JP2004231738A - Nematic liquid crystal composition and liquid crystal display element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition which has a suitably large specific resistance value and can improve behaviors against temporary electric voltage application due to the electrostaticity of a liquid crystal display element or the like without using a material largely lowering the specific resistance value, and to provide a liquid crystal composition which uses the liquid crystal composition and has good display characteristics. <P>SOLUTION: This nematic liquid crystal composition is characterized by comprising one or more compounds selected from compounds represented by general formulas (I), (III), and (IV) (at least one of L<SP>1</SP>to L<SP>5</SP>is an oxyalkylene group). The liquid crystal display element uses the nematic liquid crystal composition. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

（式中、Ｒ^１は、水素原子、炭素数１〜１２のアルキル基、少なくとも一つのハロゲンにより置換された炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基または少なくとも一つのハロゲンにより置換された炭素数２〜１２のアルケニル基を表し、これらの基中に存在する１個または２個以上のＣＨ_２基はそれぞれ独立してＯ原子が相互に直接結合しないものとして−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯ−Ｏ−により置き換えられてもよく、
【００１２】
Ａ^１およびＡ^２はそれぞれ独立して、
（ａ） トランス−１，４−シクロへキシレン基（この基中に存在する１個のＣＨ_２基または隣接していない２個以上のＣＨ_２基は−Ｏ−および／または−Ｓ−に置換されてもよい）
（ｂ） １，４−フェニレン基（この基中に存在する１個のＣＨ_２基または隣接していない２個以上のＣＨ_２基は−Ｎ−に置き換えられてもよい）
（ｃ） １，４−シクロヘキセニレン基、１，４−ビシクロ［２．２．２］オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基および１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基であり、上記の基（ａ）、基（ｂ）および基（ｃ）はそれぞれ独立してＣＮまたはハロゲンで置換されていてもよく、
ｍおよびｎはそれぞれ独立して、０、１または２であるが、ｍおよびｎの和は３以下であり、
Ｚ^１およびＺ^２はそれぞれ独立して、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−または単結合であり、
【００１３】
Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４およびＬ^５は、−Ｈ、−Ｆ、−Ｃｌ、−ＣＮ、−ＣＦ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＣＨ_２ＣＦ_３、一般式（Ｉ）におけるＲ^１と同じ定義または一般式（ＩＩ）
【化１２】

【００１４】
（式中、Ｚ^３は−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−、−ＣＯ−、−Ｏ−、−Ｓ−または単結合であり、
Ｒ^２は一般式（Ｉ）におけるＲ^１と同じ意味を表し、
ｉは２または３であり、
ｊは２または３である。）で表されるポリ（オキシアルキレン）基であり、
Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４およびＬ^５のうち少なくとも１つ以上が一般式（ＩＩ）で表されるポリ（オキシアルキレン）基であり、
Ａ^１、Ａ^２、Ｚ^１およびＺ^２が複数存在する場合は、それらは同一でもよく異なっていてもよい。）
で表される化合物を１種又は２種以上を含有し、
【００１５】
第２成分として、一般式（ＩＩＩ）
【化１３】

【００１６】
（式中、Ｒ^３は、一般式（Ｉ）におけるＲ^３と同じ意味を表し、Ｂ^１およびＢ^２はそれぞれ独立して、
（ａ） トランス−１，４−シクロへキシレン基（この基中に存在する１個のＣＨ_２基または隣接していない２個以上のＣＨ_２基は−Ｏ−および／または−Ｓ−に置換されてもよい）
（ｂ） １，４−フェニレン基（この基中に存在する１個のＣＨ_２基または隣接していない２個以上のＣＨ_２基は−Ｎ−に置き換えられてもよい）
（ｃ） １，４−シクロヘキセニレン基、１，４−ビシクロ［２．２．２］オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基および１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基であり、上記の基（ａ）、基（ｂ）および基（ｃ）はそれぞれ独立してＣＮまたはハロゲンで置換されていてもよく、
ｐおよびｑはそれぞれ独立して、０、１または２であるが、ｍおよびｎの和は３以下であり、
Ｚ^４およびＺ^５はそれぞれ独立して、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−または単結合であり、
Ｌ^６およびＬ^８はそれぞれ独立して、−Ｈ、−Ｆ、−Ｃｌであり、Ｌ^７は、−Ｈ、−Ｆ、−Ｃｌ、−ＣＮ、−ＣＦ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＣＨ_２ＣＦ_３であり、Ｂ^１、Ｂ^２、Ｚ^４およびＺ^５が複数存在する場合は、それらは同一でもよく異なっていてもよい。）
で表される化合物を１種又は２種以上を含有し、
【００１７】
第３成分として、一般式（ＩＶ）
【化１４】

【００１８】
（式中、Ｒ^４およびＲ^５は、一般式（Ｉ）におけるＲ^１と同じ意味を表し、
Ｃ^１、Ｃ^２およびＣ^３はそれぞれ独立して、
（ａ） トランス−１，４−シクロへキシレン基（この基中に存在する１個のＣＨ_２基または隣接していない２個以上のＣＨ_２基は−Ｏ−および／または−Ｓ−に置換されてもよい）
（ｂ） １，４−フェニレン基（この基中に存在する１個のＣＨ_２基または隣接していない２個以上のＣＨ_２基は−Ｎ−に置き換えられてもよい）
（ｃ） １，４−シクロヘキセニレン基、１，４−ビシクロ［２．２．２］オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基および１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基であり、上記の基（ａ）、基（ｂ）および基（ｃ）はそれぞれ独立してＣＮ、メチル基またはハロゲンで置換されていてもよく、ｒ、ｓおよびｔはそれぞれ独立して、０または１であり、かつｒ、ｓおよびｔの和が１以上であり、Ｚ^６、Ｚ^７およびＺ^８はそれぞれ独立して、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−または単結合を表す。）で表される化合物を１種又は２種以上を含有することを特徴とするネマチック液晶組成物およびこれを用いた液晶表示素子を提供する。
【００１９】
【発明の実施の形態】
以下に本発明の一例について説明する。
【００２０】
第１成分として一般式（Ｉ）から選ばれる化合物を１種もしくは２種以上を含有するが、１〜１０種が好ましく、１〜５種がさらに好ましい。上述の一般式（Ｉ）の化合物において、Ｒ^１は、水素原子、炭素数１〜１２のアルキル基、少なくとも一つのハロゲンにより置換された炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基または少なくとも一つのハロゲンにより置換された炭素数２〜１２のアルケニル基を表し、これらの基中に存在する１個または２個以上のＣＨ_２基はそれぞれ独立してＯ原子が相互に直接結合しないものとして−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯ−Ｏ−により置き換えられてもよいが、炭素数１〜１２のアルキル基、アルコシキ基、炭素数２〜１２のアルケニル基または炭素数２〜１２のアルケニルオキシ基が好ましく、中でも直鎖型アルキル基および直鎖型アルケニル基がさらに好ましく、−ＣＨ_３、−ＣＨ_２ＣＨ_３、−（ＣＨ_２）_２ＣＨ_３、−（ＣＨ_２）_３ＣＨ_３、−（ＣＨ_２）_４ＣＨ_３、−（ＣＨ_２）_５ＣＨ_３、−（ＣＨ_２）_６ＣＨ_３、−（ＣＨ_２）_７ＣＨ_３、−ＣＨ＝ＣＨ_２、−ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−（ＣＨ_２）_２ＣＨ＝ＣＨ_２、−（ＣＨ_２）_２ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−（ＣＨ_２）_４ＣＨ＝ＣＨ_２、−（ＣＨ_２）_４ＣＨ＝ＣＨＣＨ_３（Ｅ体）および−（ＣＨ_２）_６ＣＨ＝ＣＨ_２が特に好ましい。連結基Ｚ^１およびＺ^２は、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−または単結合を挙げることができ、中でも単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−または−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−がより好ましく、単結合または−ＣＨ_２ＣＨ_２−がさらに好ましく、単結合が特に好ましい。
【００２１】
環Ａ^１およびＡ^２は式群１に示すような構造が好例として挙げられる。
【化１５】

