JP4083834B2 - Liquid crystal composition containing tolan compound and liquid crystal display device - Google Patents
Liquid crystal composition containing tolan compound and liquid crystal display device Download PDFInfo
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- JP4083834B2 JP4083834B2 JP00448597A JP448597A JP4083834B2 JP 4083834 B2 JP4083834 B2 JP 4083834B2 JP 00448597 A JP00448597 A JP 00448597A JP 448597 A JP448597 A JP 448597A JP 4083834 B2 JP4083834 B2 JP 4083834B2
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- liquid crystal
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- crystal composition
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- tolan
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 83
- 239000000203 mixture Substances 0.000 title claims description 41
- -1 tolan compound Chemical class 0.000 title claims description 40
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical class C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 description 37
- 239000000126 substance Substances 0.000 description 21
- 238000000862 absorption spectrum Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000007704 transition Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- SLABLGWZCOFZMX-UHFFFAOYSA-N 2-(4-propylcyclohexyl)ethynylbenzene Chemical group C1CC(CCC)CCC1C#CC1=CC=CC=C1 SLABLGWZCOFZMX-UHFFFAOYSA-N 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- NMZPWKRKMBJEOZ-UHFFFAOYSA-N 4-propylcyclohexane-1-carbonyl chloride Chemical compound CCCC1CCC(C(Cl)=O)CC1 NMZPWKRKMBJEOZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004988 Nematic liquid crystal Substances 0.000 description 4
- 239000004990 Smectic liquid crystal Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LMCBMOAZJXJAIV-UHFFFAOYSA-N 1-ethyl-4-(4-ethynylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(C#C)C=C1 LMCBMOAZJXJAIV-UHFFFAOYSA-N 0.000 description 2
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 2
- NZCKTGCKFJDGFD-UHFFFAOYSA-N 2-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Br NZCKTGCKFJDGFD-UHFFFAOYSA-N 0.000 description 2
- BNPWVUJOPCGHIK-UHFFFAOYSA-N 3,4-difluorophenol Chemical compound OC1=CC=C(F)C(F)=C1 BNPWVUJOPCGHIK-UHFFFAOYSA-N 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- DIZZAMKAEXSJIF-UHFFFAOYSA-N (3,4-difluorophenyl) 4-bromobenzoate Chemical compound C1=C(F)C(F)=CC=C1OC(=O)C1=CC=C(Br)C=C1 DIZZAMKAEXSJIF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DOEQWHNUQQMWFL-HAQNSBGRSA-N CCCCCC[C@H]1CC[C@@H](CC1)C(Cl)=O Chemical compound CCCCCC[C@H]1CC[C@@H](CC1)C(Cl)=O DOEQWHNUQQMWFL-HAQNSBGRSA-N 0.000 description 1
