) as a third component.
[0035]
[9] A compound selected from the group consisting of the general formulas (6), (7) and (8) as the second component, containing at least one compound according to item [1] as the first component And at least one compound selected from the compound group consisting of the general formulas (9) and (10) as the third component, and as the fourth component, the general formula (11), A liquid crystal composition comprising at least one compound selected from the group consisting of (12) and (13).
[10No.[2]-[9]A liquid crystal composition comprising one or more optically active compounds in addition to the liquid crystal composition according to any one of the items.
[11No.[2]-[10]A liquid crystal display element comprising the liquid crystal composition according to any one of the items.
[0036]
No.6] And item [7The invention of item [10] relates to an N-type (Δε is negative) liquid crystal composition. The N-type liquid crystal composition can be driven by various display methods such as a vertical alignment method as described in JP-A-2-176625 and IPS. In addition,3], [4], [5], [8〕as well as〔9] Is an invention relating to a P-type (Δε is positive) liquid crystal composition, but an N-type compound can also be used as a component of such a P-type liquid crystal composition. This makes it possible not only to freely set the dielectric anisotropy value according to the intended use of the liquid crystal composition, but also to control other characteristics such as the refractive index anisotropy value and elastic constant of the liquid crystal composition. It becomes possible.
[0039]
The preferable aspect of the compound of this invention represented by General formula (2) is shown below. R of the compound represented by the general formula (2)¹And Y¹Are each independentlyLinear,An alkyl group having 1 to 20 carbon atoms,Represents an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkoxyalkyl group having 2 to 19 carbon atoms, and an alkoxyalkoxy group having 2 to 18 carbon atoms. ,One or more hydrogen atoms in these groups may be substituted with fluorine atoms or chlorine atoms,Or each independently,Hydrogen atom, halogen atom,-CN,-OCN,-NCOr-NCSRepresents.
[0040]
In the general formula (2), R¹And Y¹Specific examples of the group represented by the formula: Groups, alkynyl groups, haloalkynyl groups, alkynyloxy groups, haloalkynyloxy groups, alkoxyalkyl groups, haloalkoxyalkyl groups, alkoxyalkoxy groups, and haloalkoxyalkoxy groups.
[0041]
R¹And Y¹More specifically, the following groups or atoms can be shown as examples. -CH_Three, -C₂H_Five, -C_ThreeH₇, -C_FourH₉, -C_FiveH₁₁, -C₆H₁₃, -C₇H₁₅, -C₈H₁₇, -C₉H₁₉, -C_TenH_{twenty one}, -CFH₂, -CF₂H, -CF_Three, -CH₂CH₂F, -CH₂CHF₂, -CH₂CF_Three, -CF₂CH_Three, -CF₂CF₂H, -CFHCF_Three, -CF₂CF_Three,-(CH₂)₂CH₂F,-(CH₂)₂CHF₂,-(CH₂)₂CF_Three, -CH₂CF₂CH_Three, -CH₂CF₂CF_Three, -CF₂C₂H_Five, -C_ThreeF₇, -CF₂CFHCF_Three,-(CH₂)_ThreeCH₂F,-(CH₂)_FourCH₂F,-(CH₂)_FiveCH₂F, -CF₂C_ThreeH₇, -CH₂CF₂C₂H_Five,-(CH₂)₂CF₂CH_Three, -CF₂C_FourH₉, -CH₂CF₂CH_Three,-(CH₂)₂CF₂C₂H_Five,-(CH₂)_ThreeCF₂CH_Three,
[0042]
-OCH_Three, -OC₂H_Five, -OC_ThreeH₇, -OC_FourH₉, -OC_FiveH₁₁, -OC₆H₁₃, -OC₇H₁₅, -OC₈H₁₇, -OC₉H₁₉, -OC_TenH_{twenty one}, -OCHF₂, -OCF₂H, -OCF_Three, -OCH₂CH₂F, -OCH₂CHF₂, -OCH₂CF_Three, -OCF₂CH_Three, -OCF₂CF₂H, -OCFHCF_Three, -OCF₂CF_Three, -O (CH₂)₂CH₂F, -O (CH₂)₂CHF₂, -O (CH₂)₂CF_Three, -OCH₂CF₂CH_Three, -OCH₂CF₂CF_Three, -OCF₂C₂H_Five, -OC_ThreeF₇, -OCF₂CFHCF_Three, -O (CH₂)_ThreeCH₂F, -O (CH₂)_FourCH₂F, -O (CH₂)_FiveCH₂F, -OCF₂C_ThreeH₇, -OCH₂CF₂C₂H_Five, -O (CH₂)₂CF₂CH_Three, -OCF₂C_FourH₉, -OCH₂CF₂CH_Three, -O (CH₂)₂CF₂C₂H_Five, -O (CH₂)_ThreeCF₂CH_Three,
[0043]
-CH = CH₂, -CH = CHCH_Three, -CH = CHC₂H_Five, -CH = CHC_ThreeH₇, -CH = CHC_FourH₉, -CH₂CH = CHCH_Three, -CH₂CH = CHC₂H_Five, -CH₂CH = CHC_ThreeH₇, -CH₂CH = CHC_FourH₉,-(CH₂)₂CH = CHCH_Three,-(CH₂)₂CH = CHC₂H_Five,-(CH₂)₂CH = CHC_ThreeH₇,-(CH₂)₂CH = CHC_FourH₉, -CH₂CH = CH₂,-(CH₂)₂CH = CH₂,-(CH₂)_ThreeCH = CH₂,-(CH₂)_FourCH = CH₂,-(CH₂)_FiveCH = CH₂, -CH = CHCH = CH₂, -CH = CHCH₂CH = CH₂, -CH = CH (CH₂)₂CH = CH₂, -CH = CH (CH₂)_ThreeCH = CH₂, -CH₂CH = CH (CH₂)₂CH = CH₂,-(CH₂)₂CH = CH (CH₂)₂CH = CH₂,
