JP3882948B2 - Asymmetric azines - Google Patents
Asymmetric azines Download PDFInfo
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- JP3882948B2 JP3882948B2 JP22121296A JP22121296A JP3882948B2 JP 3882948 B2 JP3882948 B2 JP 3882948B2 JP 22121296 A JP22121296 A JP 22121296A JP 22121296 A JP22121296 A JP 22121296A JP 3882948 B2 JP3882948 B2 JP 3882948B2
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- Prior art keywords
- liquid crystal
- hydrazine
- compound
- general formula
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- 239000004973 liquid crystal related substance Substances 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- -1 1- (4-Fluorobenzylidene) -2- (4-methylbenzylidene) hydrazine 1- (4-Fluorobenzylidene) -2- (4-ethylbenzylidene) hydrazine Chemical compound 0.000 description 35
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 30
- 239000012071 phase Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000007857 hydrazones Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 2
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 2
- MAUCRURSQMOFGV-UHFFFAOYSA-N 4-propylbenzaldehyde Chemical compound CCCC1=CC=C(C=O)C=C1 MAUCRURSQMOFGV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- YQZLLGYYJWGGED-UHFFFAOYSA-N n-[(4-fluorophenyl)methylideneamino]-1-(4-propylphenyl)methanimine Chemical compound C1=CC(CCC)=CC=C1C=NN=CC1=CC=C(F)C=C1 YQZLLGYYJWGGED-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UHNIXTGGQFUWFS-UHFFFAOYSA-N 1-(4-methylphenyl)-n-[[4-(trifluoromethyl)phenyl]methylideneamino]methanimine Chemical compound C1=CC(C)=CC=C1C=NN=CC1=CC=C(C(F)(F)F)C=C1 UHNIXTGGQFUWFS-UHFFFAOYSA-N 0.000 description 1
- QAOOKEDCSJFENK-UHFFFAOYSA-N 1-(4-propylphenyl)-n-[[4-(trifluoromethoxy)phenyl]methylideneamino]methanimine Chemical compound C1=CC(CCC)=CC=C1C=NN=CC1=CC=C(OC(F)(F)F)C=C1 QAOOKEDCSJFENK-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- ARIREUPIXAKDAY-UHFFFAOYSA-N 4-butylbenzaldehyde Chemical compound CCCCC1=CC=C(C=O)C=C1 ARIREUPIXAKDAY-UHFFFAOYSA-N 0.000 description 1
- JRFVBFVDDUPPNQ-UHFFFAOYSA-N 4-heptylbenzaldehyde Chemical compound CCCCCCCC1=CC=C(C=O)C=C1 JRFVBFVDDUPPNQ-UHFFFAOYSA-N 0.000 description 1