【００２２】
中でも、式群２に記載した構造がより好ましい。
【化１６】

【００２３】
中でも、式群３に記載した構造が特に好ましい。
【化１７】

【００２４】
ｍおよびｎはそれぞれ独立して、０、１または２であり、ｍおよびｎの和が３以下であるが、ｍおよびｎの和が０および３の場合は液晶組成物への溶解性が低下することから、ｍおよびｎの和は１または２が好ましい。
【００２５】
Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４およびＬ^５は、−Ｈ、−Ｆ、−Ｃｌ、−ＣＮ、−ＣＦ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＣＨ_２ＣＦ_３、一般式（Ｉ）におけるＲ^１と同様の前述の直鎖型アルキル基、分岐型アルキル基、アルケニル基、フッ素置換アルキル基、フッ素置換アルケニル基、アルコキシル基置換アルキル基およびそれらのアルコキシル基または−［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_２ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_３、−［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_２ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_３ＯＣＨ_３、−［（ＣＨ_２）_２Ｏ］_３ＯＣＨ_２ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_２ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_３ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_４ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_３ＯＣＨ_３、−［（ＣＨ_２）_３Ｏ］_３ＯＣＨ_２ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_２ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_３ＣＨ_３、−［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_４ＣＨ−、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_３ＯＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_３ＯＣＨ_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_３ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_４ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_３ＯＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_３ＯＣＨ_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_２ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_３ＣＨ_３、−ＯＣＨ_２［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_４ＣＨ−、−ＯＣＯ［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_３、−ＯＣＯ［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_２ＣＨ_３、−ＯＣＯ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−ＯＣＯ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−ＯＣＯ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−ＯＣＯ［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_３、−ＯＣＯ［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_２ＣＨ_３、−ＯＣＯ［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−ＯＣＯ［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_２ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_２ＯＣＨ_２ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_３ＯＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_３ＯＣＨ_２ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_２ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_３ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_３Ｏ（ＣＨ_２）_４ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_３ＯＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_３ＯＣＨ_２ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_２ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_３ＣＨ_３、−Ｏ［（ＣＨ_２）_３Ｏ］_３Ｏ（ＣＨ_２）_４ＣＨ_３等のポリ（オキシアルキレン）アルキル基およびそれらのアルコキシル基が好例として挙げられるが、−Ｈ、−Ｆ、−Ｃｌ、−ＣＮ、−ＣＦ_３、一般式（Ｉ）におけるＲ^１と同様の前述の直鎖型アルキル基および直鎖型アルケニル基、または−［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_２ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３、−［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３およびそれらのアルコキシル基がより好ましく、
【００２６】
−Ｈ、−Ｆ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、−（ＣＨ_２）_２ＣＨ_３、−（ＣＨ_２）_３ＣＨ_３、−（ＣＨ_２）_４ＣＨ_３、−（ＣＨ_２）_５ＣＨ_３、−（ＣＨ_２）_６ＣＨ_３、−（ＣＨ_２）_７ＣＨ_３、−ＣＨ＝ＣＨ_２、−ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−（ＣＨ_２）_２ＣＨ＝ＣＨ_２、−（ＣＨ_２）_２ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−（ＣＨ_２）_４ＣＨ＝ＣＨ_２、−（ＣＨ_２）_４ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−Ｏ［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２ＯＣＨ_２ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_２ＣＨ_３、−Ｏ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_３ＣＨ_３および−Ｏ［（ＣＨ_２）_２Ｏ］_２Ｏ（ＣＨ_２）_４ＣＨ_３が特に好ましい。
【００２７】
Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４およびＬ^５のうち、少なくとも１つ以上が一般式（ＩＩ）で表されるポリ（オキシアルキレン）アルキル基、ポリ（オキシアルキレン）アルコキシ基またはポリ（オキシアルキレン）カルボキシル基であるが、Ｌ^３またはＬ^４がこれらの基によって置換していることが好ましく、そのとき、他のＬ^１、Ｌ^２、Ｌ^３、Ｌ^４およびＬ^５は−Ｈまたは−Ｆにより置換していることが好ましい。
【００２８】
上述のように、一般式（Ｉ）の化合物は、そのＲ^１、連結基Ｚ^１およびＺ^２、環Ａ^１およびＡ^２、ｍおよびｎ、Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４およびＬ^５の選択によって、非常に多種の化合物を包含しうるわけであるが、その各構造部位を選択することによってより広い用途分野に適合した化合物とすることができ、その結果、一般式（Ｉ）の化合物を用いることにより、従来知られていた方法では製造が困難であったものを含めて、適度に大きい比抵抗値且つ液晶表示素子の静電気等の一時的な電圧の印加に対する挙動を改善された液晶組成物を製造でき、非常に有用である。
【００２９】
さらに詳述すると、一般式（Ｉ）の化合物の中で、特に好ましい化合物として式群４に記載した化合物を挙げることができる。なお、式群中、Ｒ^１は−ＣＨ_３、−ＣＨ_２ＣＨ_３、−（ＣＨ_２）_２ＣＨ_３、−（ＣＨ_２）_３ＣＨ_３、−（ＣＨ_２）_４ＣＨ_３、−（ＣＨ_２）_５ＣＨ_３、−（ＣＨ_２）_６ＣＨ_３、−（ＣＨ_２）_７ＣＨ_３、−ＣＨ＝ＣＨ_２、−ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−（ＣＨ_２）_２ＣＨ＝ＣＨ_２、−（ＣＨ_２）_２ＣＨ＝ＣＨＣＨ_３（Ｅ体）、−（ＣＨ_２）_４ＣＨ＝ＣＨ_２、−（ＣＨ_２）_４ＣＨ＝ＣＨＣＨ_３（Ｅ体）および−（ＣＨ_２）_６ＣＨ＝ＣＨ_２を表し、Ｒ^２は−ＣＨ_３、−ＣＨ_２ＣＨ_３、−（ＣＨ_２）_２ＣＨ_３、−（ＣＨ_２）_３ＣＨ_３、−（ＣＨ_２）_４ＣＨ_３を表す。
【００３０】
【化１８】

【００３１】
一般式（Ｉ）の化合物の含有率は０．０１〜５０質量％の範囲であるが、０．０１〜４０質量％の範囲が好ましく、０．０１〜２０質量％がより好ましい。
【００３２】
第２成分として一般式（ＩＩＩ）
【化１９】

【００３３】
から選ばれる化合物を１種又は２種以上を含有するが、１〜２０種が好ましく、１〜１５種がさらに好ましい。一般式（ＩＩＩ）の式中、Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、少なくとも一つのハロゲンにより置換された炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基または少なくとも一つのハロゲンにより置換された炭素数２〜１２のアルケニル基を表し、これらの基中に存在する１個または２個以上のＣＨ_２基はそれぞれ独立してＯ原子が相互に直接結合しないものとして−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯ−Ｏ−により置き換えられてもよいが、炭素数１〜１２のアルキル基、アルコシキ基、炭素数２〜１２のアルケニル基または炭素数２〜１２のアルケニルオキシ基が好ましく、中でも直鎖型アルキル基および直鎖型アルケニル基がさらに好ましい。環Ｂ^１およびＢ^２は前述の式群１に示すような構造が好適であるが、前述の式群２に示すような構造がさらに好ましい。連結基Ｚ^４およびＺ^５は、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−または単結合を挙げることができ、中でも単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−Ｃ≡Ｃ−、−ＣＯＯ−または−ＯＣＯ−がより好ましく、単結合、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−、−ＣＯＯ−または−ＯＣＯがさらに好ましく、単結合または−ＣＯＯ−が特に好ましい。Ｌ^６およびＬ^８はそれぞれ独立して、−Ｈ、−Ｆ、−Ｃｌであるが、−Ｈまたは−Ｆが好ましい。Ｌ^７は、−Ｆ、−Ｃｌ、−ＣＮ、−ＣＦ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＣＨ_２ＣＦ_３であるが、−Ｆ、−ＣＮ、−ＣＦ_３または−ＯＣＦ_３が好ましく、−Ｆまたは−ＣＮが特に好ましい。ｐおよびｑはそれぞれ独立して、０、１または２であり、ｐ＋ｑが３以下であるが、ｐ＋ｑが１または２が好ましい。
【００３４】
一般式（ＩＩＩ）は、具体的には、一般式（ＩＩＩａ）または一般式（ＩＩＩｂ）で表される化合物が好ましい。
【化２０】

【００３５】
さらに、具体的には、一般式（ＩＩＩａ−１）〜一般式（ＩＩＩａ−１）、一般式（ＩＩＩｂ−１）または一般式（ＩＩＩｂ−２）で表される化合物が特に好ましい。
【００３６】
【化２１】

【００３７】
一般式（ＩＩＩａ−１）〜一般式（ＩＩＩａ−１）、一般式（ＩＩＩｂ−１）または一般式（ＩＩＩｂ−２）において、Ｘ^１およびＸ^２はそれぞれ独立して、−Ｈまたは−Ｆを表す。一般式（ＩＩＩ）の化合物の含有率は１〜８０質量％の範囲であるが、５〜６０質量％の範囲が好ましく、５〜５０質量％がより好ましい。
【００３８】
第３成分として、一般式（ＩＶ）
【化２２】