[0044]
-CF = CF₂, -CH = CF₂, -CH = CHF, -CH₂CF = CF₂, -CH₂CH = CFH,-(CH₂)₂CH = CF₂,-(CH₂)₂CH = CHF,-(CH₂)_ThreeCH = CF₂,-(CH₂)_ThreeCH = CHF,-(CH₂)_FourCH = CF₂,-(CH₂)_FourCH = CHF,-(CH₂)_FiveCH = CF₂,-(CH₂)_FiveCH = CHF, -CH = CHCH₂CH₂F, -CH = CHCH₂CH₂Cl, -CH = CHCH₂CHF₂, -CH = CHCH₂CF_Three, -CH = CH (CH₂)₂CH₂F, -CH = CH (CH₂)₂CHF₂, -CH = CH (CH₂)₂CF_Three, -CH = CH (CH₂)_ThreeCH₂F, -CH = CH (CH₂)_ThreeCHF₂, -CH = CH (CH₂)_ThreeCF_Three, -CH = CH (CH₂)_FourCH₂F, -CH = CH (CH₂)_FourCHF₂, -CH = CH (CH₂)_FourCF_Three, -CH₂CH = CH (CH₂)₂CH₂F, -CH₂CH = CHCH₂CH₂F,-(CH₂)₂CH = CH (CH₂)₂CH₂F,-(CH₂)₂CH = CHCH₂CH₂F, -CH = CHCH₂CH = CF₂, -CH = CH (CH₂)₂CH = CF₂, -CH = CH (CH₂)₂CF = CF₂, -CH = CH (CH₂)_ThreeCHFCH_Three,
[0045]
-OCH₂CH = CHCH_Three, -OCH₂CH = CHC₂H_Five, -OCH₂CH = CHC_ThreeH₇, -OCH₂CH = CHC_FourH₉, -O (CH₂)₂CH = CHCH_Three, -O (CH₂)₂CH = CHC₂H_Five, -O (CH₂)₂CH = CHC_ThreeH₇, -O (CH₂)₂CH = CHC_FourH₉, -OCH₂CH = CH₂, -O (CH₂)₂CH = CH₂, -O (CH₂)_ThreeCH = CH₂, -O (CH₂)_FourCH = CH₂, -O (CH₂)_FiveCH = CH₂, -OCH₂CH = CH (CH₂)₂CH = CH₂, -O (CH₂)₂CH = CH (CH₂)₂CH = CH₂,
[0046]
-OCH₂CF = CF₂, -OCH₂CH = CF₂, -OCH₂CF = CHF, -O (CH₂)₂CH = CF₂, -O (CH₂)₂CH = CHF, -O (CH₂)_ThreeCH = CF₂, -O (CH₂)_ThreeCH = CHF, -O (CH₂)_FourCH = CF₂, -O (CH₂)_FourCH = CHF, -O (CH₂)_FiveCH = CF₂, -O (CH₂)_FiveCH = CHF, -OCH₂CH = CHCH₂CH₂F, -O (CH₂)₂CH = CH (CH₂)₂CH₂F, -O (CH₂)₂CH = CHCH₂CH₂F,
[0047]
-C≡CH, -C≡CCH_Three, -C≡CC₂H_Five, -C≡CC_ThreeH₇, -C≡CC_FourH₉, -CH₂C≡CH, -CH₂C≡CCH_Three, -CH₂C≡CC₂H_Five, -CH₂C≡CC_ThreeH₇, -CH₂C≡CC_FourH₉,-(CH₂)₂C≡CH,-(CH₂)₂C≡CCH_Three,-(CH₂)₂C≡CC₂H_Five,-(CH₂)₂C≡CC_ThreeH₇,-(CH₂)₂C≡CC_FourH₉,-(CH₂)_ThreeC≡CH,-(CH₂)_ThreeC≡CCH_Three,-(CH₂)_ThreeC≡CC₂H_Five,-(CH₂)_ThreeC≡CC_ThreeH₇,-(CH₂)_ThreeC≡CC_FourH₉, -C≡CCF_Three, -C≡CC₂F_Five, -C≡CC_ThreeF₇, -CH₂C≡CCF_Three,-(CH₂)₂C≡CCF_Three,
[0048]
-OCH₂C≡CH, -OCH₂C≡CCH_Three, -OCH₂C≡CC₂H_Five, -OCH₂C≡CC_ThreeH₇, -OCH₂C≡CC_FourH₉, -O (CH₂)₂C≡CH, —O (CH₂)₂C≡CCH_Three, -O (CH₂)₂C≡CC₂H_Five, -O (CH₂)₂C≡CC_ThreeH₇, -O (CH₂)₂C≡CC_FourH₉, -O (CH₂)_ThreeC≡CH, —O (CH₂)_ThreeC≡CCH_Three, -O (CH₂)_ThreeC≡CC₂H_Five, -O (CH₂)_ThreeC≡CC_ThreeH₇, -O (CH₂)_ThreeC≡CC_FourH₉,
[0049]
-OCH₂C≡CCF_Three, -O (CH₂)₂C≡CCF_Three, -CH₂OCH_Three, -CH₂OC₂H_Five, -CH₂OC_ThreeH₇, -CH₂OC_FourH₉, -CH₂OC_FiveH₁₁,-(CH₂)₂OCH_Three,-(CH₂)₂OC₂H_Five,-(CH₂)₂OC_ThreeH₇,-(CH₂)₂OC_FourH₉,-(CH₂)₂OC_FiveH₁₁,-(CH₂)_ThreeOCH_Three,-(CH₂)_ThreeOC₂H_Five,-(CH₂)_ThreeOC_ThreeH₇,-(CH₂)_ThreeOC_FourH₉,-(CH₂)_ThreeOC_FiveH₁₁,-(CH₂)_FourOCH_Three,
[0050]
-CF₂OCH_Three, -CF₂OC₂H_Five, -CF₂OC_ThreeH₇, -CF₂OC_FourH₉, -CF₂OC_FiveH₁₁, -CH₂OCF_Three, -CH₂OC₂F_Five, -OCH₂OCH_Three, -OCH₂OC₂H_Five, -OCH₂OC_ThreeH₇, -OCH₂OC_FourH₉, -OCH₂OC_FiveH₁₁, -O (CH₂)₂OCH_Three, -O (CH₂)₂OC₂H_Five, -O (CH₂)₂OC_ThreeH₇, -O (CH₂)₂OC_FourH₉, -O (CH₂)₂OC_FiveH₁₁, -O (CH₂)_ThreeOCH_Three, -O (CH₂)_ThreeOC₂H_Five, -O (CH₂)_ThreeOC_ThreeH₇, -O (CH₂)_ThreeOC_FourH₉, -O (CH₂)_ThreeOC_FiveH₁₁, -O (CH₂)_FourOCH_Three,
[0051]
-OCH₂OCF_Three, -OCH₂OC₂F_Five,
[0052]
Hydrogen atom, halogen atom,-CN,-OCN,-NCas well as-NCS.
[0053]
When paying particular attention to the chemical and physical stability of the compound represented by the general formula (2), R¹And Y¹Is a saturated alkyl group composed of only carbon and hydrogen atoms, haloalkyl group, alkoxy group, haloalkoxy group, alkoxyalkyl group, haloalkoxyalkyl group, alkoxyalkoxy group, haloalkoxyalkoxy group, hydrogen atom, halogen atom,-CN,-OCNOr-NCIt is preferable that
[0054]
When it is desired to increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (2), R¹And Y¹Is a low-polarity substitution such as a saturated alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkoxyalkyl group, an alkoxyalkoxy group, or a hydrogen atom composed of only carbon and hydrogen atoms It is preferably a group.
[0055]
X of the compound represented by the general formula (2)¹, X², X^ThreeAnd X^FourAt least one of-O (CH ₂ ) ₂ O-It is group represented by these.
[0056]