- PPWKQEDYUMJFNK-XYPYZODXSA-N CCCCC[C@H]1CC[C@H](C(Cl)=O)CC1 Chemical compound CCCCC[C@H]1CC[C@H](C(Cl)=O)CC1 PPWKQEDYUMJFNK-XYPYZODXSA-N 0.000 description 1
- MUHNYCNALMBYPS-JOCQHMNTSA-N CCC[C@H]1CC[C@@H](CC1)C(=O)Oc1ccc(Br)cc1 Chemical compound CCC[C@H]1CC[C@@H](CC1)C(=O)Oc1ccc(Br)cc1 MUHNYCNALMBYPS-JOCQHMNTSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は液晶材料として有用なトラン化合物に関し、また、このトラン化合物を含有する液晶組成物、さらにこのトラン化合物を含有する液晶組成物を搭載した液晶表示装置に関するものである。
【０００２】
【従来の技術】
液晶表示装置は、時計、電卓をはじめワープロ、テレビ等に広く利用されている。これらの液晶表示装置の中で特に多く使用されているのは、液晶材料の光学的異方性および誘電率異方性を利用した液晶表示装置である。
【０００３】
液晶表示装置に用いられる液晶材料に要求される特性としては、液晶温度範囲が広いこと、電気光学的に速い応答速度を得るために粘度が小さいこと、広い視野角範囲、高いコントラストを得るために適切な複屈折（△ｎ）をもつこと、低い駆動電圧を得るために誘電率異方性（△ε）が大きいこと、化学的および光学的に安定であることなどが挙げられる。
【０００４】
実用されている液晶組成物は通常、室温付近に液晶相を有する化合物と、室温より高い温度領域に液晶相を有する化合物とを混合して調整される。液晶表示装置が屋外で使用し得る為には、−４０℃〜９０℃の温度範囲で安定に存在しなければならず、また誘電率異方性、屈折率異方性の温度依存性に関連して、Ｎ−Ｉ点（ネマティック−等方相転移温度）付近では急激な変化が起こるので、Ｎ−Ｉ点の高い液晶材料が必要となる。
【０００５】
また、広視野角、高コントラストを得るためには、液晶層のリターデーション△ｎ・ｄ（△ｎは液晶材料の複屈折、ｄは液晶層の厚み）を最適化する必要がある。しかし、実用に使用される液晶表示装置では液晶層の厚みｄが、ある限定された範囲で設定されており、かつ応答速度を速くすることが要求されているために、液晶層の厚みｄは薄くなる傾向が強まっている。よって、複屈折△ｎが大きな液晶材料が必要とされている。
【０００６】
駆動電圧はしきい値電圧Ｖthの値に依存し、しきい値電圧Ｖthは誘電率の異方性△εの平方根に反比例する。そのため誘電率の異方性△εが正の液晶材料を用いるとしきい値電圧Ｖthを低い値に抑えることができる。
【０００７】
これまで、種々の液晶化合物が開発され、使用されているが、以上のような特性を全て満足する単一の液晶化合物は未だに見い出されていない。そのためにいろいろな特性をもった数種の液晶化合物を混合したり、あるいは非液晶化合物を混合したりして実用に供しているのが現状であるが、やはり、充分満足できるものではない。
【０００８】
この様に混合して用いられるトラン系の化合物では、４−アルキル−４’−アルコキシトラン、４−アルキル−４’−フルオロトラン等が知られているが、充分特性を満足できるとはいえなかった。また、本発明の下記化２に示す一般式（Ｉ）で表される構造を持つ、トラン化合物については知られていなかった。
【０００９】
【発明が解決しようとする課題】
以上示したように、これまで、液晶組成物については種々検討されているが、未だ完全と言われるものは見いだされていない。また、液晶組成物に用いられる化合物は、いずれもその特性に一長一短があり、さらに液晶表示装置によって、前記要求される特性の度合いも異なるため、目的に応じた特性を与える新たな液晶化合物および、液晶添加物の出現が待ち望まれている。そこで本発明の目的は、液晶組成物に混合することによって、液晶組成物のＮ−Ｉ点を高くし、かつ複屈折△ｎを大きくすることのできる新規なトラン化合物を提供することであり、また、それを含む液晶組成物を提供することであり、さらにその液晶組成物を搭載してなる液晶表示装置を提供することである。
【００１０】
【課題を解決するための手段】
本発明は、下記一般式（Ｉ）で表されるトラン化合物を少なくとも一種含有する液晶組成物である。
【００１１】
【化２】
また、本発明の液晶表示装置は、前記一般式（Ｉ）で表されるトラン化合物を少なくとも一種含有する液晶組成物を搭載することを特徴とする液晶表示装置である。
【００１４】
本発明のトラン化合物において置換基として与えられているハロゲン原子は、塩素原子、あるいは臭素原子でもよいが、粘度及び比抵抗の観点からフッ素原子であることがさらに好ましい。
【００１５】
本発明のトラン化合物は、液晶組成物に混合することによって、液晶組成物のＮ−Ｉ点を高くし、複屈折△ｎを大きくすることのできる優れた化合物である。
【００１６】
本発明のトラン化合物は多くの液晶化合物と混合し、液晶組成物を製造することができる。本発明のトラン化合物と混合可能な液晶化合物としてはエステル系、シクロヘキシルフェニル系、ビフェニル系、ピリミジン系、ジオキサン系、トラン系などが挙げられる。更に、これらの液晶化合物を複数混合したものに本発明のトラン化合物を混合して用いることもできる。
【００１７】
本発明のトラン化合物を含有する液晶組成物は、上述のように、液晶材料として優れた特性を有し、またこの液晶組成物を搭載した液晶表示装置は、温度範囲が広く、広い視野角を持つことができる。
