JP3783384B2 - Dichroic dye, liquid crystal composition containing the dye, and liquid crystal element - Google Patents
Dichroic dye, liquid crystal composition containing the dye, and liquid crystal element Download PDFInfo
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- JP3783384B2 JP3783384B2 JP34498897A JP34498897A JP3783384B2 JP 3783384 B2 JP3783384 B2 JP 3783384B2 JP 34498897 A JP34498897 A JP 34498897A JP 34498897 A JP34498897 A JP 34498897A JP 3783384 B2 JP3783384 B2 JP 3783384B2
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- liquid crystal
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 9
- -1 n represents 0-1 Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 18
- 239000000987 azo dye Substances 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 125000000532 dioxanyl group Chemical group 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- WCLNGBQPTVENHV-MKQVXYPISA-N cholesteryl nonanoate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCCC)C1 WCLNGBQPTVENHV-MKQVXYPISA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は新規な赤色から青色のアゾ系二色性色素およびこれを含む液晶組成物ならびに液晶素子に関する。
【０００２】
【従来の技術】
現在、液晶表示としてはツイストネマチック（ＴＮ）型表示モード、スーパーツイスト（ＳＴＮ）モードなどの他に各種の表示モードが提案されている。このうち液晶に色素を溶解して用いるゲストホスト（ＧＨ）型表示方式が、広い視野角などの特徴のために、自動車などの表示パネルとして広く用いられている。
このＧＨモードに用いられる二色性色素の特性としては下記の項目
１）二色性
２）溶解性
３）耐光性
４）着色力
が優れていることが要求される。市場のニーズが大きいブラックの液晶組成物を構成する上では、通常、液晶に３原色である黄色、赤色、青系の二色性色素を混合することにより調整される。
【０００３】
二色性色素の主流であるアゾ色素は特に１）二色性、２）溶解性、４）着色力において優れており、黄色〜赤色色素として広く使用されているが、青色色素として実用されているものは少ない。一般的なアゾ色素は、ドナーとアクセプタ−が共役連結基によって結合されているいわゆる分子内ＣＴ型（Charge TransferTransition）の発色系をとることが多く、特に深色アゾ色素の場合にはその傾向が強い。そして、ドナーであるカップラーに大きな電子供与性を有する基を、又、アクセプターとなるジアゾ成分に大きな電子吸引性の基を導入すると、より深色化された色素が得られることが知られている。つまり、色素の色相を深色化するにはジアゾ成分にニトロ基やシアノ基の導入、あるいはチアゾールのようなヘテロ芳香環を用いることが有効であるわけだが、しかし二色性色素においては耐光性や溶解性に大きな難点が生じる。また、繊維用などの通常のアゾ色素の場合は、カップラーとなるベンゼン環の２、４、５位等へ電子供与性基を導入することが深色化に有効であるが、液晶用二色性色素の場合は、ベンゼン環の側方への置換基の導入は二色性の大幅な低下をもたらす傾向がある。また、ポリアゾ化によっても深色化はなされるものの、深色化に限界があり、青色色素にはなりにくいという難点を有していた。
【０００４】
そのために、青色色素としてはアントラキノン系の色素が主流となっている。しかしながらアントラキノン系の色素は、▲１▼二色性比がアゾ色素よりも小さくなる▲２▼溶解性が低い、▲３▼アゾ色素よりも吸光度が小さいために、同じ濃度を得るためには多量の色素を必要とする、▲４▼液晶の粘度を増加させる、▲５▼アゾ色素に比べて二色性のホスト液晶依存性が大きい、等の難点を有する。
また、従来の色素は最近のＴＦＴ液晶素子などに用いられているフッ素系液晶に対する溶解性等の親和性が充分ではないという問題点があった。
【０００５】
【発明が解決しようとする課題】
本発明は、色素の上記の難点の少ない赤色〜青色系の二色性色素およびこれを含む液晶組成物および液晶素子を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは上記課題に鑑み、鋭意検討した結果、アゾ色素のカップラ−成分として、下記化合物
【０００７】
【化２】
を用いることにより、色素の深色化が容易に成されることを見出し、本発明に到達した。
すなわち本発明の要旨は、下記一般式［Ｉ］