Other than the above, preferred groups include a single bond and — (CH₂)₂-, -CH = CH-, -C≡C-, -COO-, -OCO-, -CH₂O-, -OCH₂-,-(CH₂)_Four-,-(CH₂)_ThreeO-, -O (CH₂)_Three-, -CH = CHCH₂CH₂-, -CH₂CH = CHCH₂-, -CH₂CH₂CH = CH-, -CH = CHCH = CH-, -CF₂O-, -OCF₂-, -CH = CHCH₂O-, -OCH₂CH = CH-, -CF = CF-, -CH₂CF₂-, -CF₂CH₂-,-(CF₂)₂-,-(CF₂)_Four-,-(CH₂)₂COO-, -OCO (CH₂)₂-, -CH = CHCOO-, -OCOCH = CH-, -CH = CHC≡C-, and -C≡CCH = CH-.
[0057]
When paying particular attention to the chemical and physical stability of the compound represented by the general formula (2), X¹, X², X^ThreeAnd X^FourPreferred groups for-O (CH ₂ ) ₂ O-A group other than those represented by X¹, X², X^ThreeAnd X^FourPreferred groups include the following groups. Single bond,-(CH₂)₂-, -COO-, -OCO-, -CH₂O-, -OCH₂-,-(CH₂)_Four-,-(CH₂)_ThreeO-, -O (CH₂)_Three-, -CF₂O-, -OCF₂-, -CH₂CF₂-, -CF₂CH₂-,-(CF₂)₂-,-(CF₂)_Four-,-(CH₂)₂COO- and -OCO (CH₂)₂-. When it is desired to increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (2), X¹, X², X^ThreeAnd X^FourPreferred groups for-O (CH ₂ ) ₂ O-A group other than those represented by X¹, X², X^ThreeAnd X^FourPreferred groups include the following groups. Single bond,-(CH₂)₂-, -COO-, -OCO-, -CH₂O-, -OCH₂-,-(CH₂)_Four-,-(CH₂)_ThreeO-, -O (CH₂)_Three-, -CF₂O-, -OCF₂-, -CH₂CF₂-, -CF₂CH₂-,-(CF₂)₂-,-(CF₂)_Four-,-(CH₂)₂COO- and -OCO (CH₂)₂-.
[0058]
Ring A of the compound represented by the general formula (2)¹, Ring A², Ring A^Three, Ring A^FourAnd ring A^FiveOf which at least one is 2,3-difluorobenzene-1,4-diyl, 2,3-dichlorobenzene-1,4-diyl, and 2-chloro-3-fluorobenzene-1,4-diyl.
[0059]
Preferred rings other than the above include bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, cyclohex-1-ene-1,4-diyl, and 1 , 4-phenylene, the carbon atoms constituting these rings may be substituted with nitrogen atoms, oxygen atoms or sulfur atoms, and the hydrogen atoms on the rings may be substituted with halogen atoms or cyano groups Good.
[0060]
Specifically, 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohex-1-ene-1,4-diyl And 2,2-dichlorobicyclo [1.1.1] pentane-1,3-diyl. Furthermore, the ring shown below is mentioned as a ring in which the hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom or a cyano group. Bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, cyclohex-1-ene-1,4-diyl, 1,4-phenylene, 1,3-dioxane- 2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,3-dithian-2,5-diyl, 1,3-oxathian-2,5-diyl, and bicyclo [2.2.2] octane-1,4-diyl).
[0061]
When paying particular attention to the chemical and physical stability of the compound represented by the general formula (2), ring A¹, Ring A², Ring A^Three, Ring A^FourAnd ring A^FiveA preferred ring is, for example, 2,3-difluorobenzene-1,4-diyl, but other ring A¹, Ring A², Ring A^Three, Ring A^FourAnd ring A^FivePreferred examples of the ring include the following rings. 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohex-1-ene-1,4-diyl, or 2,2 Examples of the ring in which the hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom or a cyano group, such as dichlorobicyclo [1.1.1] pentane-1,3-diyl, include the rings shown below. Bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, cyclohex-1-ene-1,4-diyl, 1,4-phenylene, 1,3-dioxane- 2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridazine-3,6-diyl, 1,3-dithian-2,5-diyl, 2,3-difluorobenzene-1 , 4-diyl and 1,3-oxathian-2,5-diyl.
[0062]
When the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (2) is to be increased, ring A¹, Ring A², Ring A^Three, Ring A^FourAnd ring A^FiveA preferred ring is, for example, 2,3-difluorobenzene-1,4-diyl, but other ring A¹, Ring A², Ring A^Three, Ring A^FourAnd ring A^FivePreferred examples of the ring include the following rings. 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohex-1-ene-1,4-diyl, and 2,2 -Dichlorobicyclo [1.1.1] pentane-1,3-diyl. Examples of the ring in which the hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom or a cyano group include the following rings. Trans-cyclohexane-1,4-diyl, cyclohex-1-ene-1,4-diyl, and pyridazine-3,6-diyl.
[0063]