【００１８】
【発明の実施の形態】
本発明は、化２における一般式（Ｉ）で表されるトラン化合物を少なくとも一種含有する液晶組成物である。
【００２０】
また、本発明の液晶表示装置は、前記一般式（Ｉ）で表されるトラン化合物を少なくとも一種含有する液晶組成物を搭載してなる液晶表示装置である。
【００２１】
本発明のトラン化合物の製造方法について、化３、化４に例をあげて説明する。なお式中Ａ，Ｒ，Ｒ’，Ｘ，Ｙ，ｎ，ｍはこれまでと同じ意味を示す。
【００２２】
まず、一般式（Ｉ）で示される化合物のうち、ｎ＝１の場合は、下記化３に示したように、酸クロライド（ａ）と置換フェノール（ｂ）とをピリジン等の不活性有機溶媒中で反応させた後、反応混合物を再結晶、水洗、乾燥させ、エステル化合物（ｃ）を作製する。次にこのエステル化合物（ｃ）とアセチレン化合物（ｄ）を、トリエチルアミン等の存在下にて反応させ、水洗、乾燥、再結晶することにより一般式（Ｉａ）で表されるトラン化合物を得ることができる。
【００２３】
【化３】
次に一般式（Ｉ）で示される化合物のうち、ｍ＝１の場合は、下記化４に示したように、ブロモ安息香酸（ｅ）に塩化チオニル等のハロゲン化剤を作用させて酸塩化物（ｆ）を製造する。次に酸塩化物（ｆ）と置換フェノール（ｇ）とをピリジン等の不活性有機溶媒中で反応させた後、反応混合物を再結晶、水洗、乾燥させ、ブロモ安息香酸−置換フェニルエステル（ｈ）を作製する。さらに（ｈ）とアルキルシクロヘキシルフェニルアセチレン（ｉ）を、トリエチルアミン等の存在下にて反応させ、水洗、乾燥、再結晶することにより一般式（Ｉｂ）で表されるトラン化合物を得ることができる。置換フェノール（ｇ）を置換シクロヘキサノールにかえても同様にトラン化合物を得ることができる。
【００２５】
【化４】
【実施例】
以下、実施例を用いて本発明を、更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。また、本実施例におけるしきい値電圧Ｖthは、液晶組成物をセル厚９μｍのＴＮ型液晶表示装置に搭載して測定した値である。
【００２７】
（参考例１）
４−ブロモフェノール２６ｇ、ジメチルホルムアミド１００ｍｌ、ピリジン１３ｇを溶解し、市販のトランス−４−ｎ−プロピルシクロヘキサンカルボン酸クロライド２９ｇを滴下し、加熱、攪拌した。その後、反応物を水中に流入し、結晶を析出させ、濾別した。希塩酸、水で洗浄し、真空乾燥後、酢酸エチル、メタノールの混合溶媒にて再結晶させ、トランス−４−ｎ−プロピルシクロヘキサンカルボン酸−４−ブロモフェニルエステル４４ｇを得た。これに４−プロピルシクロヘキシルフェニルアセチレン４０ｇ、ビス（トリフェニルフォスフィン）パラジウム（II）クロライド０．０９ｇ、ヨウ化銅０．１ｇ、トリフェニルフォスフィン０．７９ｇ、トリエチルアミン４００ｍｌを加え、加熱、攪拌した。反応物を水に流入して、塩酸で中和し、結晶を析出させる。結晶を濾別後、水洗し、真空乾燥後、酢酸エチルとメタノールの混合溶媒で再結晶を行い、化５記載の化合物４５ｇを得た。この化合物は液晶相を有し、Ｃ−Ｓ点（結晶−スメクティック相転移温度）が６７℃、Ｓ−Ｎ点（スメクティック−ネマティック相転移温度）が１６１℃、Ｎ−Ｉ点が２３５℃であった。また、この化合物の赤外線吸収スペクトルを図１に示す。
【００２８】
【化５】
（参考例２）
トランス−４−ｎ−プロピルシクロヘキサンカルボン酸クロライド２９ｇの代わりにトランス−４−ｎ−ペンチルシクロヘキサンカルボン酸クロライド３３ｇを用いる以外は、参考例１と同様の方法で、化６記載の化合物４７ｇを得た。この化合物は液晶相を有し、Ｃ−Ｓ点（結晶−スメクティック相転移温度）が８６℃、Ｓ−Ｎ点（スメクティック−ネマティック相転移温度）が１３９℃、Ｎ−Ｉ点が２２６℃であった。また、この化合物の赤外線吸収スペクトルを図２に示す。
【００３０】
【化６】
（参考例３）
トランス−４−ｎ−プロピルシクロヘキサンカルボン酸クロライド２９ｇの代わりにトランス−４−ｎ−ヘキシルシクロヘキサンカルボン酸クロライド３５ｇを用いる以外は、参考例１と同様の方法で、化７記載の化合物４８ｇを得た。この化合物は液晶相を有し、Ｃ−Ｓ点（結晶−スメクティック相転移温度）が９３℃、Ｓ−Ｎ点（スメクティック−ネマティック相転移温度）が１３３℃、Ｎ−Ｉ点が２３５℃であった。また、この化合物の赤外線吸収スペクトルを図３に示す。
【００３２】
【化７】
（参考例４）
トランス−４−ｎ−プロピルシクロヘキサンカルボン酸クロライド２９ｇの代わりにトランス−４−ｎ−エチルシクロヘキサンカルボン酸クロライド２７ｇを、４−プロピルシクロヘキシルフェニルアセチレン４０ｇの代わりに４−（４−エチルフェニル）フェニルアセチレン３９ｇを用いる以外は、参考例１と同様の方法で、化８記載の化合物４４ｇを得た。この化合物はネマティック液晶相を有し、Ｃ−Ｎ点（結晶−ネマティック相転移温度）が１６０℃、Ｎ−Ｉ点が２３４℃であった。また、この化合物の赤外線吸収スペクトルを図４に示す。
【００３４】
【化８】
（参考例５）
４−プロピルシクロヘキシルフェニルアセチレン４０ｇの代わりに４−（４−エチルフェニル）フェニルアセチレン３９ｇを用いる以外は、参考例１と同様の方法で、化９記載の化合物４４ｇを得た。この化合物はネマティック液晶相を有し、Ｃ−Ｎ点（結晶−ネマティック相転移温度）が１６０℃、Ｎ−Ｉ点が２３３℃であった。また、この化合物の赤外線吸収スペクトルを図５に示す。
【００３６】
【化９】
（実施例６）