【００３９】
から選ばれる化合物を１種又は２種以上を含有するが、１〜２０種が好ましく、１〜１５種がさらに好ましい。一般式（ＩＶ）の式中、Ｒ^４およびＲ^５は、それぞれ独立的に水素原子、炭素数１〜１２のアルキル基、少なくとも一つのハロゲンにより置換された炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基または少なくとも一つのハロゲンにより置換された炭素数２〜１２のアルケニル基を表し、これらの基中に存在する１個または２個以上のＣＨ_２基はそれぞれ独立してＯ原子が相互に直接結合しないものとして−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯ−Ｏ−により置き換えられてもよいが、炭素数１〜１２のアルキル基、アルコシキ基、炭素数２〜１２のアルケニル基または炭素数２〜１２のアルケニルオキシ基が好ましく、中でも直鎖型アルキル基および直鎖型アルケニル基がさらに好ましい。環Ｃ^１、Ｃ^２およびＣ^３は式群５
【００４０】
【化２３】

【００４１】
に示すような構造が好適であるが、式群６
【化２４】

【００４２】
に示すような構造がさらに好ましい。連結基Ｚ^６、Ｚ^７およびＺ^８は、それぞれ独立して、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）Ｏ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−または単結合を挙げることができ、中でも単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_３）ＣＨ（ＣＨ_３）−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−がより好ましく、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−がさらに好ましい。ｒ、ｓおよびｔはそれぞれ独立して、０または１であり、かつｒ、ｓおよびｔの和が１以上であるが、ｒ、ｓおよびｔの和が２または３が好ましい。
【００４３】
一般式（ＩＶ）は、具体的には、一般式（ＩＶａ）、一般式（ＩＶｂ）または一般式（ＩＶｃ）で表される化合物が好ましい。
【化２５】

【００４４】
さらに、具体的には、一般式（ＩＶａ−１）〜一般式（ＩＶａ−３）、一般式（ＩＶｂ−１）、一般式（ＩＶｂ−２）または一般式（ＩＶｃ−１）で表される化合物が特に好ましい。
【化２６】

【００４５】
一般式（ＩＶａ−１）〜一般式（ＩＶａ−３）、一般式（ＩＶｂ−１）、一般式（ＩＶｂ−２）または一般式（ＩＶｃ−１）において、Ｙ^１、Ｙ^２、Ｙ^３およびＹ^４は、それぞれ独立して、−Ｈ、−Ｆまたはメチル基を表すが、−Ｈが好ましい。Ｚ^１０は、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−、または単結合を表すが、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−または単結合が好ましい。Ｚ^１１は、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−を表すが、−Ｃ≡Ｃ−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−が好ましい。一般式（ＩＶ）の化合物の含有率は５〜９５質量％の範囲であるが、１０〜９０質量％の範囲が好ましく、２５〜９０質量％がより好ましい。
【００４６】
この液晶組成物はネマチック相上限温度が６０℃以上であることが好ましく、８０℃以上がより好ましく、９０℃以上が特に好ましい。Δｎは０．０６〜０．３０の範囲であることが好ましく、０．０７〜０．１８が更に好ましい範囲であり、０．０７〜０．１６の範囲がＴＮ−ＬＣＤのセル厚の設計に特に好ましく、０．１２〜０．１８の範囲がＳＴＮ−ＬＣＤのセル厚の設計に特に好ましい。誘電率異方性（Δε）は、１以上２０以下が好ましいが、１以上１５以下が特に好ましい。
【００４７】
本発明の液晶組成物は、上記の化合物以外に、通常のネマチック液晶、スメクチック液晶、コレステリック液晶、２色性色素などを含有していてもよい。又、ＴＮ−ＬＣＤのリバースツイストドメイン防止のためやＳＴＮ−ＬＣＤの螺旋構造を誘起するため、カイラル剤を添加しても良い。カイラル剤は通常市販されているものを使用することができる。例えば、コレステリルノナノエート（ＣＮ）、メルク社製Ｓ−８１１、Ｒ−８１１、ＣＢ−１５、Ｃ−１５などが挙げられる。温度上昇によって誘起螺旋ピッチが長くなるものと短くなるものが知られているが、これらの一方を１種あるいは２種以上を用いても良く、両者を組み合わせて１種あるいは２種以上用いても良い。例えば、ＴＮ−ＬＣＤ、ＳＴＮ−ＬＣＤ、ＴＦＴ−ＬＣＤにおいては、基板間の厚みｄと誘起螺旋ピッチｐの商ｄ／ｐは、０．００１〜２４の範囲から選ぶことができるが、０．０１〜１２の範囲が好ましく、０．１〜２の範囲がより好ましく、０．１〜１．５の範囲が更に好ましく、０．１〜１の範囲が更により好ましく、０．１〜０．８の範囲が特に好ましい。
上記ネマチック液晶組成物はＴＮ−ＬＣＤ、ＳＴＮ−ＬＣＤ、ＯＣＢ−ＬＣＤ、高分子分散型液晶表示素子、フェーズチェンジ型コレステリック液晶表示素子に有用であるが、ＴＮ−ＬＣＤ、ＳＴＮ−ＬＣＤに特に有用である。また、透過型あるいは反射型の液晶表示素子に用いることができる。
【００４８】
本発明のＴＮ液晶表示素子は目的に応じて、ねじり角を８０°から１３０°の範囲で選択することができ、８５°から１１０°が好ましい。本発明のＳＴＮ液晶表示素子は目的に応じて、ねじり角を１８０°から２７０°の範囲で選択することができ、２２０°から２６０°が好ましい。
【００４９】
本発明の液晶組成物を使用することにより、適度に大きい比抵抗値を有し、かつ液晶表示素子に対して一時的に静電気で印加された電圧が十分速い時間で緩和することができる。
【００５０】
【実施例】
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。又、以下の実施例及び比較例の組成物における「％」は『質量％』を意味する。
【００５１】
実施例中、測定した特性は以下の通りである。
Ｔ_Ｎ−Ｉ ：ネマチック相−等方性液体相転移温度（℃）
Δε ：誘電率異方性（２５℃）
Δｎ ：複屈折率（２５℃）
ρ ：比抵抗値（Ω・ｃｍ）
帯電時間：液晶組成物をセルに注入し、静電気ガンを用いて点灯状態にした後、元の電圧無印加状態に戻るまでの時間（秒）
【００５２】
化合物記載に下記の略号を使用する。
−ｎ 数字 ：−Ｃ_ｎＨ_２ｎ＋１ （アルキル側鎖は数字、代表するときはＲとする。）
−Ｏｎ ：−ＯＣ_ｎＨ_２ｎ＋１
−ｎｄｍ ：−（Ｃ_ｎＨ_２ｎ＋１−ＣＨ＝ＣＨ−（ＣＨ_２）_ｍ−１）
ｎｄｍ− ：Ｃ_ｎＨ_２ｎ＋１−ＣＨ＝ＣＨ−（ＣＨ_２）_ｍ−１−
−Ｏｄ（ｍ）ｎ ：−Ｏ（Ｃ_ｎＨ_２ｎ＋１−ＣＨ＝ＣＨ−（ＣＨ_２）_ｍ−２）
ｄ（ｍ）ｎＯ− ：Ｃ_ｎＨ_２ｎ＋１−ＣＨ＝ＣＨ−（ＣＨ_２）_ｍ−２Ｏ−
連結基
−ＶＯ− ：−ＣＯＯ− −Ｔ− ：−Ｃ≡Ｃ−
−２− ：−ＣＨ_２ＣＨ_２−
置換基
−ＣＮ ：−Ｃ≡Ｎ −Ｆ ：−Ｆ
環
Ｐｈ ：１，４−フェニレン基 Ｐｈ１：３−フルオロ−１，４−フェニレン基
Ｐｈ２：３，５−ジフルオロ−１，４−フェニレン基
Ｍａ ：ピリミジン−２，５−ジイル基
Ｃｙ ：１，４−シクロヘキシレン基
【００５３】
（実施例１、実施例２、比較例１、比較例２）
以下に示すネマチック液晶組成物（ＬＣ１）および（ＬＣ２）を調製し、その物性値を測定し、その結果を表１に示す。
【表１】

得られた液晶組成物ＬＣ１およびＬＣ２は、高い比抵抗値を示している。次に、上述のネマチック液晶組成物ＬＣ１およびＬＣ２に、化合物（Ｉｂ−２）
【００５４】
【化２７】

を加えた液晶組成物（ＬＣ３〜ＬＣ６）を調製した。また、比較のために、ネマチック液晶組成物ＬＣ１およびＬＣ２にクラウンエーテル（１８Ｋ６）
【化２８】

【００５５】
を加えた液晶組成物（ＬＣ７〜ＬＣ１０）を調製した。また、別の比較のために、アミン化合物（３ＣＰＮ）
【化２９】

を加えた液晶組成物（ＬＣ１１〜ＬＣ１４）を調製した。それらの比抵抗値ならびに８．３μｍのＴＮセルに注入したときの帯電特性を測定し、その結果を表２および表３に示す。
【００５６】
【表２】