【０００９】
【化３】
（式中、Ｘは水素原子、アルキル基、アルコキシ基、アルコキシアルキル基、アルキルスルホニル基、ハロゲン原子、トリフルオロメトキシ基、Ｒ−ＯＣＯ−、Ｒ−ＣＯＯ−、Ｒｆ−、Ｒｆ−Ｓ−、Ｒｆ−ＳＯ２−、Ｒｆ−ＯＣＯ−の基を示し、Ｒはアルキル基；アルキル基、アルコキシ基、シクロヘキシル基、アルキルシクロヘキシル基で置換されていてもよいフェニル基；アルキル基、アルコキシ基、シクロヘキシル基、アルキルシクロヘキシル基で置換されていてもよいシクロヘキシル基を示し、Ｒｆは３個以上のフッ素原子で置換されたアルキル基を示し、Ｗは低級アルキル基を示し、Ｚ1 〜Ｚ3 は、それぞれ水素原子、ハロゲン原子、メチル基、メトキシ基またはトリフルオロメチル基を示し、またＺ1 とＺ2 、Ｚ4 とＺ5 は互いに連結して脂肪族環、芳香族環または含窒素芳香環を形成してもよく、ｎは０〜１、ｐは０〜２の数を表す。）で表されるアゾ系二色性色素、これを含む液晶組成物および液晶素子に存する。
【００１１】
【発明の実施の形態】
本発明のアゾ系二色性色素は、例えば下記の式［II］
【００１２】
【化４】
で示される化合物と下記の式［III ］
【００１４】
【化５】
（式中、Ｘ、ｎ、Ｚ1 〜Ｚ6 、Ｗ、ｐは前示一般式［Ｉ］に於けると同義。）で示される化合物に、公知のジアゾ化カップリング反応を適用することにより合成することができる。
【００１６】
前示一般式［Ｉ］におけるＸの具体例としては水素原子；メチル基、エチル基、直鎖状または分岐鎖のプロピル基、ブチル基、ヘプチル基、オクチル基、ドデシル基、オクタデシル基などのアルキル基；エトキシ基、ブトキシ基などのアルコキシ基；エトキシメチル基、ブトキシメチル基、エトキシエチル基、ブトキシエチル基などのアルコキシアルキル基；ブチルスルホニル基などのアルキルスルホニル基；フッ素原子、塩素原子などのハロゲン原子が挙げられ、Ｒの具体例としてはエチル基、直鎖状または分岐鎖のプロピル基、ブチル基、ヘプチル基、オクチル基などのアルキル基；プロピル基、ブチル基、ヘプチル基、オクチル基などのアルキル基で置換されたフェニル基；エトキシ基、ブトキシ基などのアルコキシ基で置換されたフェニル基；シクロヘキシル基、プロピルシクロヘキシル基、ブチルシクロヘキシル基などのアルキル基で置換されていても良いシクロヘキシル基で置換されたフェニル基；プロピル基、ブチル基、ヘプチル基、オクチル基などのアルキル基で置換されたアルキルシクロヘキシル基；エトキシ基、ブトキシ基などのアルコキシ基で置換されたシクロヘキシル基：シクロヘキシル基、プロピルシクロヘキシル基、ブチルシクロヘキシル基などのアルキル基で置換されていても良いシクロヘキシル基で置換されたシクロヘキシル基を示し、Ｒｆの具体例としてはトリフルオロメチル基、パーフルオロブチル基、パーフルオロヘキシル基、２ー（パーフルオロブチル）エチル基などの３個以上のフッ素原子で置換されたアルキル基などが挙げられ、Ｗの具体例としてはメチル基、エチル基、プロピル基などの低級アルキル基が挙げられ、Ｚ1 とＺ2 、Ｚ4 とＺ5 は互いに連結してテトラリン環の一部などの脂肪族環、ナフタリン環の一部などの芳香族環またはキノリン環の一部などの含窒素芳香環を形成してもよい。
【００１７】
本発明の液晶組成物は前示一般式［Ｉ］で示されるアゾ系二色性色素を、［液晶デバイスハンドブック；日本学術振興会第１４２委員会編（１９８９）；p154〜p192,p715 〜p722］記載のネマチックあるいはスメクチック相を示すビフェニル系、フェニルシクロヘキサン系、フェニルピリミジン系、シクロヘキシルシクロヘキサン系などの各種の液晶化合物または液晶組成物に公知の方法で混合することにより容易に調製することができる。
【００１８】
本発明に用いるホスト液晶材料としては、下記一般式［IV］で表される液晶化合物を主成分とするフッ素系液晶材料、
【００１９】
【化６】
（式中、環Ｂは、シクロヘキサン環、ベンゼン環、シラシクロヘキサン環、ジオキサン環、ピリミジン環を表し、ｑは１〜３の整数を表す。−Ｚ−は単結合、−ＣＯＯ−，−ＣＨ2 ＣＨ2 −、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を示す。さらにＹ1 〜Ｙ3 は水素原子；炭素数１〜７のアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基；フッ素基、塩素基等のハロゲン原子；これらアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基及びハロゲン原子を置換基として有する炭素数１〜７の置換アルキル基、置換アルコキシ基、置換アルコキシアルキル基、置換アルケニル基；置換シクロヘキシル基もしくは置換フェニル基を表し、Ｙ4 は炭素数１〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基を示す。）
または下記一般式［Ｖ］及び一般式［VI］で表される液晶化合物を主成分とするＮｎ型液晶材料、
【００２１】
【化７】
【化８】
（式中、環Ｂは、シクロヘキサン環、ベンゼン環、シラシクロヘキサン環、ジオキサン環、ピリミジン環を表し、ｑは１〜３の整数を表す。−Ｚ−は単結合、−ＣＯＯ−，−ＣＨ2 ＣＨ2 −、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を示す。さらにＹ5 及びＹ6 は水素原子；炭素数１〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基もしくはこれらアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基、ハロゲン原子を置換基として有する置換シクロヘキシル基もしくは置換フェニル基を表す。さらにＹ7 及びＹ8 は水素原子；フッ素基、塩素基等のハロゲン原子を示し、Ｙ9 及びＹ10は炭素数１〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基もしくはこれらアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基、ハロゲン原子を置換基として有する置換シクロヘキシル基を示す。）