４−ブロモ安息香酸１００ｇに塩化チオニル１２０ｇを加え、９０℃まで加熱しながら６時間攪拌し、反応終了後、過剰の塩化チオニルを留去した。約２０ｍｍＨｇで減圧蒸留し、蒸留温度１９０〜２００℃でブロモ安息香酸クロライド８５ｇを得た。３，４−ジフルオロフェノール５０ｇ、ジメチルホルムアミド１５０ｍｌ、ピリジン３１ｇを溶解し、３０℃以下で攪拌しながら、得られたブロモ安息香酸クロライドを約１時間で滴下した。その後、７０℃まで加熱して、１０時間攪拌して、反応物を１０倍量の水に投入し、結晶を析出させた。濾別した後、希塩酸、水の順で洗浄、４０℃で真空乾燥し、酢酸エチルで再結晶して、４−ブロモ安息香酸−（３，４−ジフルオロフェニル）エステル５０ｇを得た。これに４−プロピルシクロヘキシルフェニルアセチレン４０ｇ、ビス（トリフェニルフォスフィン）パラジウム（II）クロライド０．１１ｇ、ヨウ化銅０．１２ｇ、トリフェニルフォスフィン０．９６ｇ、トリエチルアミン４００ｍｌを加え、９０℃まで加熱しながら１０時間攪拌した。反応終了後、１０倍量の水に投入し、結晶を析出させ、濾別し、水洗した。４０℃で真空乾燥し、酢酸エチルとメタノールの混合溶媒で再結晶し、化１０記載の化合物４３ｇを得た。この化合物はネマティック液晶相を有し、Ｃ−Ｎ点（結晶−ネマティック相転移温度）が１０４℃、Ｎ−Ｉ点が２３５℃であった。また、この化合物の赤外線吸収スペクトルを図６に示す。
【００３８】
【化１０】
（実施例７）
３，４−ジフルオロフェノール５０ｇの代わりに４−メチルフェノール４１ｇを用いる以外は、実施例６と同様の方法で、化１１記載の化合物４０ｇを得た。この化合物は液晶相を有し、Ｃ−Ｓ点（結晶−スメクティック相転移温度）が１２４℃、Ｓ−Ｎ点（スメクティック−ネマティック相転移温度）が１３２℃、Ｎ−Ｉ点が２３５℃であった。また、この化合物の赤外線吸収スペクトルを図７に示す。
【００４０】
【化１１】
（参考例８）
市販のネマティック液晶組成物ＺＬＩ−１１３２（メルク社製）９５重量部に、参考例１で製造した本発明のトラン化合物を５重量部加え、液晶組成物を作製した。その液晶組成物の特性を下記表１に示す。
【００４２】
ここで、ＺＬＩ−１１３２のみからなる液晶組成物の特性は、Ｎ−Ｉ点７２．０℃、Δｎ０．１３８、粘度２７．９ｃＰ、Ｖth１．８３Ｖであった。
【００４３】
【表１】
（参考例９〜１２、実施例１３、１４）
参考例８と同様に、液晶組成物ＺＬＩ−１１３２（メルク社製）９５重量部に参考例２〜５、実施例６、７で製造したトラン化合物を５重量部加え、液晶組成物を作成した。その液晶組成物の特性を表１に併せて示す。
【００４５】
表１には、各実施例の番号と同時に、用いたトラン化合物の化学式を記載した。また、トラン化合物を加えないＺＬＩ−１１３２のみからなる液晶組成物の特性も記載した。
【００４６】
表１から明らかなように、トラン化合物を含有する本発明の液晶組成物は、粘性やしきい値電圧Ｖｔｈをあまり損なうことなく、Ｎ−Ｉ点を高くし、複屈折△ｎを大きくすることができる。
【００４７】
【発明の効果】
トラン化合物を混合することによって、本発明の液晶組成物は、基の液晶組成物の粘性やしきい値電圧Ｖｔｈをそれほどかえることなく、Ｎ−Ｉ点を高くし、また複屈折を大きくすることができる。そのため、本発明の液晶組成物は液晶材料として優れた特性を有し、またこの液晶組成物を搭載した液晶表示装置は、温度範囲が広く、広い視野角を持つ。さらに、トラン化合物は種々の化合物との充分な相互溶解性が得られ、液晶組成物の構成物質として多くの液晶材料と組み合わせて使用することができ、液晶組成物の特性改良に有用なものである。
【図面の簡単な説明】
【図１】参考例のトラン化合物の赤外線吸収スペクトルを表す図である。
【図２】参考例のトラン化合物の赤外線吸収スペクトルを表す図である。
【図３】参考例のトラン化合物の赤外線吸収スペクトルを表す図である。
【図４】参考例のトラン化合物の赤外線吸収スペクトルを表す図である。
【図５】参考例のトラン化合物の赤外線吸収スペクトルを表す図である。
【図６】本発明のトラン化合物の赤外線吸収スペクトルを表す図である。
【図７】本発明のトラン化合物の赤外線吸収スペクトルを表す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a tolan compound useful as a liquid crystal material, a liquid crystal composition containing the tolan compound, and a liquid crystal display device equipped with the liquid crystal composition containing the tolan compound.
[0002]
[Prior art]
Liquid crystal display devices are widely used in clocks, calculators, word processors, televisions, and the like. Among these liquid crystal display devices, a liquid crystal display device that uses the optical anisotropy and dielectric anisotropy of a liquid crystal material is particularly frequently used.
[0003]
The characteristics required for liquid crystal materials used in liquid crystal display devices include a wide liquid crystal temperature range, a low viscosity to obtain an electro-optically fast response speed, a wide viewing angle range, and a high contrast. Examples thereof include an appropriate birefringence (Δn), a large dielectric anisotropy (Δε) for obtaining a low driving voltage, and a chemical and optical stability.