In general formula (2), it is preferable that at least one of the parts represented by general formula (3) or general formula (4) is a group represented by general formula (5). Specifically, the following groups can be shown.
[0064]
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[0065]
The compound of the present invention according to claim 1 has a negative dielectric anisotropy value having a large absolute value. Therefore, a liquid crystal composition having a negative dielectric anisotropy value can be adjusted by mainly using the compound of the present invention. This liquid crystal composition is a device that uses a liquid crystal composition having a negative dielectric anisotropy value, such as a vertical alignment method described in JP-A-2-176625, IPS, and the like. It is useful for creation. In addition, since the dielectric anisotropy value can be appropriately set by mixing and using the compound of the present invention in another liquid crystal compound or composition, the application range of other liquid crystal compounds or compositions can be set. Can be spread. The compounds of the present invention according to claims 1 to 4 have a small elastic constant, and the temperature dependence of the constant is also small. Therefore, a novel liquid crystal composition having a low driving voltage can be prepared by using the compound of the present invention.
[0066]
The compound of the present invention described in claim 1 has good compatibility with other liquid crystal compounds. For this reason, when the compound of this invention is mix | blended with a liquid crystal composition, problems, such as precipitation of a compound, do not occur easily. In addition, the compound of the present invention can be blended in a large amount in the liquid crystal composition, and as a result, the excellent characteristics of the compound of the present invention can be strongly reflected in the liquid crystal composition.
[0067]
The compound of the present invention according to claim 1 can obtain a refractive index anisotropy value of a desired size by designing its structure appropriately. That is, when a particularly high refractive index anisotropy value is required, a ring containing many sites having a resonance structure such as an aromatic ring may be selected. When a low refractive index anisotropy value is required, a ring containing a lot of sites not having a resonance structure such as a trans-cyclohexane-1,4-diyl ring may be selected. More specifically, the compound of the present invention represented by the general formula (2) is represented by R¹, Y¹, X¹, X², X^Three, X^Four, Ring A¹, Ring A², Ring A^Three, Ring A^Four, Ring A^Five, A¹, A², A^Three, A^FourAnd a^FiveBy appropriately selecting, a refractive index anisotropy value having a desired size can be obtained. More specifically, ring A¹, Ring A², Ring A^Three, Ring A^FourAnd ring A^Five The refractive index anisotropy value can be adjusted by appropriately selecting. That is, when a particularly high refractive index anisotropy value is required, a ring containing many sites having a resonance structure such as an aromatic ring may be selected. When a low refractive index anisotropy value is required, a ring containing a lot of sites not having a resonance structure such as a trans-cyclohexane-1,4-diyl ring may be selected. By freely selecting the refractive index anisotropy value, the degree of freedom in designing the liquid crystal panel is increased.
[0068]
All of the compounds of the present invention according to claim 1 have a low viscosity, and even when used in a large amount in a liquid crystal composition, the viscosity of the entire liquid crystal composition is not significantly increased. Further, the temperature dependency of the viscosity, in particular, the temperature dependency at a low temperature is extremely small. By using the liquid crystalline compound having this excellent viscosity, a liquid crystal composition having high-speed response can be prepared. The compound of the present invention according to claim 1 is chemically and physically stable, and the liquid crystal composition using the compound has high specific resistance and high voltage holding ratio. It has high stability against external factors such as ultraviolet rays and heating, and has sufficient chemical and physical stability as a component of a practical liquid crystal composition.