または下記一般式［VII ］および一般式［VIII］で表される液晶化合物を主成分とするシアノ系液晶材料が挙げられる。
【００２４】
【化９】
【化１０】
（式中、環Ｂは、シクロヘキサン環、ベンゼン環、シラシクロヘキサン環、ジオキサン環、ピリミジン環を表し、ｑは１〜３の整数を表す。−Ｚ−は単結合、−ＣＯＯ−，−ＣＨ2 ＣＨ2 −、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を示す。さらにＹ11及びＹ13は炭素数１〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基；シアノ基を示し、Ｙ12、Ｙ14は炭素数１〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、アルケニル基を示す。）
【００２７】
また本発明の液晶組成物はコレステリルノナノエートなどの、液晶相を示しても示さなくても良い光学活性化合物を含有しても良く、あるいは紫外線吸収剤、酸化防止剤などの各種の添加剤を含有しても良い。
このようにして得られた液晶組成物を、少なくとも一方が透明な電極付基板間に挟持することにより、ゲストホスト効果を応用した素子［松本正一、角田市良”液晶の最新技術”工業調査会、34(1983);J.L.Fergason,SID85Digest,68(1985)等］などを構成することができる。
【００２８】
【実施例】
以下の実施例により本発明をさらに具体的に説明する。
実施例１
下記構造式で示されるアゾ化合物
【００２９】
【化１１】
０．４６ｇをＮ−メチル−２−ピロリドン１５ｍｌに溶解し、３５％塩酸０．３ｍｌ添加後、０〜５℃まで冷却し、亜硝酸ナトリウム０．０８ｇを含む水溶液を添加して、２時間同温で撹拌してジアゾ化させた。他方、下記のカップラー
【００３１】
【化１２】
０．２０ｇをＮ−メチル−２−ピロリドン少量と混合し、先のジアゾ液に添加して約２時間反応させた。
反応後、室温にてメタノールで希釈して析出物を濾過、水洗、乾燥して得られた結晶をカラムクロマトにより精製して下記構造式
【００３３】
【化１３】
の色素０．１７ｇを得た。
このアゾ色素を商品名ZLI-1565（E.MERCK 社製）として市販されているフェニルシクロヘキサン系液晶混合物に１wt% の濃度で溶解させ青色のゲストホスト液晶組成物を調製した。これをポリイミド系樹脂を塗布、硬化、ラビング処理した透明電極付きガラス基板を対向させ、液晶が平行配向となるように構成したギャップ９μのセルに封入した。
この青色に着色したセルの配向方向に平行な直線偏光に対する吸光度（Ａ//）および配向方向に垂直な直線偏光に対する吸光度（Ａ⊥）を測定し、その吸収ピーク（λmax ：６０７nm）におけるオ−ダ−パラメ−タ−（Ｓ）を下記の式
【００３５】
【数１】
Ｓ＝（Ａ//−Ａ⊥）／（Ａ//＋２Ａ⊥）
【００３６】
から求めた結果、Ｓ＝０．７４であった。
上記のZLI −1565の代わりに商品名ZLI-4792（E.MERCK 社製）として市販されているフッ系液晶混合物を用いて、同様にしてオ−ダ−パラメ−タ−を求めた結果、Ｓ＝０．７５（λmax ６００nm）であった。
【００３７】
参考例
実施例１の方法において、カップラーをジアルキルタイプのカップリング成分である
【００３８】
【化１４】
に代えて得られた
【００４０】
【化１５】
のフェニルシクロヘキサン系液晶混合物：商品名ZLI-1565（E.MERCK 社製）中における色相は暗紫色、λmax ５４７ｎｍであり、先の実施例に比較してλmax が６０ｎｍ短波長であった。オーダーパラメーター（Ｓ）は０．７６であった。
同色素のフッ系液晶混合物：商品名ZLI-4792（E.MERCK 社製）中における色相は暗紫色、λmax ５４３ｎｍであり、先の実施例に比較してλmax が５７ｎｍ短波長であった。オーダーパラメーター（Ｓ）は０．７６であった。
【００４２】
実施例２
前記の実施例に準じた方法により得られた各種アゾ化合物のフッ系液晶混合物：商品名ZLI-4792（E.MERCK 社製）中におけるオ−ダ−パラメ−タ−（Ｓ）と色相を表−１に示す。
【００４３】
【表１】
【表２】
【表３】
【表４】
【発明の効果】
本発明の高い二色性と高い着色力をもつ赤色〜青色系の二色性色素およびこれを含む液晶組成物により、コントラストおよび耐久性に優れた表示素子などの液晶素子を構成することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel red to blue azo dichroic dye, a liquid crystal composition containing the same, and a liquid crystal element.
[0002]
[Prior art]