[0004]
The liquid crystal composition in practical use is usually prepared by mixing a compound having a liquid crystal phase near room temperature and a compound having a liquid crystal phase in a temperature region higher than room temperature. In order for the liquid crystal display device to be used outdoors, it must exist stably in the temperature range of −40 ° C. to 90 ° C. and is related to the temperature dependence of dielectric anisotropy and refractive index anisotropy. Then, since a rapid change occurs near the NI point (nematic-isotropic phase transition temperature), a liquid crystal material having a high NI point is required.
[0005]
In order to obtain a wide viewing angle and high contrast, it is necessary to optimize the retardation Δn · d of the liquid crystal layer (Δn is the birefringence of the liquid crystal material and d is the thickness of the liquid crystal layer). However, in the liquid crystal display device used for practical use, the thickness d of the liquid crystal layer is set within a certain limited range and it is required to increase the response speed. The tendency to become thinner is increasing. Therefore, a liquid crystal material having a large birefringence Δn is required.
[0006]
The drive voltage depends on the value of the threshold voltage Vth, and the threshold voltage Vth is inversely proportional to the square root of the dielectric anisotropy Δε. Therefore, when a liquid crystal material having a positive dielectric anisotropy Δε is used, the threshold voltage Vth can be suppressed to a low value.
[0007]
Various liquid crystal compounds have been developed and used so far, but no single liquid crystal compound satisfying all the above characteristics has yet been found. For this reason, several types of liquid crystal compounds having various characteristics are mixed or non-liquid crystal compounds are mixed and put into practical use, but it is still not satisfactory.
[0008]
As such a tolan compound used by mixing, 4-alkyl-4′-alkoxytolane, 4-alkyl-4′-fluorotolane and the like are known, but it cannot be said that the characteristics can be sufficiently satisfied. It was. Further, a tolan compound having a structure represented by the general formula (I) shown in the following chemical formula 2 of the present invention has not been known.