- NQVZPRUSNWNSQH-UHFFFAOYSA-N 4-pentylbenzaldehyde Chemical compound CCCCCC1=CC=C(C=O)C=C1 NQVZPRUSNWNSQH-UHFFFAOYSA-N 0.000 description 1
- FZLUYKWRQOVIAW-UHFFFAOYSA-N FC1=CC=C(C=NN=CC2=CC=C(C=C2)CCCC)C=C1 Chemical compound FC1=CC=C(C=NN=CC2=CC=C(C=C2)CCCC)C=C1 FZLUYKWRQOVIAW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- 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】
本発明は有機電子材料や医農薬、特に電気光学的液晶表示用ネマチック液晶材料として有用な非対称アジン類に関する。
【０００２】
【従来の技術】
液晶表示素子は、時計、電卓をはじめとして、各種測定機器、自動車用パネル、ワードプロセッサー、電子手帳、プリンター、コンピューター、テレビ等に用いられるようになっている。液晶表示方式としては、その代表的なものにＴＮ（捩れネマチック）型、ＳＴＮ（超捩れネマチック）型、ＤＳ（動的光散乱）型、ＧＨ（ゲスト・ホスト）型あるいはＦＬＣ（強誘電性液晶）等があり、また駆動方式としても従来のスタティック駆動からマルチプレックス駆動が一般的になり、さらに単純マトリックス方式、最近ではアクティブマトリックス方式が実用化されている。これらの表示方式や駆動方式に応じて、液晶材料としても種々の特性が要求されており、このためこれまでにも非常に多くの液晶化合物が合成されている。
【０００３】
こうした液晶化合物の中で、一般式（Ａ）
【０００４】
【化２】
（式中、Ｒaはアルキル基を表す。）で表されるアジン誘導体は比較的古くから知られており、（ｉ）液晶相上限温度が高い、（ｉｉ）化学的に比較的安定、（ｉｉｉ）製造が容易かつ安価である、等の特性を有する優れた液晶材料である。しかも、本発明者らの検討によると、現在汎用されている液晶組成物に添加することにより、その応答時間を非常に改善できる効果を有することが確認されている。
【０００６】
しかしながら、この（Ａ）の化合物はその融点が高く、他の液晶化合物との相溶性が悪いという問題点があった。
この問題点を改善した化合物として、特開昭５４−８７６８８号公報には一般式（Ｂ）
【０００７】
【化３】
（式中、Ｒaはアルキル基を、ＲbはＲaと異なるアルキル基を表す。）で表される非対称アジン類が報告されている。この（Ｂ）の化合物は（Ａ）の化合物と同程度に高い液晶相上限温度を示すのに加えて、（Ａ）の化合物と比較して融点が低く他の液晶化合物との相溶性も良いといった優れた特徴を有する。
【０００９】
ただし、この（Ｂ）の化合物は誘電率異方性が小さいいわゆるＮ型の液晶であり、液晶組成物の閾値電圧を低減することはできない。
上記の特開昭５４−８７６８８号公報には、一般式（Ｃ）
【００１０】
【化４】
（式中、Ｒaはアルキル基を表す。）で表されるシアノベンゼン誘導体である非対称アジン類が報告されている。この（Ｃ）の化合物は誘電率異方性が大きいいわゆるＰ型液晶であり、低い閾値電圧が要求される場合にも有効である。しかしながら（Ｃ）の化合物はシアノ基が存在するために粘性が増大し応答性においては（Ａ）や（Ｂ）の化合物には及ばない。従って、高速応答性を必要とする用途やあるいは信頼性が重視される用途には適していない。
【００１２】
Ｐ型液晶でありながら粘性を低下させるためには、極性基としてフッ素等のハロゲン原子やトリフルオロメトキシ基等のフッ素置換アルコキシル基やアルキル基を用いることが効果的である。アジン系の液晶化合物でこうした極性基を有する化合物としては唯一、上記の特開昭５４−８７６８８号公報に式（Ｄ）の化合物が記載されている。
【００１３】
【化５】
しかしながら、この（Ｄ）の化合物はアジン骨格中に存在するメチル分岐基のために、ネマチック相の上限温度が７５℃と低く、６９℃以下ではスメクチック相を発現してしまい、さらに粘性が上昇して高速応答には適さない化合物となっている。
【００１５】
従って、アジン系のＰ型液晶化合物であって、粘性が低く、低電圧駆動と高速応答が可能であり、かつネマチック相上限温度の高い液晶化合物が求められる。
【００１６】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、上記の目的に応じるため、非対称アジン系の新規Ｐ型液晶化合物を提供し、さらにこれを用いて高速応答と低電圧駆動が可能な液晶組成物を提供する。
【００１７】
【課題を解決するための手段】
本発明は、上記課題を解決するために、
１． 一般式（Ｉ）
【００１８】
【化６】