【００５７】
ネマチック液晶組成物ＬＣ３、ＬＣ４は、液晶組成物ＬＣ１と比較し、高い比抵抗値を保持しながら、帯電時間を大幅に短縮することができた。それに対し、化合物（Ｉｂ−２）の代わりにクラウンエーテル１８Ｋ６を加えた場合は、実施例１同様の帯電時間を短縮する効果は認められるが、比抵抗値が、ＬＣ１の比抵抗値と比較して約１／１００と大幅に低下してしまった。また、化合物（Ｉｂ−２）の代わりにアミン化合物３ＣＰＮを加えた場合は、実施例１同様の帯電時間を短縮する効果は認められるが、比抵抗値が、ＬＣ１の比抵抗値と比較して約１／１０と大幅に低下し、さらに時間経過とともに黄変してしまった。
【００５８】
【表３】

ネマチック液晶組成物ＬＣ５、ＬＣ６は、液晶組成物ＬＣ２と比較し、高い比抵抗値を保持しながら、帯電時間を大幅に短縮することができた。それに対し、化合物（Ｉｂ−２）の代わりにクラウンエーテル１８Ｋ６を加えた場合は、実施例２同様の帯電時間を短縮する効果は認められるが、比抵抗値が、ＬＣ１の比抵抗値と比較して約１／１００と大幅に低下してしまった。また、化合物（Ｉｂ−２）の代わりにアミン化合物３ＣＰＮを加えた場合は、実施例１同様の帯電時間を短縮する効果は認められるが、比抵抗値が、ＬＣ１の比抵抗値と比較して約１／１０と大幅に低下し、さらに時間経過とともに黄変してしまった。
【００５９】
（実施例３、実施例４）
さらに、ネマチック液晶組成物（ＬＣ１５）および（ＬＣ１６）を調製し、その物性値を測定し、その結果を表４に示す。
【表４】

得られた液晶組成物ＬＣ１５およびＬＣ１６は、高い比抵抗値を示している。実施例１、２と同様に、液晶組成物ＬＣ１５に化合物（Ｉｂ−２）を加えた液晶組成物（ＬＣ１７、ＬＣ１８）を調製し、その比抵抗値ならびに８．３μｍのＴＮセルに注入したときの帯電特性を測定し、その結果を表５に示す。
【００６０】
【表５】

ネマチック液晶組成物ＬＣ１７、ＬＣ１８は、液晶組成物ＬＣ１５と比較し、高い比抵抗値を保持しながら、帯電時間を大幅に短縮することができた。
【００６１】
実施例１、２と同様に、液晶組成物ＬＣ１６に化合物（Ｉｂ−２）を加えた液晶組成物（ＬＣ１９、ＬＣ２０）に、さらにｄ／ｐ＝０．５となるようにカイラル化合物Ｓ−８１１を調製し、その比抵抗値ならびに６．０μｍの２４０度ツイストＳＴＮセルに注入したときの帯電特性を測定し、その結果を表６に示す。
【００６２】
【表６】

ネマチック液晶組成物ＬＣ１９、ＬＣ２０は、液晶組成物ＬＣ１６と比較し、高い比抵抗値を保持しながら、帯電時間を大幅に短縮することができた。
【００６３】
【発明の効果】
本発明のネマチック液晶組成物は、比抵抗値が低下する等の信頼性を損なうことなく、液晶表示素子の静電気等の一時的な電圧の印加に対する挙動を改善することができる。そのため、液晶表示素子の製造工程で発生する静電気による帯電をすみやかに緩和することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a nematic liquid crystal composition useful as a liquid crystal display material, and a liquid crystal display device using the same.
[0002]
[Prior art]
In a manufacturing process of a liquid crystal display element such as a twisted nematic, a super-twisted nematic, or an active matrix, when a protective film stuck on a surface of the liquid crystal display element is peeled off, an electric field of static electricity is generated in the element. This electric field often orients the liquid crystal composition in the non-lighted portion, that is, turns on, and the orientation continues until the electric field is discharged. The time required for this electric field to be discharged cannot be ignored, and the work must be interrupted not only in the manufacturing process but also in the inspection process or the shipping process such as the work to wipe off the dirt on the element surface. Will be worsened.
[0003]
Such a problem can be alleviated by, for example, lowering the specific resistance value of the liquid crystal composition (Patent Document 1). That is, in a liquid crystal composition having a low specific resistance, even when a temporary voltage such as static electricity is applied, the alignment state when no voltage is applied can be quickly restored. For example, the specific resistance of the liquid crystal composition in a nematic liquid crystal display element is usually 1 × 10¹¹Ωcm or more, but this is 1 × 10¹⁰When the resistance is reduced to the order of Ωcm, the relaxation becomes fast enough to perform normal work, and the effect can be confirmed. 1x10 more⁹When the resistance is reduced to the order of Ωcm, the relaxation becomes very fast, and even if a temporary voltage such as static electricity is applied, a change in the orientation state can hardly be confirmed. However, 1 × 10¹¹In a liquid crystal display element using a liquid crystal composition of Ωcm or less, power consumption is often increased, and furthermore, an electric short circuit is caused, which may cause defective display such as burning of characters. Therefore, there is a need for the development of a liquid crystal composition having a moderately large specific resistance value and a behavior with respect to the application of a temporary voltage such as static electricity of a liquid crystal display element, that is, sufficiently fast relaxation to the application of a temporary voltage such as static electricity. Have been.
[0004]
As a method of relaxing the application of a temporary voltage such as static electricity in the above-described liquid crystal composition, for example, a method of adding an ionic substance such as Cryptand (Patent Document 2) can be mentioned. However, the ionic component in the liquid crystal composition has a problem that it is adsorbed by a polymer film such as polyimide in a liquid crystal display element at a part of an injection port or the like, and often causes display unevenness. .
[0005]
Similarly, as a method of relaxing the application of the temporary voltage, a method of adding an alcohol such as ethylene glycol and a copolymer thereof, or an amine such as a polyalkylamine can be mentioned (Patent Documents 3 and 4). . However, in order to sufficiently obtain the effect, it is necessary to add a large amount, and as the addition ratio increases, nematic-isolation of a liquid crystal composition, which is one of the items indicating the reliability of a liquid crystal display device, is performed. There is a problem that the tropic phase transition temperature is greatly reduced.
[0006]
Alternatively, as a method of similarly relaxing the application of the temporary voltage, a method of adding a so-called crown ether such as a cyclic polyether may be mentioned (Patent Document 5). However, crown ethers are highly toxic, such as giving significant irritation to human skin or eyes, and have the problem that the working environment in the production of liquid crystal display devices may be dangerous.
[0007]
Further, these materials tend to greatly lower the specific resistance by the addition, but when a liquid crystal composition having a high specific resistance is used before the addition, the specific resistance becomes 1 × 10¹¹A liquid crystal composition of about Ωcm can be obtained. However, when a material that significantly lowers the specific resistance is added, the specific resistance becomes 1 × 10¹¹Since a problem similar to that of a composition less than Ωcm occurs, it has been desired to develop a liquid crystal composition having a short relaxation time for applying a temporary voltage such as static electricity.
[0008]
[Patent Document 1]
Japanese Patent Publication No. 64-7640 (2 pages)
[Patent Document 2]
Japanese Patent Application No. 4-28788 (2 pages)
[Patent Document 3]
JP-A-51-68483 (2 pages)
[Patent Document 4]
JP-A-9-67577 (page 4)
[Patent Document 5]
Tokuhyo Hei 11-508286 (2 pages)
[0009]
[Problems to be solved by the invention]
By providing a liquid crystal composition having a moderately large specific resistance value and improving the behavior of a liquid crystal display element against the application of a temporary voltage such as static electricity without using a material that significantly lowers the specific resistance. is there. That is, the present invention provides a liquid crystal composition which is sufficiently fast to relax a temporary voltage application such as static electricity.
[0010]
[Means for Solving the Problems]
The present inventors have studied a nematic liquid crystal composition using a poly (oxyalkylene) -substituted benzene compound, and have completed the present invention.
That is, the present invention provides a liquid crystal composition described below.
[0011]
As the first component, the general formula (I)
Embedded image

(Where R¹Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted by at least one halogen, an alkenyl group having 2 to 12 carbon atoms, or a carbon number substituted by at least one halogen. Represents 2 to 12 alkenyl groups, and represents one or more CH₂The groups may each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O-, such that the O atoms are not directly bonded to each other;
[0012]
A¹And A²Are each independently
(A) trans-1,4-cyclohexylene group (one CH present in this group)₂A group or two or more CHs that are not adjacent₂Groups may be substituted with -O- and / or -S-)
(B) 1,4-phenylene group (one CH present in this group)₂A group or two or more CHs that are not adjacent₂The group may be replaced by -N-)
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
And the groups (a), (b) and (c) may be each independently substituted with CN or halogen;
m and n are each independently 0, 1 or 2, but the sum of m and n is 3 or less;
Z¹And Z²Is each independently -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO- or a single bond;
[0013]
L¹, L², L³, L⁴And L⁵Is -H, -F, -Cl, -CN, -CF₃, -OCH₂F, -OCHF₂, -OCF₃, -CH₂CF₃R in the general formula (I)¹Has the same definition or general formula (II)
Embedded image