[0069]
The phase transition temperature of the compound of the present invention according to claim 1 can be adjusted by appropriately selecting the number of rings. That is, when a high clearing point is required, a compound having 4 or more rings, when a moderate clearing point is required, a tricyclic compound, and when a particularly low clearing point is required, a bicyclic compound Should be selected. More specifically, the compound of the present invention represented by the general formula (2) is a¹, A², A^Three, A^FourAnd a^FiveThe phase transition temperature can be adjusted by appropriately selecting. That is, when a particularly high clearing point is required, a¹+ A²+ A^Three+ A^Four+ A^FiveIf a compound with 4 or more rings, which is ≧ 4, needs a moderate clearing point, a¹+ A²+ A^Three+ A^Four+ A^Five= 3 when a tricyclic compound requires a particularly low clearing point a¹+ A²+ A^Three+ A^Four+ A^FiveA bicyclic compound in which = 2 is selected.
[0070]
Thus, the compound of the present invention according to claim 1 has various physical properties suitable as an electro-optical display material. By using the compound of the present invention, a novel liquid crystal composition having good characteristics can be prepared. In addition, by appropriately designing the structure according to the application, a liquid crystalline compound having desired characteristics, a liquid crystal composition using the same, and a liquid crystal display device can be obtained. For example, the compound of the present invention is characterized by exhibiting a large negative dielectric anisotropy value, but it can be used only for a liquid crystal composition having a negative dielectric anisotropy value, and is positive. It can be added to a composition having a dielectric anisotropy value to adjust the dielectric anisotropy value and other characteristics. More specifically, the compound of the present invention and the liquid crystal composition using the same are described in various display systems using a compound or composition having a negative dielectric anisotropy value (for example, described in JP-A-2-176625). Used for vertical alignment method, IPS, ECB (HAN or DAP, etc.), DS, GH, PC, etc., especially vertical alignment method as described in JP-A-2-176625, and IPS it can. However, various display systems that use not only those systems but also compounds and compositions having a positive dielectric anisotropy value (for example, TN, STN, or TN-based AM (TFT or MIM)) Etc.) for improving and adjusting various properties of liquid crystal compositions (for example, dielectric anisotropy value, elastic constant, refractive index anisotropy value, viscosity, or chemical / physical stability). Can do.
[0071]
Hereinafter, the liquid crystal composition of the present invention will be described. The liquid crystal composition according to the present invention preferably contains at least one of the compounds according to claim 1 in a proportion of 0.1 to 99.9% by weight in order to develop excellent characteristics. More specifically, the liquid crystal composition provided by the present invention has the general formula (6) depending on the purpose of the liquid crystal composition in addition to the first component containing at least one compound according to claim 1. It completes by mixing the compound selected from the compound group represented by-(16) in a suitable ratio. Preferred examples of the compound represented by the general formulas (6) to (8) used in the liquid crystal composition of the present invention include the following compounds. (R²And Y²Represents the same meaning as described above. )
[0072]
Embedded image