（式中、Ｒは炭素原子数１〜１２のアルキル基又はアルコキシル基を表し、Ｚはフッ素原子、塩素原子、−ＯＣＦ3、−ＯＣＦ2Ｈ、−ＣＦ3又は−ＯＣＨ2ＣＦ3を表す。）で表される化合物。
２． 一般式（Ｉ）において、Ｚがフッ素原子であるところの上記１記載の化合物。
３． 一般式（Ｉ）において、Ｚが−ＯＣＦ3であるところの上記１記載の化合物。
４． 一般式（Ｉ）において、Ｒが炭素原子数１〜７の直鎖状アルキル基であるところの上記１、２又は３記載の化合物。
５． 上記１記載の一般式（Ｉ）の化合物を含有する液晶組成物。
を前記課題の解決手段として見出した。
【００２０】
【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。
一般式（Ｉ）において、Ｒは炭素原子数は１〜７が好ましく、直鎖状アルキル基がさらに好ましい。Ｚはフッ素原子又は−ＯＣＦ3が好ましい。
【００２１】
一般式（Ｉ）の化合物は以下のようにして製造することができる。
即ち、一般式（ＩＩ）
【００２２】
【化７】
（式中、Ｒは一般式（Ｉ）におけるとおなじ意味を表す。）で表されるヒドラゾンと一般式（ＩＩＩ）
【００２４】
【化８】
（式中、Ｚは一般式（Ｉ）におけるとおなじ意味を表す。）で表されるベンズアルデヒド誘導体とを反応させることにより容易に得ることができる。この際に、式（ＩＶ）や式（Ｖ）等の対称系のアジン
【００２６】
【化９】
（式中、Ｒ及びＺは一般式（Ｉ）と同じ意味を表す。）
の生成を抑止するためにアミンの存在下に反応させることが好ましい。
アミン類としては２級アミンあるいは３級アミンが好ましく、３級アミンが特に好ましい。さらに３級アミンとしてはトリエチルアミン、トリメチルアミン、トリブチルアミン等のトリアルキルアミン、N,N-ジメチルアニリン、N,N-ジエチルアニリン等の芳香族アミン、ピリジン等の環状アミン類等が用いられるが、トリエチルアミン等のトリアルキルアミンが特に好ましい。
【００２８】
アミンの使用量は（ＩＩ）のヒドラゾンに対して0.1〜20モル量が好ましく、0.5〜10モル量がさらに好ましい。
これらアミン類は（ＩＩ）のヒドラゾンと（ＩＩＩ）のベンズアルデヒドとを反応させる際に系内に添加してもよいが、（ＩＩ）のヒドラゾンを調製する際に、後処理の工程で加えておくことによりアミンを含んだヒドラゾンと（ＩＩＩ）のベンズアルデヒドを反応させても良い。即ち、一般式（ＶＩ）
【００２９】
【化１０】
（式中、Ｒは一般式（Ｉ）におけると同じ意味を表す。）で表されるベンズアルデヒド誘導体をエタノール等の溶媒中で大過剰のヒドラジンと反応させて（ＩＩ）のヒドラゾンを調製し、反応終了後ジクロロメタン等の水に不溶の溶媒を加え、水洗を繰り返して過剰のヒドラジンを除去する。溶媒の大半を溜去後、必要に応じてアミンを追加し、エタノール等の溶媒中で（ＩＩＩ）のベンズアルデヒドを加え反応させる。この反応は冷却下に、あるいは加熱下に行ってもよいが、通常は室温付近で実施することが好ましい。反応終了後は同様にジクロロメタン等の水に不溶の溶媒を加え、水洗を繰り返した後、溶媒を溜去し、メタノール等の溶媒から再結晶して精製する。また、必要に応じて塩基性アルミナによるカラムクロマトグラフィーを用いて、精製することも好ましい。
【００３１】
斯くして製造された一般式（Ｉ）のアジン誘導体の例をその相転移温度とともに第１表に掲げる。
【００３２】
【表１】
表中、Ｃｒは結晶相を、Ｓは帰属不明のスメクチック相を、ＳＡはスメクチックＡ相を、Ｎはネマチック相を、またＩは等方性液体相をそれぞれ表す。相転移温度は「℃」を表す。
【００３４】
第１表からわかるように、本発明の一般式（Ｉ）の化合物はいずれも高いネマチック相上限温度を示す。
一般式（Ｉ）の化合物を従来の液晶組成物に添加することにより得られる優れた効果は以下のように明らかである。
【００３５】
ホスト液晶（Ｈ）
【００３６】
【化１１】
（式中、「％」は『重量％』を表す。）
を調製した。このホスト液晶（Ｈ）は１１６．７℃以下でネマチック相を示し、その融点は１１℃である。これを厚さ４．５μｍのＴＮセルに封入して液晶素子を作製し、その応答時間を測定したところ２１．５ｍ秒であった。ここで応答時間は立ち上がり時間と立ち下がり時間が等しくなる電界印加時の測定値である。また、この素子のしきい値電圧を測定したところ１．８８Ｖであった。
【００３８】
次に、ホスト液晶（Ｈ）８０重量％及び第１表中のＮｏ．（Ｉ−２）
【００３９】
【化１２】
の化合物２０重量％からなる液晶組成物（Ｍ−２）を調製した。この（Ｍ−２）のネマチック相上限温度（ＴN-I）は１０４℃であり、ホスト液晶（Ｈ）よりわずかに低下した。また、この組成物を０℃で２４時間放置したが、結晶の析出等は観察できなかった。これを用いて同様にして素子を作成し、その応答時間を測定したところ、１４ｍ秒と大幅に高速化することができた。次に、その閾値電圧を測定したところ、２．０７Ｖであり、ホスト液晶（Ｈ）よりやや高くなった。
【００４１】