[0014]
(Where Z³Is -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO-, -CO-, -O-, -S- or a single bond;
R²Is R in the general formula (I)¹Has the same meaning as
i is 2 or 3;
j is 2 or 3. A) a poly (oxyalkylene) group represented by
L¹, L², L³, L⁴And L⁵At least one of which is a poly (oxyalkylene) group represented by the general formula (II),
A¹, A², Z¹And Z²When there exist two or more, they may be the same or different. )
Containing one or more compounds represented by
[0015]
As the second component, a compound represented by general formula (III)
Embedded image

[0016]
(Where R³Is R in the general formula (I)³Has the same meaning as¹And B²Are each independently
(A) trans-1,4-cyclohexylene group (one CH present in this group)₂A group or two or more CHs that are not adjacent₂Groups may be substituted with -O- and / or -S-)
(B) 1,4-phenylene group (one CH present in this group)₂A group or two or more CHs that are not adjacent₂The group may be replaced by -N-)
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
And the groups (a), (b) and (c) may be each independently substituted with CN or halogen;
p and q are each independently 0, 1 or 2, but the sum of m and n is 3 or less;
Z⁴And Z⁵Is each independently -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO- or a single bond;
L⁶And L⁸Is each independently -H, -F, -Cl;⁷Is -H, -F, -Cl, -CN, -CF₃, -OCH₂F, -OCHF₂, -OCF₃, -CH₂CF₃And B¹, B², Z⁴And Z⁵When there exist two or more, they may be the same or different. )
Containing one or more compounds represented by
[0017]
As the third component, the general formula (IV)
Embedded image

[0018]
(Where R⁴And R⁵Is R in the general formula (I)¹Has the same meaning as
C¹, C²And C³Are each independently
(A) trans-1,4-cyclohexylene group (one CH present in this group)₂A group or two or more CHs that are not adjacent₂Groups may be substituted with -O- and / or -S-)
(B) 1,4-phenylene group (one CH present in this group)₂A group or two or more CHs that are not adjacent₂The group may be replaced by -N-)
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
Wherein the groups (a), (b) and (c) may be each independently substituted with CN, methyl or halogen, and r, s and t Is each independently 0 or 1, and the sum of r, s and t is 1 or more;⁶, Z⁷And Z⁸Is each independently -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO-, -CH = NN-CH- or a single bond. The present invention provides a nematic liquid crystal composition comprising one or more compounds represented by the formula (1) and a liquid crystal display device using the same.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, an example of the present invention will be described.
[0020]
One or more compounds selected from the general formula (I) are contained as the first component, but 1 to 10 are preferable, and 1 to 5 are more preferable. In the compounds of the above general formula (I), R¹Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted by at least one halogen, an alkenyl group having 2 to 12 carbon atoms, or a carbon number substituted by at least one halogen. Represents 2 to 12 alkenyl groups, and represents one or more CH₂The groups may each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O-, as though the O atoms are not directly bonded to each other, An alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms is preferable, and among them, a linear alkyl group and a linear alkenyl group are more preferable.₃, -CH₂CH₃,-(CH₂)₂CH₃,-(CH₂)₃CH₃,-(CH₂)₄CH₃,-(CH₂)₅CH₃,-(CH₂)₆CH₃,-(CH₂)₇CH₃, -CH = CH₂, -CH = CHCH₃(E-form),-(CH₂)₂CH = CH₂,-(CH₂)₂CH = CHCH₃(E-form),-(CH₂)₄CH = CH₂,-(CH₂)₄CH = CHCH₃(E-form) and-(CH₂)₆CH = CH₂Is particularly preferred. Linking group Z¹And Z²Is -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO- or a single bond. Among them, a single bond, -CH₂CH₂-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-Or -CH (CH₃) CH (CH₃)-Is more preferable, and a single bond or -CH₂CH₂Is more preferable, and a single bond is particularly preferable.
[0021]
Ring A¹And A²A good example is a structure as shown in Formula Group 1.
Embedded image

[0022]
Among them, the structure described in Formula Group 2 is more preferable.
Embedded image

[0023]
Among them, the structure described in Formula Group 3 is particularly preferable.
Embedded image

[0024]
m and n are each independently 0, 1 or 2, and the sum of m and n is 3 or less. When the sum of m and n is 0 and 3, the solubility in the liquid crystal composition is reduced. Therefore, the sum of m and n is preferably 1 or 2.
[0025]
L¹, L², L³, L⁴And L⁵Is -H, -F, -Cl, -CN, -CF₃, -OCH₂F, -OCHF₂, -OCF₃, -CH₂CF₃R in the general formula (I)¹And the above-mentioned straight-chain alkyl group, branched alkyl group, alkenyl group, fluorine-substituted alkyl group, fluorine-substituted alkenyl group, alkoxyl-substituted alkyl group and their alkoxyl groups or-[(CH₂)₂O]₂OCH₃,-[(CH₂)₂O]₂OCH₂CH₃,-[(CH₂)₂O]₂O (CH₂)₂CH₃,-[(CH₂)₂O]₂O (CH₂)₃CH₃,-[(CH₂)₂O]₂O (CH₂)₄CH₃,-[(CH₂)₃O]₂OCH₃,-[(CH₂)₃O]₂OCH₂CH₃,-[(CH₂)₃O]₂O (CH₂)₂CH₃,-[(CH₂)₃O]₂O (CH₂)₃CH₃,-[(CH₂)₃O]₂O (CH₂)₄CH₃,-[(CH₂)₂O]₃OCH₃,-[(CH₂)₂O]₃OCH₂CH₃,-[(CH₂)₂O]₃O (CH₂)₂CH₃,-[(CH₂)₂O]₃O (CH₂)₃CH₃,-[(CH₂)₂O]₃O (CH₂)₄CH₃,-[(CH₂)₃O]₃OCH₃,-[(CH₂)₃O]₃OCH₂CH₃,-[(CH₂)₃O]₃O (CH₂)₂CH₃,-[(CH₂)₃O]₃O (CH₂)₃CH₃,-[(CH₂)₃O]₃O (CH₂)₄CH-, -OCH₂[(CH₂)₂O]₂OCH₃, -OCH₂[(CH₂)₂O]₂OCH₂CH₃, -OCH₂[(CH₂)₂O]₂O (CH₂)₂CH₃, -OCH₂[(CH₂)₂O]₂O (CH₂)₃CH₃, -OCH₂[(CH₂)₂O]₂O (CH₂)₄CH₃, -OCH₂[(CH₂)₃O]₂OCH₃, -OCH₂[(CH₂)₃O]₂OCH₂CH₃, -OCH₂[(CH₂)₃O]₂O (CH₂)₂CH₃, -OCH₂[(CH₂)₃O]₂O (CH₂)₃CH₃, -OCH₂[(CH₂)₃O]₂O (CH₂)₄CH₃, -OCH₂[(CH₂)₂O]₃OCH₃, -OCH₂[(CH₂)₂O]₃OCH₂CH₃, -OCH₂[(CH₂)₂O]₃O (CH₂)₂CH₃, -OCH₂[(CH₂)₂O]₃O (CH₂)₃CH₃, -OCH₂[(CH₂)₂O]₃O (CH₂)₄CH₃, -OCH₂[(CH₂)₃O]₃OCH₃, -OCH₂[(CH₂)₃O]₃OCH₂CH₃, -OCH₂[(CH₂)₃O]₃O (CH₂)₂CH₃, -OCH₂[(CH₂)₃O]₃O (CH₂)₃CH₃, -OCH₂[(CH₂)₃O]₃O (CH₂)₄CH-, -OCO [(CH₂)₂O]₂OCH₃, -OCO [(CH₂)₂O]₂OCH₂CH₃, -OCO [(CH₂)₂O]₂O (CH₂)₂CH₃, -OCO [(CH₂)₂O]₂O (CH₂)₃CH₃, -OCO [(CH₂)₂O]₂O (CH₂)₄CH₃, -OCO [(CH₂)₃O]₂OCH₃, -OCO [(CH₂)₃O]₂OCH₂CH₃, -OCO [(CH₂)₃O]₂O (CH₂)₂CH₃, -OCO [(CH₂)₃O]₂O (CH₂)₃CH₃, -O [(CH₂)₂O]₂OCH₃, -O [(CH₂)₂O]₂OCH₂CH₃, -O [(CH₂)₂O]₂O (CH₂)₂CH₃, -O [(CH₂)₂O]₂O (CH₂)₃CH₃, -O [(CH₂)₂O]₂O (CH₂)₄CH₃, -O [(CH₂)₃O]₂OCH₃, -O [(CH₂)₃O]₂OCH₂CH₃, -O [(CH₂)₃O]₂O (CH₂)₂CH₃, -O [(CH₂)₃O]₂O (CH₂)₃CH₃, -O [(CH₂)₃O]₂O (CH₂)₄CH₃, -O [(CH₂)₂O]₃OCH₃, -O [(CH₂)₂O]₃OCH₂CH₃, -O [(CH₂)₂O]₃O (CH₂)₂CH₃, -O [(CH₂)₂O]₃O (CH₂)₃CH₃, -O [(CH₂)₂O]₃O (CH₂)₄CH₃, -O [(CH₂)₃O]₃OCH₃, -O [(CH₂)₃O]₃OCH₂CH₃, -O [(CH₂)₃O]₃O (CH₂)₂CH₃, -O [(CH₂)₃O]₃O (CH₂)₃CH₃, -O [(CH₂)₃O]₃O (CH₂)₄CH₃And the like. Poly (oxyalkylene) alkyl groups and their alkoxyl groups are preferred examples of —H, —F, —Cl, —CN, —CF₃R in the general formula (I)¹And the above-mentioned straight-chain alkyl group and straight-chain alkenyl group, or-[(CH₂)₂O]₂OCH₃,-[(CH₂)₂O]₂OCH₂CH₃,-[(CH₂)₂O]₂O (CH₂)₂CH₃,-[(CH₂)₂O]₂O (CH₂)₃CH₃,-[(CH₂)₂O]₂O (CH₂)₄CH₃And their alkoxyl groups are more preferred,
[0026]
-H, -F, -CH₃, -CH₂CH₃,-(CH₂)₂CH₃,-(CH₂)₃CH₃,-(CH₂)₄CH₃,-(CH₂)₅CH₃,-(CH₂)₆CH₃,-(CH₂)₇CH₃, -CH = CH₂, -CH = CHCH₃(E-form),-(CH₂)₂CH = CH₂,-(CH₂)₂CH = CHCH₃(E-form),-(CH₂)₄CH = CH₂,-(CH₂)₄CH = CHCH₃(E-form), -O [(CH₂)₂O]₂OCH₃, -O [(CH₂)₂O]₂OCH₂CH₃, -O [(CH₂)₂O]₂O (CH₂)₂CH₃, -O [(CH₂)₂O]₂O (CH₂)₃CH₃And -O [(CH₂)₂O]₂O (CH₂)₄CH₃Is particularly preferred.
[0027]
L¹, L², L³, L⁴And L⁵And at least one of them is a poly (oxyalkylene) alkyl group, a poly (oxyalkylene) alkoxy group or a poly (oxyalkylene) carboxyl group represented by the general formula (II),³Or L⁴Is preferably substituted by these groups, at which time another L¹, L², L³, L⁴And L⁵Is preferably substituted by -H or -F.
[0028]
As mentioned above, the compound of general formula (I) has its R¹, Linking group Z¹And Z², Ring A¹And A², M and n, L¹, L², L³, L⁴And L⁵Can include a very wide variety of compounds, but by selecting each of its structural sites, it can be made to be a compound suited to a wider field of application, and as a result, the compound of the general formula (I) By using a compound, the behavior of a liquid crystal display element with respect to a temporary application of a temporary voltage such as static electricity has been improved, including those which have been difficult to produce by a conventionally known method, including a moderately large specific resistance value. A liquid crystal composition can be manufactured and is very useful.
[0029]
More specifically, among the compounds of the general formula (I), the compounds described in the formula group 4 are particularly preferred. In the formula group, R¹Is -CH₃, -CH₂CH₃,-(CH₂)₂CH₃,-(CH₂)₃CH₃,-(CH₂)₄CH₃,-(CH₂)₅CH₃,-(CH₂)₆CH₃,-(CH₂)₇CH₃, -CH = CH₂, -CH = CHCH₃(E-form),-(CH₂)₂CH = CH₂,-(CH₂)₂CH = CHCH₃(E-form),-(CH₂)₄CH = CH₂,-(CH₂)₄CH = CHCH₃(E-form) and-(CH₂)₆CH = CH₂And R²Is -CH₃, -CH₂CH₃,-(CH₂)₂CH₃,-(CH₂)₃CH₃,-(CH₂)₄CH₃Represents
[0030]
Embedded image