Currently, various display modes have been proposed as liquid crystal displays in addition to a twisted nematic (TN) type display mode, a super twist (STN) mode, and the like. Among these, a guest-host (GH) type display method in which a dye is dissolved in a liquid crystal is widely used as a display panel for automobiles or the like because of its wide viewing angle.
As characteristics of the dichroic dye used in the GH mode, the following items 1) dichroism 2) solubility 3) light resistance 4) excellent coloring power are required. In constructing a black liquid crystal composition having a great market need, the liquid crystal is usually adjusted by mixing three primary colors yellow, red and blue dichroic dyes.
[0003]
The azo dyes that are the mainstream of dichroic dyes are particularly excellent in 1) dichroism, 2) solubility, and 4) coloring power, and are widely used as yellow to red dyes, but are practically used as blue dyes. There are few things. Common azo dyes often adopt a so-called intramolecular CT type (Charge Transfer Transition) coloration system in which a donor and an acceptor are bonded by a conjugated linking group, and this tendency is particularly the case with deep color azo dyes. strong. Further, it is known that when a group having a large electron donating property is introduced into a coupler as a donor and a large electron withdrawing group is introduced into a diazo component as an acceptor, a deeper dye is obtained. . In other words, it is effective to introduce a nitro group or a cyano group in the diazo component or use a heteroaromatic ring such as thiazole to deepen the hue of the dye. And a great difficulty in solubility. In addition, in the case of ordinary azo dyes for fibers and the like, it is effective for deepening the color to introduce an electron donating group into the 2, 4, 5 position of the benzene ring serving as a coupler. In the case of sexual dyes, introduction of a substituent to the side of the benzene ring tends to cause a significant decrease in dichroism. Further, although deepening is also achieved by polyazotization, there is a limitation that there is a limit to deepening and it is difficult to be a blue pigment.
[0004]
For this reason, anthraquinone dyes are mainly used as blue dyes. However, anthraquinone dyes are: (1) dichroic ratio is smaller than that of azo dyes, (2) low solubility, and (3) less absorbance than azo dyes. And (4) increase the viscosity of the liquid crystal, and (5) the dichroic host liquid crystal is more dependent on the host liquid crystal than the azo dye.