[0073]
Embedded image

[0074]
Embedded image

[0075]
The compounds represented by the general formulas (6) to (8) are compounds having a positive dielectric anisotropy value, have excellent thermal stability and chemical stability, and have a high voltage holding ratio. Alternatively, it is a particularly preferable compound when preparing a liquid crystal composition for TFT which requires high reliability such as a large specific resistance value. When adjusting the liquid crystal composition for TFT, the usage-amount of the compound represented by General formula (6)-(8) is the range of 0.1-99.9 weight% with respect to the total weight of a liquid crystal composition. However, it is preferably 10 to 97% by weight, more preferably 40 to 95% by weight. Moreover, you may further contain the compound represented by General formula (11)-(13) for the purpose of viscosity adjustment. The compounds represented by the general formulas (6) to (8) can also be used when preparing a liquid crystal composition for STN or TN. In that case, the amount used is preferably 50% by weight or less.
[0076]
Preferred examples of the compounds represented by the general formulas (9) to (10) used in the liquid crystal composition of the present invention include the following compounds. (R^Three, Y^ThreeAnd R^FourRepresents the same meaning as described above. )
[0077]
Embedded image

[0078]
Embedded image

[0079]
The compounds represented by the general formulas (9) to (10) have a positive dielectric anisotropy value and a large value, and are used particularly for the purpose of reducing the threshold voltage of the liquid crystal composition. It is also used for the purpose of expanding the nematic range such as adjusting the refractive index anisotropy value and increasing the clearing point. Furthermore, it is used for the purpose of improving the steepness of the VT curve of the liquid crystal composition for STN or TN.
[0080]
The compounds represented by the general formulas (9) to (10) are preferable compounds, particularly when preparing liquid crystal compositions for STN and TN. When the amount of the compounds represented by the general formulas (9) to (10) is increased, the threshold voltage of the liquid crystal composition is decreased and the viscosity is increased. Therefore, as long as the viscosity of the liquid crystal composition satisfies the required characteristics, it is advantageous to use a large amount because it can be driven at a low voltage. The amount of the compounds represented by the general formulas (9) to (10) can be used in the range of 0.1 to 99.9% by weight when adjusting the liquid crystal composition for STN or TN. Is 10 to 97% by weight, more preferably 40 to 95% by weight.
[0081]
Preferred examples of the compounds represented by the general formulas (11) to (13) used in the liquid crystal composition of the present invention include the following compounds. (R^FiveAnd R⁶Represents the same meaning as described above. )
[0082]
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[0083]
The compounds represented by the general formulas (11) to (13) have a small absolute value of dielectric anisotropy and are close to neutrality. The compound represented by the general formula (11) is mainly used for the purpose of adjusting the viscosity or adjusting the refractive index anisotropy value. The compounds represented by the general formulas (12) and (13) are used for the purpose of expanding the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. Increasing the amount of the compounds represented by the general formulas (11) to (13) increases the threshold voltage of the liquid crystal composition and decreases the viscosity. Therefore, as long as the required value of the threshold voltage of the liquid crystal composition is satisfied, it can be used in a large amount. The amount of the compounds represented by the general formulas (11) to (13) is preferably 40% by weight, more preferably 35% by weight or less when preparing a liquid crystal composition for TFT. Moreover, when adjusting the liquid crystal composition for STN or TN, it is preferably 70% by weight or less, more preferably 60% by weight or less.
[0084]
Preferred examples of the compounds represented by the general formulas (14) to (16) used in the liquid crystal composition of the present invention include the following compounds. (R⁷And R⁸Represents the same meaning as described above. )
[0085]
Embedded image

[0086]
The compounds represented by the general formulas (14) to (16) are compounds having a negative dielectric anisotropy as in the case of the compound according to claim 1 of the present invention. It is used as a base compound or for controlling the dielectric anisotropy of a P-type liquid crystal composition. As another application, the compound represented by the general formula (14) is a bicyclic compound, and is mainly used for the purpose of adjusting the threshold voltage, adjusting the viscosity, or adjusting the refractive index anisotropy value. The compound represented by the general formula (15) is used for the purpose of expanding the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. The compound represented by the general formula (16) is used not only for the purpose of expanding the nematic range but also for the purpose of reducing the threshold voltage and the value of refractive index anisotropy.
[0087]
The compounds represented by the general formulas (14) to (16) are mainly used in N-type liquid crystal compositions. Increasing the amount of use decreases the threshold voltage of the liquid crystal composition but increases the viscosity. . Therefore, it is desirable to use a small amount as long as the threshold voltage requirement of the liquid crystal composition is satisfied. However, since the absolute value of the negative dielectric anisotropy is 5 or less, if it is less than 40% by weight, low voltage driving may not be possible. The amount of the compounds represented by the general formulas (14) to (16) is preferably 40% by weight or more, more preferably 50 to 95% by weight when preparing a liquid crystal composition for an N-type TFT. is there. Further, for the purpose of controlling the elastic constant and controlling the voltage-transmittance curve (VT curve) of the liquid crystal composition, the compounds represented by the general formulas (14) to (16) are converted into P-type compositions. Sometimes mixed. In this case, the amount of the compound represented by the general formulas (14) to (16) is preferably 30% by weight or less.
[0088]
In addition, except for special cases such as OCB (Optically Compensated Birefringence) liquid crystal composition, the liquid crystal composition of the present invention usually adjusts the necessary twist angle by inducing the helical structure of the liquid crystal composition, An optically active compound is added for the purpose of preventing reverse twist. In the present invention, any of the known optically active compounds used for such purposes can be used, and preferred optically active compounds include the following.
[0089]
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[0090]
In the liquid crystal composition of the present invention, these optically active compounds are usually added to adjust the twist pitch. The twist pitch is preferably adjusted in the range of 40 to 200 μm in the case of a liquid crystal composition for TFT and TN. If it is the liquid crystal composition for STN, it is preferable to adjust to the range of 6-20 micrometers. Further, in the case of bistable TN (Bistable TN), it is preferable to adjust to a range of 1.5 to 4 μm. Two or more kinds of optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch.
[0091]
The liquid crystal composition of the present invention can also be used as a liquid crystal composition for GH by adding a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, or tetrazine. Can be used. Alternatively, NCAP produced by microencapsulating nematic liquid crystals, and liquid crystals for polymer dispersed liquid crystal display elements (PDLCDs) represented by polymer network liquid crystal display elements (PNLCDs) produced by producing three-dimensional network polymers in the liquid crystals. It can also be used as a composition. In addition, it can be used as a liquid crystal composition for DS.
[0092]
The liquid crystal composition of the present invention is prepared by a conventional method. In general, a method of dissolving various components at a high temperature is employed.
[0093]
The compound of the present invention according to claim 1 can be easily produced by a known synthetic organic chemical method. An example of the production method is shown in Reaction Scheme 1.
[0094]
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[0095]
Hereinafter, the synthesis route will be described. The compound represented by Formula 1 is lithiated with a base such as sec-butyllithium, and then reacted with iodine to obtain a compound represented by Formula 2. The obtained compound of formula 2 is represented by formula 3 by reacting with ethylene glycol in the presence of a base such as sodium hydride in a mixed solvent of DMF (N, N-dimethylformamide) and THF (tetrahydrofuran). To the desired compound.
[0096]
【Example】
Hereinafter, the production methods and use examples of the compounds of the present invention will be described in more detail by way of examples. In addition, this invention does not receive a restriction | limiting at all by an Example. In the description of the examples, N represents the specified concentration (gram equivalent / l), M represents the molar concentration (mol / l), and Δε (dielectric anisotropy value) of the liquid crystal compound is the following base liquid crystal A85 wt%. And an extrapolated value (measured at 25 ° C.) from a composition consisting of 15 wt% of the compound and Δn (refractive index anisotropy value) is calculated from the following compound based on the base liquid crystal B 85 wt% and the compound 15 wt%. The measured value (measured at 25 ° C.) of the composition is expressed. Composition of mother liquid crystal A
[0097]
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[0098]
It is represented by the above general formula, and an alkyl group (R⁹, R^Ten) Different ester compounds were mixed at the following ratios to obtain mother liquid crystals A.