[0009]
[Problems to be solved by the invention]
As described above, various studies have been made on the liquid crystal composition so far, but what is said to be complete has not yet been found. In addition, the compounds used in the liquid crystal composition all have advantages and disadvantages, and since the degree of the required characteristics varies depending on the liquid crystal display device, a new liquid crystal compound that imparts characteristics according to the purpose, and The appearance of liquid crystal additives is awaited. Accordingly, an object of the present invention is to provide a novel tolan compound capable of increasing the N-I point of the liquid crystal composition and increasing the birefringence Δn by mixing with the liquid crystal composition, Moreover, it is providing the liquid crystal composition containing it, and also providing the liquid crystal display device mounted with the liquid crystal composition.
[0010]
[Means for Solving the Problems]
The present invention is a liquid crystal composition containing at least one tolan compound represented by the following general formula (I) .
[0011]
[Chemical 2]
Moreover, the liquid crystal display device of the present invention is a liquid crystal display device comprising a liquid crystal composition containing at least one tolan compound represented by the general formula (I).
[0014]
The halogen atom given as a substituent in the tolan compound of the present invention may be a chlorine atom or a bromine atom, but is more preferably a fluorine atom from the viewpoint of viscosity and specific resistance.
[0015]
The tolan compound of the present invention is an excellent compound capable of increasing the NI point of the liquid crystal composition and increasing the birefringence Δn by mixing with the liquid crystal composition.
[0016]
The tolan compound of the present invention can be mixed with many liquid crystal compounds to produce a liquid crystal composition. Examples of the liquid crystal compound that can be mixed with the tolan compound of the present invention include ester-based, cyclohexylphenyl-based, biphenyl-based, pyrimidine-based, dioxane-based, and tolan-based compounds. Furthermore, the tolan compound of this invention can also be mixed and used for what mixed these liquid crystal compounds.
[0017]
As described above, the liquid crystal composition containing the tolan compound of the present invention has excellent characteristics as a liquid crystal material, and a liquid crystal display device equipped with this liquid crystal composition has a wide temperature range and a wide viewing angle. Can have.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
This onset Ming, the tolan compound represented by the general formula (I) in Formula 2 is a liquid crystal composition which contains at least one kind.
[0020]
The liquid crystal display device of the present invention is a liquid crystal display device on which a liquid crystal composition containing at least one kind of the tolan compound represented by the general formula (I) is mounted.
[0021]
The production method of the tolan compound of the present invention will be described with reference to chemical examples 3 and 4. In the formula, A, R, R ′, X, Y, n, and m have the same meaning as before.
[0022]
First, among the compounds represented by the general formula (I), when n = 1, an acid chloride (a) and a substituted phenol (b) are combined with an inert organic solvent such as pyridine as shown in Chemical Formula 3 below. After reacting in the reaction mixture, the reaction mixture is recrystallized, washed with water and dried to produce the ester compound (c). Next, the ester compound (c) and the acetylene compound (d) are reacted in the presence of triethylamine or the like, washed with water, dried and recrystallized to obtain the tolan compound represented by the general formula (Ia). it can.
[0023]
[Chemical 3]
Next, among the compounds represented by the general formula (I), when m = 1, as shown in the following chemical formula 4, a halogenating agent such as thionyl chloride is allowed to act on bromobenzoic acid (e) for acidification. Article (f) is produced. Next, after reacting the acid chloride (f) and the substituted phenol (g) in an inert organic solvent such as pyridine, the reaction mixture is recrystallized, washed with water and dried, and the bromobenzoic acid-substituted phenyl ester (h ). Furthermore, the tolan compound represented by the general formula (Ib) can be obtained by reacting (h) with alkylcyclohexylphenylacetylene (i) in the presence of triethylamine, washing with water, drying and recrystallization. A tolan compound can be obtained in the same manner by replacing the substituted phenol (g) with a substituted cyclohexanol.
[0025]
[Formula 4]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited to these Examples. Further, the threshold voltage Vth in this example is a value measured by mounting the liquid crystal composition on a TN liquid crystal display device having a cell thickness of 9 μm.