[0031]
The content of the compound of the general formula (I) is in the range of 0.01 to 50% by mass, preferably in the range of 0.01 to 40% by mass, more preferably 0.01 to 20% by mass.
[0032]
General formula (III) as the second component
Embedded image

[0033]
The compound contains one or more compounds selected from the group consisting of, but preferably 1 to 20, and more preferably 1 to 15. In the formula of the general formula (III), R³Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted by at least one halogen, an alkenyl group having 2 to 12 carbon atoms, or a carbon number substituted by at least one halogen. Represents 2 to 12 alkenyl groups, and represents one or more CH₂The groups may each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O-, as though the O atoms are not directly bonded to each other, An alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms is preferable, and among them, a linear alkyl group and a linear alkenyl group are more preferable. Ring B¹And B²Is preferably a structure as shown in the above formula group 1, but more preferably a structure as shown in the above formula group 2. Linking group Z⁴And Z⁵Is -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO- or a single bond. Among them, a single bond, -CH₂CH₂-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -C≡C-, -COO- or -OCO-, more preferably a single bond, -CH₂CH₂-, -C≡C-, -COO- or -OCO are more preferable, and a single bond or -COO- is particularly preferable. L⁶And L⁸Are each independently -H, -F or -Cl, preferably -H or -F. L⁷Is -F, -Cl, -CN, -CF₃, -OCH₂F, -OCHF₂, -OCF₃, -CH₂CF₃Where -F, -CN, -CF₃Or -OCF₃Is preferable, and -F or -CN is particularly preferable. p and q are each independently 0, 1 or 2, and p + q is 3 or less, and p + q is preferably 1 or 2.
[0034]
Specifically, the compound represented by the general formula (III) is preferably a compound represented by the general formula (IIIa) or the general formula (IIIb).
Embedded image

[0035]
Furthermore, specifically, compounds represented by general formulas (IIIa-1) to (IIIa-1), (IIIb-1) or (IIIb-2) are particularly preferable.
[0036]
Embedded image

[0037]
In the general formulas (IIIa-1) to (IIIa-1), (IIIb-1) or (IIIb-2), X¹And X²Each independently represents -H or -F. The content of the compound of the general formula (III) is in the range of 1 to 80% by mass, preferably in the range of 5 to 60% by mass, more preferably 5 to 50% by mass.
[0038]
As the third component, the general formula (IV)
Embedded image

[0039]
The compound contains one or more compounds selected from the group consisting of, but preferably 1 to 20, and more preferably 1 to 15. In the formula of the general formula (IV), R⁴And R⁵Are each independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted by at least one halogen, an alkenyl group having 2 to 12 carbon atoms or at least one halogen. A alkenyl group having 2 to 12 carbon atoms, wherein one or more CH₂The groups may each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O-, as though the O atoms are not directly bonded to each other, An alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms is preferable, and among them, a linear alkyl group and a linear alkenyl group are more preferable. Ring C¹, C²And C³Is expression group 5
[0040]
Embedded image

[0041]
Although the structure shown in FIG.
Embedded image

[0042]
Are more preferable. Linking group Z⁶, Z⁷And Z⁸Is each independently -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -CF₂CF₂-, -CF = CF-, -CH₂O-, -OCH₂-, -OCH (CH₃)-, -CH (CH₃) O-,-(CH₂)₄-,-(CH₂)₃O-, -O (CH₂)₃-, -C≡C-, -CF₂O-, -OCF₂-, -COO-, -OCO-, -COS-, -SCO-, -CH = NN-CH- or a single bond. Among them, a single bond, -CH₂CH₂-, -CH = CH-, -CH (CH₃) CH₂-, -CH₂CH (CH₃)-, -CH (CH₃) CH (CH₃)-, -C≡C-, -COO-, -OCO- or -CH = NN = CH-, more preferably a single bond, -CH₂CH₂—, —CH ＝ CH—, —C≡C—, —COO—, —OCO— or —CH ＝ NN—CH— are more preferred. r, s and t are each independently 0 or 1, and the sum of r, s and t is 1 or more, and the sum of r, s and t is preferably 2 or 3.
[0043]
Specifically, the compound represented by Formula (IV) is preferably a compound represented by Formula (IVa), Formula (IVb) or Formula (IVc).
Embedded image

[0044]
Further, specifically, it is represented by the general formulas (IVa-1) to (IVa-3), (IVb-1), (IVb-2) or (IVc-1). Compounds are particularly preferred.
Embedded image