[0099]
Composition of mother liquid crystal B
[0100]
Embedded image

[0101]
A terminal alkyl group (R¹¹, R¹²) Are mixed to obtain mother liquid crystals B at the following ratios.

[0102]
Example 1
Synthesis of 1,2-bis-((2,3-difluoro-4-n-propyloxy) phenyloxy) ethane (3)
1st stage
Synthesis of 2,3-difluoro-4-n-propyloxyiodobenzene (2) To a solution of 2,3-difluoro-n-propyloxybenzene (1) (86.09 g, 0.500 mol) in THF (1000 ml), A 1.56 M sec-butyllithium hexane solution (385 ml, 0.600 mol) was added dropwise at −78 ° C. over 30 minutes, and the mixture was stirred for 30 minutes to obtain a solution of 2,3-difluoro-4-ethoxyphenyllithium. It was. To this solution was added dropwise a solution of iodine (304.6 g, 1.20 mol) in THF (500 ml) at the same temperature, and the mixture was reacted at −10 ° C. for 2 hours. After completion of the reaction, water (1000 ml) was added to the reaction solution, followed by extraction with toluene (2200 ml). The obtained organic layer was washed with water (800 ml) and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: hexane) to give 2,3-difluoro-4-n-propyloxyiodobenzene (2) (98.35 g, 0. 330 mol; yield 66%).
MS / 298 (M⁺).
[0103]
Second stage
Synthesis of 1,2-bis-((2,3-difluoro-4-n-propyloxy) phenyloxy) ethane (3)
A mixture of ethylene glycol (8.07 g, 0.130 mol), DMF (200 ml) and THF (200 ml) was cooled to −10 ° C., and sodium hydride (9.60 g, 0.400 mol) was added at the same temperature over 30 minutes. Added. After reacting at the same temperature for 2 hours, a solution of 2,3-difluoro-4-n-propyloxyiodobenzene (2) (98.30 g, 0.330 mol) obtained in the first stage in THF (300 ml) was added. It was added dropwise over 30 minutes. The reaction solution was gradually warmed to room temperature and reacted at room temperature for 10 hours. After completion of the reaction, water (100 ml) was added to the reaction solution under ice cooling, and then the solvent was distilled off under reduced pressure. Water (500 ml) was added to the residue and then extracted with toluene (1200 ml). The obtained organic layer was washed with water (500 ml) and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: toluene) and then recrystallized (hexane: toluene = 1: 1) to give 1,2-bis-((2,3 -Difluoro-4-n-propyloxy) phenyloxy) ethane (3) (22.52 g, 0.0560 mol; yield 43%) was obtained.
MS / 402 (M⁺), Δε = −11.3, Δn = 0.138.
[0104]
According to the method of Example 1, the following compounds can be synthesized.
[0105]
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[0106]
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[0107]
【The invention's effect】
As described above, the present invention has a negative dielectric anisotropy value having a large absolute value, a low viscosity, a controlled optical anisotropy value, a high specific resistance value, and a high voltage holding ratio. In addition, it has become possible to provide a liquid crystal compound that is stable against heat and ultraviolet irradiation, a liquid crystal composition containing the same, and a liquid crystal display device formed using the liquid crystal composition.

Claims (11)

General formula (2)

(Wherein R ¹ and Y ¹ are each independently a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group, Represents an alkynyl group, an alkynyloxy group, an alkoxyalkyl group having 2 to 19 carbon atoms, or an alkoxyalkoxy group having 2 to 18 carbon atoms , and one or more hydrogen atoms in these groups are substituted with a fluorine atom or a chlorine atom. Or each independently represents a hydrogen atom, a halogen atom, -CN , -OCN , -NC or -NCS , wherein X ¹ , X ² , X ³ and X ⁴ are each independently a single bond,- (CH ₂ ) ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₄ —, — (CH _{2 ) 3 O -, - O (} CH 2) 3 -, - CH _{CHCH 2 CH 2 -, - CH} 2 CH = CHCH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCH = CH -, - CF 2 O -, - OCF 2 -, - CH = CHCH 2 O _{-, - OCH 2 CH = CH} -, - CF = CF -, - CH 2 CF 2 -, - CF 2 CH 2 -, - (CF 2) 2 -, - (CF 2) 4 -, - (CH 2 _{) 2 COO -, - OCO (} CH 2) 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH = CHC≡C -, - C≡CCH = CH-, or -O _{(CH 2)} 2 is O-, ring ^{a 1,} ring ^{a 2,} ring ^{a 3,} ring ^{a 4} and ring ^{a 5} are each independently trans - cyclohexylene-1,4-diyl, cyclohex-1-ene-1,4 Diyl, 1,4-phenylene or bicyclo [1,1,1] pentane-1, -Rings represented by diyl, the carbon atoms constituting these rings may be substituted with nitrogen, oxygen or sulfur atoms, and hydrogen atoms on the rings are substituted with halogen atoms or cyano groups A ¹ , a ² , a ³ , a ⁴ and a ⁵ each independently represents 0 or 1, and in general formula (3) or general formula (4)