In addition, the conventional dye has a problem that the affinity such as solubility in fluorine-based liquid crystal used in recent TFT liquid crystal elements is not sufficient.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a red to blue dichroic dye with less of the above-mentioned difficulties of the dye, a liquid crystal composition containing the same, and a liquid crystal element.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have found that the following compounds as coupler components of azo dyes:
[Chemical 2]
As a result, it was found that deep coloration of the dye can be easily achieved by using the present invention, and the present invention has been achieved.
That is, the gist of the present invention is the following general formula [I]
[0009]
[Chemical 3]
(Wherein X represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylsulfonyl group, a halogen atom, a trifluoromethoxy group, R—OCO—, R—COO—, Rf—, Rf—S—, Rf) —SO 2 —, Rf—OCO—, wherein R is an alkyl group; an alkyl group, an alkoxy group, a cyclohexyl group, a phenyl group optionally substituted with an alkylcyclohexyl group; an alkyl group, an alkoxy group, a cyclohexyl group, an alkyl Represents a cyclohexyl group which may be substituted with a cyclohexyl group, Rf represents an alkyl group substituted with 3 or more fluorine atoms, W represents a lower alkyl group, Z 1 to Z 3 are each a hydrogen atom, halogen atom, a methyl group, a methoxy group or a trifluoromethyl group, also Z 1 and Z 2, Z 4 and Z 5 are each An azo dichroic dye represented by the following formula: an aliphatic ring, an aromatic ring or a nitrogen-containing aromatic ring, and n represents 0 to 1 and p represents a number of 0 to 2. It exists in the liquid crystal composition and liquid crystal element containing this.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The azo dichroic dye of the present invention is, for example, the following formula [II]
[0012]
[Formula 4]
And the following formula [III]
[0014]
[Chemical formula 5]
(Wherein X, n, Z 1 to Z 6 , W and p are as defined in the general formula [I] above), by applying a known diazotization coupling reaction to the compound represented by Can be synthesized.
[0016]
Specific examples of X in the general formula [I] shown above are hydrogen atom; alkyl such as methyl group, ethyl group, linear or branched propyl group, butyl group, heptyl group, octyl group, dodecyl group, octadecyl group, etc. Group: alkoxy group such as ethoxy group and butoxy group; alkoxyalkyl group such as ethoxymethyl group, butoxymethyl group, ethoxyethyl group and butoxyethyl group; alkylsulfonyl group such as butylsulfonyl group; halogen such as fluorine atom and chlorine atom Examples of R include specific examples of R, such as an ethyl group, a linear or branched propyl group, a butyl group, a heptyl group, and an octyl group; a propyl group, a butyl group, a heptyl group, an octyl group, and the like. A phenyl group substituted with an alkyl group; a phenyl group substituted with an alkoxy group such as an ethoxy group or a butoxy group; Nyl group; phenyl group substituted by cyclohexyl group which may be substituted by alkyl group such as cyclohexyl group, propylcyclohexyl group and butylcyclohexyl group; substituted by alkyl group such as propyl group, butyl group, heptyl group and octyl group A substituted cyclohexyl group; a cyclohexyl group substituted with an alkoxy group such as an ethoxy group or a butoxy group: a cyclohexyl group substituted with a cyclohexyl group which may be substituted with an alkyl group such as a cyclohexyl group, a propylcyclohexyl group or a butylcyclohexyl group Specific examples of Rf include alkyl groups substituted with three or more fluorine atoms such as trifluoromethyl group, perfluorobutyl group, perfluorohexyl group, 2- (perfluorobutyl) ethyl group, and the like. W Methyl group Specific examples thereof include an ethyl group, and a lower alkyl group such as propyl group, an aliphatic ring such as Z 1 and Z 2, Z 4 and Z 5 are part of the tetralin ring by combining to each other, naphthalene ring A nitrogen-containing aromatic ring such as a part of the aromatic ring or a part of the quinoline ring may be formed.
[0017]
The liquid crystal composition of the present invention comprises an azo dichroic dye represented by the general formula [I] shown above [Liquid Crystal Device Handbook; edited by Japan Society for the Promotion of Science, 142nd Committee (1989); p154 to p192, p715 to p722. It can be easily prepared by mixing by a known method various liquid crystal compounds or liquid crystal compositions such as biphenyl, phenylcyclohexane, phenylpyrimidine, cyclohexylcyclohexane and the like exhibiting a nematic or smectic phase.