[0027]
( Reference Example 1)
26 g of 4-bromophenol, 100 ml of dimethylformamide and 13 g of pyridine were dissolved, and 29 g of commercially available trans-4-n-propylcyclohexanecarboxylic acid chloride was added dropwise, and the mixture was heated and stirred. Thereafter, the reaction product was poured into water to precipitate crystals, which were separated by filtration. The extract was washed with dilute hydrochloric acid and water, dried under vacuum, and recrystallized with a mixed solvent of ethyl acetate and methanol to obtain 44 g of trans-4-n-propylcyclohexanecarboxylic acid-4-bromophenyl ester. To this was added 40 g of 4-propylcyclohexylphenylacetylene, 0.09 g of bis (triphenylphosphine) palladium (II) chloride, 0.1 g of copper iodide, 0.79 g of triphenylphosphine, and 400 ml of triethylamine, and the mixture was heated and stirred. . The reaction is poured into water and neutralized with hydrochloric acid to precipitate crystals. The crystals were separated by filtration, washed with water, dried under vacuum, and recrystallized with a mixed solvent of ethyl acetate and methanol to obtain 45 g of the compound described in Chemical formula 5. This compound has a liquid crystal phase and has a CS point (crystal-smectic phase transition temperature) of 67 ° C, an SN point (smectic-nematic phase transition temperature) of 161 ° C, and an NI point of 235 ° C. It was. Moreover, the infrared absorption spectrum of this compound is shown in FIG.
[0028]
[Chemical formula 5]
( Reference Example 2)
47 g of the compound described in Chemical formula 6 was obtained in the same manner as in Reference Example 1 , except that 33 g of trans-4-n-pentylcyclohexanecarboxylic acid chloride was used instead of 29 g of trans-4-n-propylcyclohexanecarboxylic acid chloride. . This compound has a liquid crystal phase and has a CS point (crystal-smectic phase transition temperature) of 86 ° C, an SN point (smectic-nematic phase transition temperature) of 139 ° C, and an NI point of 226 ° C. It was. The infrared absorption spectrum of this compound is shown in FIG.
[0030]
[Chemical 6]
( Reference Example 3 )
48 g of the compound described in Chemical formula 7 was obtained in the same manner as in Reference Example 1 except that 35 g of trans-4-n-hexylcyclohexanecarboxylic acid chloride was used instead of 29 g of trans-4-n-propylcyclohexanecarboxylic acid chloride. . This compound has a liquid crystal phase, and has a CS point (crystal-smectic phase transition temperature) of 93 ° C, an SN point (smectic-nematic phase transition temperature) of 133 ° C, and an NI point of 235 ° C. It was. The infrared absorption spectrum of this compound is shown in FIG.
[0032]
[Chemical 7]
(Reference Example 4)
Instead of 29 g of trans-4-n-propylcyclohexanecarboxylic acid chloride, 27 g of trans-4-n-ethylcyclohexanecarboxylic acid chloride was used, and instead of 40 g of 4-propylcyclohexylphenylacetylene, 39 g of 4- (4-ethylphenyl) phenylacetylene was used. 44 g of the compound described in Chemical formula 8 was obtained in the same manner as in Reference Example 1 except that This compound had a nematic liquid crystal phase and had a CN point (crystal-nematic phase transition temperature) of 160 ° C. and an NI point of 234 ° C. Moreover, the infrared absorption spectrum of this compound is shown in FIG.
[0034]
[Chemical 8]
(Reference Example 5)
44 g of the compound described in Chemical formula 9 was obtained in the same manner as in Reference Example 1 except that 39 g of 4- (4-ethylphenyl) phenylacetylene was used instead of 40 g of 4-propylcyclohexylphenylacetylene. This compound had a nematic liquid crystal phase and had a CN point (crystal-nematic phase transition temperature) of 160 ° C. and an NI point of 233 ° C. The infrared absorption spectrum of this compound is shown in FIG.
[0036]
[Chemical 9]
(Example 6)
120 g of thionyl chloride was added to 100 g of 4-bromobenzoic acid and stirred for 6 hours while heating to 90 ° C. After the reaction was completed, excess thionyl chloride was distilled off. Distillation under reduced pressure at about 20 mmHg gave 85 g of bromobenzoic acid chloride at a distillation temperature of 190 to 200 ° C. 50 g of 3,4-difluorophenol, 150 ml of dimethylformamide and 31 g of pyridine were dissolved, and the resulting bromobenzoic acid chloride was added dropwise over about 1 hour while stirring at 30 ° C. or lower. Then, it heated to 70 degreeC and stirred for 10 hours, the reaction material was thrown into 10 times amount water, and the crystal | crystallization was deposited. After separation by filtration, the mixture was washed with diluted hydrochloric acid and water in that order, dried in vacuo at 40 ° C., and recrystallized with ethyl acetate to obtain 50 g of 4-bromobenzoic acid- (3,4-difluorophenyl) ester. To this was added 40 g of 4-propylcyclohexylphenylacetylene, 0.11 g of bis (triphenylphosphine) palladium (II) chloride, 0.12 g of copper iodide, 0.96 g of triphenylphosphine, and 400 ml of triethylamine, and heated to 90 ° C. The mixture was stirred for 10 hours. After completion of the reaction, it was poured into 10 times the amount of water to precipitate crystals, filtered off and washed with water. It was vacuum dried at 40 ° C. and recrystallized with a mixed solvent of ethyl acetate and methanol to obtain 43 g of the compound described in
[0038]
[Chemical Formula 10]
(Example 7)
40 g of the compound described in Chemical formula 11 was obtained in the same manner as in Example 6 except that 41 g of 4-methylphenol was used instead of 50 g of 3,4-difluorophenol. This compound has a liquid crystal phase, and has a CS point (crystal-smectic phase transition temperature) of 124 ° C, an SN point (smectic-nematic phase transition temperature) of 132 ° C, and an NI point of 235 ° C. It was. The infrared absorption spectrum of this compound is shown in FIG.