Either one of the parts represented by general formula (5)

(Wherein W ³ , W ⁴ , W ⁵ and W ⁶ each independently represents a fluorine atom or a chlorine atom, and n represents 2 ). A liquid crystal composition comprising at least two components, comprising at least one liquid crystalline compound according to claim 1. As a 1st component, at least 1 type of the compound of Claim 1 is contained, and as a 2nd component, at least 1 type of compound selected from the compound group which consists of General formula (6), (7) and (8) is included. A liquid crystal composition containing the liquid crystal composition.

(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, and one or more methylene groups not adjacent to each other in the alkyl group may be substituted with an oxygen atom or —CH═CH—, , One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and Y ² represents a fluorine atom, a chlorine atom, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H, -CFH _2, represent -OCF ₂ CF ₂ H or -OCF ₂ CFHCF _3, L ¹ and L ² represents a hydrogen atom or a fluorine atom each independently, Z ¹ and Z ² are each independently - (CH ₂ ) _2— , — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH— or a single bond, and ring Q ¹ is trans-cyclohexane-1,4 -Diyl, 1,3-dioxane-2,5-diyl, or a hydrogen atom is replaced by a fluorine atom Represents optionally substituted 1,4-phenylene, ring Q ² represents trans-cyclohexane-1,4-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and And each atom constituting these compounds may be substituted with the isotope thereof.) Containing at least one compound according to claim 1 as a first component, and containing at least one compound selected from the compound group consisting of general formulas (9) and (10) as a second component; A liquid crystal composition.

Wherein R ³ and R ⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, and one or more methylene groups not adjacent to each other in the alkyl group are substituted with an oxygen atom or —CH═CH—. One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, Y ³ represents a cyano group or —C≡C—CN, and ring Q ³ represents trans Represents cyclohexane-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl, wherein ring Q ⁴ is trans-cyclohexane-1,4-diyl , Pyrimidine-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and ring Q ⁵ represents trans-cyclohexane-1,4-diyl or 1,4-phenylene. represents, Z ³ is - (C _{2) 2} -, - COO- or a single bond, L ^3, L ⁴ and L ⁵ represents a hydrogen atom or a fluorine atom each independently, b, c and d each independently represents 0 or 1 In addition, the atoms constituting these compounds may be substituted with isotopes thereof.) As a first component, at least one compound according to claim 1 is contained, and as a second component, at least one compound selected from the compound group consisting of the general formulas (6), (7) and (8) is used. A liquid crystal composition containing at least one compound selected from the compound group consisting of general formulas (11), (12) and (13) as a third component.

Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 10 carbon atoms, and one or more methylene groups not adjacent to each other in the alkyl group are substituted with an oxygen atom or —CH═CH—. In addition, one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and ring Q ⁶ , ring Q ⁷ and ring Q ⁸ are each independently trans-cyclohexane. -1,4-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and Z ⁴ and Z ⁵ each independently represent —C≡ C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH— or a single bond is represented, and the atoms constituting these compounds may be substituted with the isotopes thereof. As a 1st component, at least 1 type of the compound of Claim 1 is contained, and as a 2nd component, at least 1 type of compound selected from the compound group which consists of General formula (14), (15) and (16) is included. A liquid crystal composition containing the liquid crystal composition.

(Wherein R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 10 carbon atoms, and one or more methylene groups not adjacent to each other in the alkyl group are substituted with an oxygen atom or —CH═CH—). One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and ring Q ⁹ and ring Q ¹⁰ are each independently trans-cyclohexane-1,4 -Represents diyl or 1,4-phenylene, L ⁶ and L ⁷ each independently represent a hydrogen atom or a fluorine atom, but at the same time do not represent a hydrogen atom, Z ⁶ and Z ⁷ each independently represent- (CH ₂ ) ₂ —, —COO— or a single bond is represented, and atoms constituting these compounds may be substituted with isotopes thereof. As a first component, at least one compound according to claim 1 is contained, and as a second component, at least one compound selected from the compound group consisting of the general formulas (11), (12) and (13) is used. A liquid crystal composition containing at least one compound selected from the group consisting of the general formulas (14), (15) and (16) as a third component. As a 1st component, at least 1 type of the compound of Claim 1 is contained, and as a 2nd component, at least 1 type of compound selected from the compound group which consists of the said General formula (9) and (10) is contained, A liquid crystal composition comprising at least one compound selected from the group consisting of the general formulas (11), (12) and (13) as a third component. As a first component, at least one compound according to claim 1 is contained, and as a second component, at least one compound selected from the compound group consisting of the general formulas (6), (7) and (8) is used. It contains at least one compound selected from the compound group consisting of the general formulas (9) and (10) as a third component, and the general formulas (11) and (12) as a fourth component And a liquid crystal composition containing at least one compound selected from the group consisting of (13) and (13). A liquid crystal composition comprising one or more optically active compounds in addition to the liquid crystal composition according to claim 2 . The liquid crystal display element comprised using the liquid-crystal composition in any one of Claims 2-10 .