[0018]
As the host liquid crystal material used in the present invention, a fluorine-based liquid crystal material mainly composed of a liquid crystal compound represented by the following general formula [IV],
[0019]
[Chemical 6]
(In the formula, ring B represents a cyclohexane ring, a benzene ring, a silacyclohexane ring, a dioxane ring or a pyrimidine ring, q represents an integer of 1 to 3. -Z- represents a single bond, -COO-, -CH 2. CH 2 —, —CH═CH— or —C≡C—, wherein Y 1 to Y 3 are a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkoxyalkyl group, an alkenyl group; Halogen atoms such as chlorine groups; these alkyl groups, alkoxy groups, alkoxyalkyl groups, alkenyl groups, and substituted alkyl groups having 1 to 7 carbon atoms, substituted alkoxy groups, substituted alkoxyalkyl groups, substituted alkenyl groups having the halogen atom as a substituent. Represents a substituted cyclohexyl group or a substituted phenyl group, and Y 4 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an alkeni; Represents a sulfur group.)
Or an Nn-type liquid crystal material mainly composed of a liquid crystal compound represented by the following general formula [V] and general formula [VI],
[0021]
[Chemical 7]
[Chemical 8]
(In the formula, ring B represents a cyclohexane ring, a benzene ring, a silacyclohexane ring, a dioxane ring or a pyrimidine ring, q represents an integer of 1 to 3. -Z- represents a single bond, -COO-, -CH 2. CH 2 —, —CH═CH— or —C≡C—, wherein Y 5 and Y 6 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an alkenyl group, or these alkyl groups. , An alkoxy group, an alkoxyalkyl group, an alkenyl group, a substituted cyclohexyl group or a substituted phenyl group having a halogen atom as a substituent, and Y 7 and Y 8 represent a hydrogen atom; a halogen atom such as a fluorine group or a chlorine group, Y 9 and Y 10 are alkyl groups having 1 to 10 carbon atoms, alkoxy groups, alkoxyalkyl groups, alkenyl groups, or these alkyl groups, alkoxy groups. , An alkoxyalkyl group, an alkenyl group, and a substituted cyclohexyl group having a halogen atom as a substituent.
Or the cyano type liquid crystal material which has as a main component the liquid crystal compound represented by the following general formula [VII] and general formula [VIII] is mentioned.
[0024]
[Chemical 9]
[Chemical Formula 10]
(In the formula, ring B represents a cyclohexane ring, a benzene ring, a silacyclohexane ring, a dioxane ring or a pyrimidine ring, q represents an integer of 1 to 3. -Z- represents a single bond, -COO-, -CH 2. CH 2 —, —CH═CH— or —C≡C—, wherein Y 11 and Y 13 are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an alkenyl group; 12 and Y 14 each represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group or an alkenyl group.
[0027]
The liquid crystal composition of the present invention may contain an optically active compound that may or may not exhibit a liquid crystal phase, such as cholesteryl nonanoate, or various additives such as an ultraviolet absorber and an antioxidant. It may be contained.
A device applying the guest-host effect by sandwiching the liquid crystal composition thus obtained between substrates with transparent electrodes [Shinichi Matsumoto, Ryo Tsunoda, “Advanced Technology of Liquid Crystal”, Industrial Research Association, 34 (1983); JLFergason, SID85 Digest, 68 (1985), etc.].
[0028]
【Example】
The following examples further illustrate the present invention.
Example 1
An azo compound represented by the following structural formula:
Embedded image
0.46 g is dissolved in 15 ml of N-methyl-2-pyrrolidone, 0.3 ml of 35% hydrochloric acid is added, cooled to 0 to 5 ° C., an aqueous solution containing 0.08 g of sodium nitrite is added, and the mixture is added for 2 hours. The mixture was diazotized by stirring at a high temperature. On the other hand, the following coupler [0031]
Embedded image
0.20 g was mixed with a small amount of N-methyl-2-pyrrolidone, added to the diazo solution, and reacted for about 2 hours.
After the reaction, it is diluted with methanol at room temperature, and the precipitate is filtered, washed with water, and dried. The resulting crystals are purified by column chromatography to obtain the following structural formula:
Embedded image
0.17 g of a dye was obtained.