[0040]
Embedded image
( Reference Example 8)
5 parts by weight of the tolan compound of the present invention produced in Reference Example 1 was added to 95 parts by weight of a commercially available nematic liquid crystal composition ZLI-1132 (manufactured by Merck) to prepare a liquid crystal composition. The characteristics of the liquid crystal composition are shown in Table 1 below.
[0042]
Here, the characteristics of the liquid crystal composition comprising only ZLI-1132 were an NI point of 72.0 ° C., Δn of 0.138, a viscosity of 27.9 cP, and a Vth of 1.83 V.
[0043]
[Table 1]
(Reference Examples 9-12, Examples 13 and 14)
In the same manner as in Reference Example 8, 5 parts by weight of the Tolan compound prepared in Reference Examples 2 to 5 and Examples 6 and 7 was added to 95 parts by weight of the liquid crystal composition ZLI-1132 (manufactured by Merck) to prepare a liquid crystal composition. . The characteristics of the liquid crystal composition are also shown in Table 1.
[0045]
Table 1 shows the chemical formulas of the tolan compounds used together with the numbers of the respective examples. In addition, the characteristics of a liquid crystal composition comprising only ZLI-1132 without adding a tolan compound are also described.
[0046]
As is apparent from Table 1, the liquid crystal composition of the present invention containing a tolan compound increases the NI point and increases the birefringence Δn without significantly impairing the viscosity and the threshold voltage Vth. Can do.
[0047]
【The invention's effect】
By mixing the tolan compound, the liquid crystal composition of the present invention can increase the N-I point and increase the birefringence without changing the viscosity or threshold voltage Vth of the liquid crystal composition. Can do. Therefore, the liquid crystal composition of the present invention has excellent characteristics as a liquid crystal material, and a liquid crystal display device equipped with this liquid crystal composition has a wide temperature range and a wide viewing angle. Furthermore, tolan compounds have sufficient mutual solubility with various compounds and can be used in combination with many liquid crystal materials as constituents of liquid crystal compositions, and are useful for improving the properties of liquid crystal compositions. is there.
[Brief description of the drawings]
FIG. 1 is a diagram showing an infrared absorption spectrum of a tolan compound of a reference example .
FIG. 2 is a diagram showing an infrared absorption spectrum of a tolan compound of a reference example .
FIG. 3 is an infrared absorption spectrum of the tolan compound of Reference Example .
FIG. 4 is an infrared absorption spectrum of a tolan compound of Reference Example .
FIG. 5 is an infrared absorption spectrum of the tolan compound of Reference Example .
FIG. 6 is an infrared absorption spectrum of the tolan compound of the present invention.
FIG. 7 is a diagram showing an infrared absorption spectrum of a tolan compound of the present invention.
Claims (2)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00448597A JP4083834B2 (en) | 1997-01-14 | 1997-01-14 | Liquid crystal composition containing tolan compound and liquid crystal display device |
| US09/005,686 US5972244A (en) | 1997-01-14 | 1998-01-13 | Tolan compound and liquid crystal composition containing the same |
| US09/314,297 US6174573B1 (en) | 1997-01-14 | 1999-05-19 | Tolan compound and liquid crystal composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00448597A JP4083834B2 (en) | 1997-01-14 | 1997-01-14 | Liquid crystal composition containing tolan compound and liquid crystal display device |
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| Publication Number | Publication Date |
|---|---|
| JPH10195025A JPH10195025A (en) | 1998-07-28 |
| JP4083834B2 true JP4083834B2 (en) | 2008-04-30 |
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|---|---|---|---|
| JP00448597A Expired - Fee Related JP4083834B2 (en) | 1997-01-14 | 1997-01-14 | Liquid crystal composition containing tolan compound and liquid crystal display device |
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| Country | Link |
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| JP (1) | JP4083834B2 (en) |
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| JPH10195025A (en) | 1998-07-28 |
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