これに対して、Ｎ型のアジン誘導体である（Ｂ−１）
【００４２】
【化１３】
２０重量％及びホスト液晶（Ｈ）８０重量％からなる液晶組成物（Ｍ−Ｂ）を調製した。
（Ｍ−Ｂ）のネマチック相上限温度（ＴN-I）は１１５．６℃で、ホスト液晶（Ｈ）と同程度であり、（Ｍ−２）よりわずかに高くなった。次に、同様にして液晶素子を作成しその応答時間を測定したところ、１５．３ｍ秒と（Ｍ−２）にはやや及ばないもののやはり、ホスト液晶（Ｈ）よりかなり高速になった。ところが、この素子の閾値電圧を測定したところ２．５４Ｖであり、ホスト液晶（Ｈ）や（Ｍ−２）と比較して大幅に上昇してしまった。
【００４４】
以上から、本発明の化合物が、閾値電圧を上昇させたり、その温度範囲を低下させることなく、その応答時間を大幅に改善するうえにおいて、非常に有効であることがわかる。
【００４５】
【実施例】
以下に本発明の実施例を示し、本発明を更に説明する。しかし、本発明はこれらの実施例に限定されるものではない。
【００４６】
化合物の構造は、核磁気共鳴スペクトル（ＮＭＲ）、質量スペクトル（ＭＳ）及び赤外吸収スペクトル（ＩＲ）により確認し、相転移温度の測定は温度調節ステージを備えた偏光顕微鏡と示差走査熱量計（ＤＳＣ）を併用して行った。また、組成物における「％」は『重量％』を表す。
（実施例１） １−（４−フルオロベンジリデン）−２−（４−プロピルベンジリデン）ヒドラジン（第１表中Ｎｏ．（Ｉ−２）の化合物）の合成
【００４７】
【化１４】
ヒドラジン１水和物１４０ｇに４−プロピルベンズアルデヒド５０ｇをエタノール２５０ｍＬに溶解して加え、室温で１時間攪拌した。ジクロロメタン４００ｍＬを加えた後、３００ｍＬの飽和炭酸水素ナトリウム水溶液で３回洗滌した。有機層にトリエチルアミン１５ｍＬを加え、無水硫酸ナトリウムで脱水乾燥させた。減圧下に溶媒を溜去し、トリエチルアミン１５ｍＬを追加し、エタノール２５０ｍＬ及び４−フルオロベンズアルデヒド４３ｇを加え、室温でさらに６時間攪拌した。ジクロロメタン４００ｍＬを加え、３００ｍＬの飽和炭酸水素ナトリウム水溶液で洗滌後、減圧下に溶媒を溜去した。残渣をアルミナ（塩基性）カラムクロマトグラフィー（ジクロロメタン）を用いて精製し、さらにメタノールから再結晶させて、１−（４−フルオロベンジリデン）−２−（４−プロピルベンジリデン）ヒドラジン２６．９ｇを得た。この化合物の融点は７０．５℃であり、９６．５℃までネマチック相を示した。
【００４９】
また、上記において、４−プロピルベンズアルデヒドに換えて、４−メチルベンズアルデヒド、４−エチルベンズアルデヒド、４−ブチルベンズアルデヒド、４−ペンチルベンズアルデヒド、４−ヘプチルベンズアルデヒド、又は４−メトキシベンズアルデヒドを用いることにより、以下の化合物を得た。
【００５０】
１−（４−フルオロベンジリデン）−２−（４−メチルベンジリデン）ヒドラジン
１−（４−フルオロベンジリデン）−２−（４−エチルベンジリデン）ヒドラジン（第１表中Ｎｏ．（Ｉ−１）の化合物）
１−（４−フルオロベンジリデン）−２−（４−ブチルベンジリデン）ヒドラジン（第１表中Ｎｏ．（Ｉ−３）の化合物）
１−（４−フルオロベンジリデン）−２−（４−ペンチルベンジリデン）ヒドラジン
１−（４−フルオロベンジリデン）−２−（４−ヘプチルベンジリデン）ヒドラジン
１−（４−フルオロベンジリデン）−２−（４−メトキシベンジリデン）ヒドラジン
（実施例２） １−（４−トリフルオロメトキシベンジリデン）−２−（４−プロピルベンジリデン）ヒドラジン（第１表中Ｎｏ．（Ｉ−４）の化合物）の合成
【００５１】
【化１５】
実施例１において４−フルオロベンズアルデヒドに換えて、４−トリフルオロメトキシベンゼンを用いた以外は実施例１と同様にして、１−（４−トリフルオロメトキシベンジリデン）−２−（４−プロピルベンジリデン）ヒドラジンを得た。この化合物の相転移温度は第１表にまとめて示した。
【００５３】
同様にして以下の化合物を得た。
１−（４−トリフルオロメトキシベンジリデン）−２−（４−メチルベンジリデン）ヒドラジン
１−（４−トリフルオロメトキシベンジリデン）−２−（４−エチルベンジリデン）ヒドラジン
１−（４−トリフルオロメトキシベンジリデン）−２−（４−ブチルベンジリデン）ヒドラジン
１−（４−トリフルオロメトキシベンジリデン）−２−（４−ペンチルベンジリデン）ヒドラジン
１−（４−トリフルオロメトキシベンジリデン）−２−（４−ヘプチルベンジリデン）ヒドラジン
１−（４−トリフルオロメトキシベンジリデン）−２−（４−メトキシベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−メチルベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−エチルベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−プロピルベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−ブチルベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−ペンチルベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−ヘプチルベンジリデン）ヒドラジン