This azo dye was dissolved at a concentration of 1 wt% in a phenylcyclohexane liquid crystal mixture marketed under the trade name ZLI-1565 (manufactured by E. MERCK) to prepare a blue guest-host liquid crystal composition. The glass substrate with a transparent electrode coated, cured and rubbed with a polyimide resin was opposed to this, and sealed in a cell with a gap of 9 μm so that the liquid crystal was aligned in parallel.
The absorbance (A // ) for the linearly polarized light parallel to the alignment direction of the blue colored cell and the absorbance (A に 対 す る) for the linearly polarized light perpendicular to the alignment direction were measured, and the absorbance at the absorption peak (λmax: 607 nm) was measured. The dial parameter (S) is expressed by the following formula:
[Expression 1]
S = (A // -A⊥) / (A // + 2A⊥)
[0036]
Was found to be S = 0.74.
As a result of obtaining the order parameter in the same manner by using a fluorinated liquid crystal mixture marketed under the trade name ZLI-4792 (manufactured by E. MERCK) instead of the above ZLI-1565, S = 0.75 (λmax 600 nm).
[0037]
Reference Example In the method of Example 1, the coupler is a dialkyl type coupling component.
Embedded image
Obtained instead of [0040]
Embedded image
The hue in a phenylcyclohexane-based liquid crystal mixture: trade name ZLI-1565 (manufactured by E. MERCK) was dark purple, λmax 547 nm, and λmax was 60 nm shorter than the previous examples. The order parameter (S) was 0.76.
The hue of the same dye in a fluorine-based liquid crystal mixture: trade name ZLI-4792 (manufactured by E. MERCK) was dark purple, λmax 543 nm, and λmax was 57 nm shorter than the previous examples. The order parameter (S) was 0.76.
[0042]
Example 2
The fluorinated liquid crystal mixture of various azo compounds obtained by the method according to the above-mentioned examples: the order parameter (S) and hue in the trade name ZLI-4792 (manufactured by E. MERCK) -1.
[0043]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
【The invention's effect】
A liquid crystal device such as a display device excellent in contrast and durability can be constituted by the red-blue dichroic dye having high dichroism and high coloring power and a liquid crystal composition containing the same. .
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP34498897A JP3783384B2 (en) | 1997-12-15 | 1997-12-15 | Dichroic dye, liquid crystal composition containing the dye, and liquid crystal element |
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| JP34498897A JP3783384B2 (en) | 1997-12-15 | 1997-12-15 | Dichroic dye, liquid crystal composition containing the dye, and liquid crystal element |
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| JP2002327176A (en) | 2001-03-01 | 2002-11-15 | Toshiba Corp | Guest-host liquid crystal composition and liquid crystal display device |
| CN104725894B (en) * | 2010-06-14 | 2017-06-06 | 巴斯夫欧洲公司 | Black dichroic dye |
| JP6007470B2 (en) * | 2010-09-14 | 2016-10-12 | 三菱化学株式会社 | Dichroic dye, liquid crystal composition, and liquid crystal element |
| KR20180050306A (en) * | 2015-09-04 | 2018-05-14 | 디아이씨 가부시끼가이샤 | Nematic liquid crystal composition and liquid crystal display element using the same |
| WO2018151295A1 (en) | 2017-02-17 | 2018-08-23 | 富士フイルム株式会社 | Liquid crystal display device |
| CN112940525A (en) * | 2019-12-10 | 2021-06-11 | 江苏和成新材料有限公司 | Azo dye and preparation method and application thereof |
| WO2024043261A1 (en) * | 2022-08-26 | 2024-02-29 | 日本化薬株式会社 | Azo compound or salt thereof, and polarizing film, polarizing plate and liquid crystal display device comprising same |
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| JPS5657850A (en) * | 1979-10-18 | 1981-05-20 | Nippon Kanko Shikiso Kenkyusho:Kk | Azo compound and dichromatic dye for liquid crystal consisting of the same |
| JPS5884858A (en) * | 1981-11-16 | 1983-05-21 | Mitsubishi Chem Ind Ltd | Azo-based multicolor dyestuff and liquid crystal composition and display containing the same |
| JPS58142968A (en) * | 1982-02-18 | 1983-08-25 | Casio Comput Co Ltd | Two-color dye for liquid crystal |
| JPH0613704B2 (en) * | 1982-10-21 | 1994-02-23 | 三菱化成株式会社 | Liquid crystal composition containing azo polychromatic dye |
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