[0045]
In the general formulas (IVa-1) to (IVa-3), (IVb-1), (IVb-2) or (IVc-1), Y¹, Y², Y³And Y⁴Represents each independently -H, -F or a methyl group, preferably -H. Z¹⁰Is -CH₂CH₂-, -CH = CH-, -COO-, -OCO-, or a single bond, but -CH₂CH₂-, -CH = CH- or a single bond is preferred. Z¹¹Represents -C≡C-, -COO-, -OCO- or -CH = NN-CH-, but -C≡C- or -CH = NN-CH- is preferable. The content of the compound of the formula (IV) is in the range of 5 to 95% by mass, preferably in the range of 10 to 90% by mass, more preferably 25 to 90% by mass.
[0046]
The liquid crystal composition preferably has a maximum nematic phase temperature of 60 ° C. or higher, more preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher. Δn is preferably in the range of 0.06 to 0.30, more preferably 0.07 to 0.18, and the range of 0.07 to 0.16 is suitable for designing the cell thickness of the TN-LCD. Particularly preferred is a range of 0.12 to 0.18 for designing the cell thickness of the STN-LCD. The dielectric anisotropy (Δε) is preferably 1 or more and 20 or less, particularly preferably 1 or more and 15 or less.
[0047]
The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, a dichroic dye, and the like, in addition to the above compounds. In addition, a chiral agent may be added to prevent a reverse twist domain of the TN-LCD and to induce a helical structure of the STN-LCD. As the chiral agent, a commercially available chiral agent can be used. For example, cholesteryl nonanoate (CN), S-811, R-811, CB-15, C-15 manufactured by Merck, and the like can be mentioned. It is known that the induced helical pitch becomes longer and shorter as the temperature rises, but one or two or more of these may be used, or one or two or more of them may be used in combination. good. For example, in TN-LCD, STN-LCD, and TFT-LCD, the quotient d / p of the thickness d between the substrates and the induced helical pitch p can be selected from the range of 0.001 to 24, but is 0.01 to 0.01. To 12, preferably 0.1 to 2, more preferably 0.1 to 1.5, even more preferably 0.1 to 1, more preferably 0.1 to 0.8. Is particularly preferred.
The above nematic liquid crystal composition is useful for TN-LCD, STN-LCD, OCB-LCD, polymer dispersed liquid crystal display device, and phase change type cholesteric liquid crystal display device, but is particularly useful for TN-LCD and STN-LCD. is there. Further, it can be used for a transmissive or reflective liquid crystal display device.
[0048]
The twisting angle of the TN liquid crystal display device of the present invention can be selected in the range of 80 ° to 130 ° depending on the purpose, and is preferably 85 ° to 110 °. The twist angle of the STN liquid crystal display device of the present invention can be selected from the range of 180 ° to 270 °, and preferably from 220 ° to 260 °.
[0049]
By using the liquid crystal composition of the present invention, a voltage having a moderately large specific resistance value and a voltage temporarily applied to the liquid crystal display element by static electricity can be relaxed in a sufficiently fast time.
[0050]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
[0051]
The characteristics measured in the examples are as follows.
T_NI        ： Nematic phase-isotropic liquid phase transition temperature (℃)
Δε: dielectric anisotropy (25 ° C.)
Δn: birefringence (25 ° C.)
ρ: Specific resistance value (Ω · cm)
Charging time: The time (in seconds) from injecting the liquid crystal composition into the cell, turning it on using an electrostatic gun, and returning to the state where no voltage was applied.
[0052]
The following abbreviations are used in describing the compounds.
-N number: -C_nH_{2n + 1}  (The alkyl side chain is a number, and R is representative.)
-On: -OC_nH_{2n + 1}
-Ndm:-(C_nH_{2n + 1}-CH = CH- (CH₂)_m-1)
ndm-: C_nH_{2n + 1}-CH = CH- (CH₂)_m-1−
-Od (m) n: -O (C_nH_{2n + 1}-CH = CH- (CH₂)_m-2)
d (m) nO-: C_nH_{2n + 1}-CH = CH- (CH₂)_m-2O-
Linking group
-VO-: -COO- -T-: -C≡C-
-2-: -CH₂CH₂−
Substituent
-CN: -C≡N -F: -F
ring
Ph: 1,4-phenylene group Ph1: 3-fluoro-1,4-phenylene group
Ph2: 3,5-difluoro-1,4-phenylene group
Ma: pyrimidine-2,5-diyl group
Cy: 1,4-cyclohexylene group
[0053]
(Example 1, Example 2, Comparative Example 1, Comparative Example 2)
The following nematic liquid crystal compositions (LC1) and (LC2) were prepared, and their physical properties were measured. The results are shown in Table 1.
[Table 1]

The obtained liquid crystal compositions LC1 and LC2 show high specific resistance values. Next, the compound (Ib-2) was added to the above nematic liquid crystal compositions LC1 and LC2.
[0054]
Embedded image

Was added to prepare liquid crystal compositions (LC3 to LC6). For comparison, the nematic liquid crystal compositions LC1 and LC2 were added with crown ether (18K6).
Embedded image

[0055]
Was added to prepare a liquid crystal composition (LC7 to LC10). For another comparison, the amine compound (3CPN)
Embedded image

Was added to prepare liquid crystal compositions (LC11 to LC14). Their specific resistance values and charging characteristics when injected into a 8.3 μm TN cell were measured, and the results are shown in Tables 2 and 3.
[0056]
[Table 2]

[0057]
The nematic liquid crystal compositions LC3 and LC4 were able to significantly shorten the charging time while maintaining a higher specific resistance value than the liquid crystal composition LC1. On the other hand, when crown ether 18K6 was added instead of compound (Ib-2), the effect of shortening the charging time as in Example 1 was recognized, but the specific resistance was lower than that of LC1. Therefore, it was greatly reduced to about 1/100. When the amine compound 3CPN was added instead of the compound (Ib-2), the effect of shortening the charging time as in Example 1 was recognized, but the specific resistance was lower than that of LC1. It decreased significantly to about 1/10, and yellowed over time.
[0058]
[Table 3]

The nematic liquid crystal compositions LC5 and LC6 were able to significantly shorten the charging time while maintaining a higher specific resistance value than the liquid crystal composition LC2. On the other hand, when crown ether 18K6 was added instead of compound (Ib-2), the effect of shortening the charging time as in Example 2 was observed, but the specific resistance was lower than that of LC1. Therefore, it was greatly reduced to about 1/100. When the amine compound 3CPN was added instead of the compound (Ib-2), the effect of shortening the charging time as in Example 1 was recognized, but the specific resistance was lower than that of LC1. It decreased significantly to about 1/10, and yellowed over time.
[0059]
(Example 3, Example 4)
Further, nematic liquid crystal compositions (LC15) and (LC16) were prepared, and their physical property values were measured. The results are shown in Table 4.
[Table 4]

The obtained liquid crystal compositions LC15 and LC16 show high specific resistance values. In the same manner as in Examples 1 and 2, liquid crystal compositions (LC17, LC18) were prepared by adding compound (Ib-2) to liquid crystal composition LC15, and its specific resistance and injection into a 8.3 μm TN cell were performed. Was measured, and the results are shown in Table 5.
[0060]
[Table 5]

The nematic liquid crystal compositions LC17 and LC18 were able to significantly shorten the charging time while maintaining a higher specific resistance value than the liquid crystal composition LC15.
[0061]
Similarly to Examples 1 and 2, the chiral compound S-811 was added to the liquid crystal compositions (LC19, LC20) obtained by adding the compound (Ib-2) to the liquid crystal composition LC16 so that d / p = 0.5. Was prepared, and its specific resistance and charging characteristics when injected into a 240-degree twisted STN cell of 6.0 μm were measured. The results are shown in Table 6.
[0062]
[Table 6]

The nematic liquid crystal compositions LC19 and LC20 were able to significantly reduce the charging time while maintaining a higher specific resistance value than the liquid crystal composition LC16.
[0063]
【The invention's effect】
The nematic liquid crystal composition of the present invention can improve the behavior of a liquid crystal display element with respect to temporary application of a voltage such as static electricity without impairing reliability such as a decrease in specific resistance. For this reason, charging due to static electricity generated in the manufacturing process of the liquid crystal display element can be promptly reduced.