１−（４−トリフルオロメチルベンジリデン）−２−（４−メトキシベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−メチルベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−エチルベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−プロピルベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−ブチルベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−ペンチルベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−ヘプチルベンジリデン）ヒドラジン
１−（４−ジフルオロメトキシベンジリデン）−２−（４−メトキシベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−メチルベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−エチルベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−プロピルベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−ブチルベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−ペンチルベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−ヘプチルベンジリデン）ヒドラジン
１−［４−（２，２，２−トリフルオロエトキシ）ベンジリデン］−２−（４−メトキシベンジリデン）ヒドラジン
（実施例３） 液晶組成物の調製（１）
ホスト液晶（Ｈ）
【００５４】
【化１６】
は１１６．７℃以下でネマチック相を示し、その融点は１１℃である。これを厚さ４．５μｍのＴＮセルに充填して液晶素子を作製し、測定した応答時間は２１．５ｍ秒であった。（立ち下がり時間と立ち上がり時間が等しくなる電圧印加時）また、この素子の閾値電圧は１．８８Ｖであった。
【００５６】
このホスト液晶（Ｈ）８０％及び実施例１で得た（Ｉ−２）の化合物２０％からなる液晶組成物（Ｍ−２）を調製したところ、ネマチック相上限温度（ＴN-I）は１０４℃であり、あまり低下しなかった。同様にして液晶素子を作製し、その応答時間を測定したところ、１４．０ｍ秒と大幅に高速化されていることがわかった。また、この素子の閾値電圧は２．０７Ｖであり、あまり上昇していなかった。
【００５７】
なお、この組成物を０℃で２４時間放置したが、結晶の析出は見られなかった。
（実施例４） 液晶組成物の調製（２）
ホスト液晶（Ｈ）８０％及び実施例２で得た（Ｉ−４）の化合物２０％からなる液晶組成物（Ｍ−４）を調製した。この（Ｍ−４）のネマチック相上限温度（ＴN-I）は９８℃であり、（Ｍ−２）よりわずかに低くなった。同様にして液晶素子を作製し、その応答時間を測定したところ１５．８ｍ秒であり、（Ｍ−２）よりもやや遅いが、ホスト液晶（Ｈ）と比較するとやはり大幅に改善することができた。また、同様にして素子を作製し閾値電圧を測定したところ、１．８５Ｖであり、（Ｍ−２）よりも低減することができた。
【００５８】
なお、この組成物を０℃で２４時間放置したが、やはり結晶の析出は見られなかった。
（比較例）
ホスト液晶（Ｈ）の８０％及びＮ型のアジン誘導体である（Ｂ−１）
【００５９】
【化１７】
の化合物２０％からなる液晶組成物（Ｍ−Ｂ）を調製した。
（Ｍ−Ｂ）のネマチック相上限温度（ＴN-I）は１１５．６℃で、ホスト液晶（Ｈ）と同程度であり、（Ｍ−２）や（Ｍ−４）よりわずかに高くなった。次に、同様にして液晶素子を作製しその応答時間を測定したところ、１５．３ｍ秒であり、（Ｍ−２）にはやや及ばないもののやはり、ホスト液晶（Ｈ）よりかなり高速になった。ところが、この素子の閾値電圧を測定したところ、２．５４Ｖと（Ｈ）や（Ｍ−２）あるいは（Ｍ−４）と比較して大幅に上昇してしまった。
【００６１】
以上から、本発明の化合物が、閾値電圧を上昇させたり、その温度範囲を低下させることなく、その応答時間を大幅に改善するうえにおいて、非常に有効であることがわかる。
【００６２】
【発明の効果】