Claims (12)

As the first component, the general formula (I)

(In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with at least one halogen, an alkenyl group having 2 to 12 carbon atoms, or at least one halogen. Represents an alkenyl group having 2 to 12 carbon atoms, and one or two or more CH ₂ groups present in these groups independently represent —O— assuming that O atoms are not directly bonded to each other. , -S-, -CO-, -COO-, -OCO- or -OCO-O-,
A ¹ and A ² are each independently
(A) trans-1,4-2 or more CH ₂ groups xylene group (one CH ₂ group or not adjoining present in this group cycloheteroalkyl is replaced by -O- and / or -S- May be done)
(B) 1,4-phenylene group (the two or more CH ₂ groups not one CH ₂ group or adjacent present in the radical may be replaced by a-N-)
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, wherein the groups (a), (b) and (c) are Each may be independently substituted with CN or halogen,
m and n are each independently 0, 1 or 2, but the sum of m and n is 3 or less;
Z ¹ and ^{Z 2} are each _{independently, -CH 2 CH 2 -, -} CH = CH -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CH (CH 3) _{CH (CH 3) -, -} CF 2 CF 2 -, - CF = CF -, - CH 2 O -, - OCH 2 -, - OCH (CH 3) -, - CH (CH 3) O -, - ( _{CH 2) 4 -, - (} CH 2) 3 O -, - O (CH 2) 3 -, - C≡C -, - CF 2 O -, - OCF 2 -, - COO -, - OCO -, - COS-, -SCO- or a single bond;
L ¹ , L ² , L ³ , L ⁴ and L ⁵ represent —H, —F, —Cl, —CN, —CF ₃ , —OCH ₂ F, —OCHF ₂ , —OCF ₃ , —CH ₂ CF ₃ The same definition as R ¹ in the general formula (I) or the general formula (II)

(Wherein Z ³ is —CH ₂ CH ₂ —, —CH ＝ CH—, —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH (CH _{3 ) -, - CF 2 CF 2} -, - CF = CF -, - CH 2 O -, - OCH 2 -, - OCH (CH 3) -, - CH (CH 3) O -, - (CH 2) 4 _{-, - (CH 2) 3} O -, - O (CH 2) 3 -, - C≡C -, - CF 2 O -, - OCF 2 -, - COO -, - OCO -, - COS -, - SCO-, -CO-, -O-, -S- or a single bond;
R ² has the same meaning as R ¹ in formula (I);
i is 2 or 3;
j is 2 or 3. A) a poly (oxyalkylene) group represented by
At least one of L ¹ , L ² , L ³ , L ⁴ and L ⁵ is a poly (oxyalkylene) group represented by the general formula (II);
When a plurality of A ¹ , A ² , Z ¹ and Z ² are present, they may be the same or different. )
Containing one or more compounds represented by
As the second component, a compound represented by the general formula (III)

(Wherein, R ³ has the same meaning as R ³ in formula (I), and B ¹ and B ² each independently represent
(A) trans-1,4-2 or more CH ₂ groups xylene group (one CH ₂ group or not adjoining present in this group cycloheteroalkyl is replaced by -O- and / or -S- May be done)
(B) 1,4-phenylene group (the two or more CH ₂ groups not one CH ₂ group or adjacent present in the radical may be replaced by a-N-)
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, wherein the groups (a), (b) and (c) are Each may be independently substituted with CN or halogen,
p and q are each independently 0, 1 or 2, but the sum of p and q is 3 or less;
Z ⁴ and ^{Z 5} are each _{independently, -CH 2 CH 2 -, -} CH = CH -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CH (CH 3) _{CH (CH 3) -, -} CF 2 CF 2 -, - CF = CF -, - CH 2 O -, - OCH 2 -, - OCH (CH 3) -, - CH (CH 3) O -, - ( _{CH 2) 4 -, - (} CH 2) 3 O -, - O (CH 2) 3 -, - C≡C -, - CF 2 O -, - OCF 2 -, - COO -, - OCO -, - COS-, -SCO- or a single bond;
L ⁶ and ^{L 8} are each independently, -H, -F, a -Cl, ^{L 7} _{is, -F, -Cl, -CN, -CF} 3, -OCH 2 F, -OCHF 2, -OCF ₃ is _-CH 2 CF ^_3, if the B ^1, B ^{2, Z 4} and ^{Z 5} there are a plurality, they may be different may be the same. )
Containing one or more compounds represented by
As the third component, the general formula (IV)

(Wherein R ⁴ and R ⁵ represent the same meaning as R ¹ in formula (I);
C ¹ , C ² and C ³ are each independently
(A) trans-1,4-2 or more CH ₂ groups xylene group (one CH ₂ group or not adjoining present in this group cycloheteroalkyl is replaced by -O- and / or -S- May be done)
(B) 1,4-phenylene group (the two or more CH ₂ groups not one CH ₂ group or adjacent present in the radical may be replaced by a-N-)
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, wherein the groups (a), (b) and (c) are Each independently may be substituted with CN, methyl group or halogen,
r, s and t are each independently 0 or 1,
Z ^{6, Z 7} and ^{Z 8} are each _{independently, -CH 2 CH 2 -, -} CH = CH -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CH ( _{CH 3) CH (CH 3)} -, - CF 2 CF 2 -, - CF = CF -, - CH 2 O -, - OCH 2 -, - OCH (CH 3) -, - CH (CH 3) O- _{, - (CH 2) 4 -} , - (CH 2) 3 O -, - O (CH 2) 3 -, - C≡C -, - CF 2 O -, - OCF 2 -, - COO -, - OCO —, —COS—, —SCO—, —CH ＝ N—N ＝ CH— or a single bond. A nematic liquid crystal composition comprising one or more compounds represented by formula (1). General formula (Ia)

(In the formula, R ¹ , A ¹ , A ² , Z ¹ , Z ² , m, n, L ¹ , L ² , L ⁴ and L ⁵ are each independently the same as in the general formula (I) in claim 1) R ² , i and j each independently represent the same meaning as in the general formula (II) in claim 1, and Z ³ represents —OCH ₂ —, —OCO—, —O— or a single bond. 2. The nematic liquid crystal composition according to claim 1, comprising a compound represented by the formula: General formula (Ib)

(Wherein, R ¹ , A ¹ , A ² , Z ¹ , Z ² , m, n, L ¹ , L ² , L ³ and L ⁵ are each independently the same as in the general formula (I) in claim 1) R ² , i and j each independently represent the same meaning as in the general formula (II) in claim 1, and Z ³ represents —OCH ₂ —, —OCO—, —O— or a single bond. 2. The nematic liquid crystal composition according to claim 1, comprising a compound represented by the formula: Formula (IIIa) and Formula (IIIb)

(Wherein, R ³ , B ¹ , B ² , Z ⁴ , p, L ⁶ , L ⁷ and L ⁸ each independently represent the same meaning as R ¹ in claim 1). The nematic liquid crystal composition according to any one of claims 1 to 3, comprising one or more compounds selected from the group consisting of: Formula (IVa), Formula (IVb) and Formula (IVc)

(Wherein, R ⁴ , R ⁵ , C ¹ , C ² or C ³ each independently represent the same meaning as R ¹ in claim 1, and Z ⁹ represents —CH ₂ CH ₂ —, —CH ＝ CH— _{, -CH (CH 3) CH 2} -, - CH 2 CH (CH 3) -, - CF 2 CF 2 -, - CF = CF -, - CH 2 O -, - C≡C -, - CF 2 O _{-, - OCF 2 -, -} COO -, - OCO -, -. the CH = N-N = CH- or one compound selected from the group consisting of compounds represented by) represents a single bond or two The nematic liquid crystal composition according to any one of claims 1 to 4, comprising the above. Formula (IIIa-1), Formula (IIIa-2), Formula (IIIa-3), Formula (IIIa-4), Formula (IIIa-5), Formula (IIIb-1) and Formula (IIIb-2)

(Wherein, R ³ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms, and X ¹ and X ^{1 2} independently represent a hydrogen atom or a fluorine atom; L ⁶ and L ⁸ each independently represent —H or —F; L ⁷ represents —F, —CN, —CF ₃ , —OCH ₂ F, -OCHF _2, -OCF _3, represents a _-CH 2 CF _3. of claims 1 to 5 a compound selected from the group consisting of compounds represented by) containing one or more kinds according to any one Nematic liquid crystal composition. The general formula (IV) is represented by the general formulas (IVa-1), (IVa-2), (IVa-3), (IVb-1), (IVb-2) and (IVc). -1)

(Wherein R ³ and R ⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms) Wherein Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent —H, —F or a methyl group, and Z ¹⁰ represents —CH ₂ CH ₂ —, —CH ＝ CH—, —COO—, —OCO— or a single bond, and Z ¹¹ represents —C≡C—, —COO—, —OCO— or —CH ＝ N—N ＝ CH—. The nematic liquid crystal composition according to any one of claims 1 to 5, wherein the composition comprises one or more compounds. The content of the compound of the general formula (I), the general formula (Ia), the general formula (Ib), the general formula (Ic) or the general formula (Id) is in the range of 0.01 to 50% by mass. 8. The nematic liquid crystal composition according to any of 7. 9. The nematic liquid crystal composition according to claim 1, wherein the dielectric anisotropy (Δε) is in the range of 1 to 20. A liquid crystal display device using the liquid crystal composition according to claim 1. A super-twisted nematic (STN) liquid crystal display device using the liquid crystal composition according to claim 1 and having a twist angle of 180 ° to 270 °. A twisted nematic (TN) liquid crystal display device using the liquid crystal composition according to claim 1, wherein the twist angle is 80 ° to 130 °.