本発明により提供される、一般式（Ｉ）で表される非対称Ｐ型アジン誘導体である新規液晶化合物は熱、光等に対し化学的に安定で、液晶性に優れ、しかも工業的にも容易に製造することができる。得られた一般式（Ｉ）の化合物は、従来の液晶化合物あるいは液晶組成物との相溶性にも優れ、この添加により液晶組成物の応答時間を大幅に改善することができる。しかもその閾値電圧をほとんど上昇させることがない。
【００６３】
従って、温度範囲が広く、低電圧駆動と高速応答が可能な液晶表示素子用の液晶材料の構成成分として非常に実用的である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to asymmetric azines useful as organic electronic materials and medical pesticides, particularly as nematic liquid crystal materials for electro-optical liquid crystal displays.
[0002]
[Prior art]
Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, etc., including watches and calculators. Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), or FLC (ferroelectric liquid crystal). In addition, as a driving method, a multiplex drive is generally used instead of a conventional static drive, and a simple matrix method and recently an active matrix method have been put into practical use. Various characteristics are required as a liquid crystal material in accordance with these display methods and driving methods, and so many liquid crystal compounds have been synthesized so far.
[0003]
Among these liquid crystal compounds, the general formula (A)
[0004]
[Chemical 2]
(Wherein R a represents an alkyl group), the azine derivative represented by the formula has been known for a relatively long time, (i) the liquid crystal phase upper limit temperature is high, (ii) chemically relatively stable, iii) It is an excellent liquid crystal material having characteristics such as easy manufacture and low cost. Moreover, according to the study by the present inventors, it has been confirmed that by adding to a liquid crystal composition that is currently widely used, the response time can be greatly improved.
[0006]
However, the compound (A) has a problem that its melting point is high and compatibility with other liquid crystal compounds is poor.
As a compound which has improved this problem, Japanese Patent Application Laid-Open No. 54-87688 discloses a general formula (B).
[0007]
[Chemical 3]
(Wherein R a represents an alkyl group and R b represents an alkyl group different from R a ), and asymmetric azines have been reported. In addition to the liquid crystal phase upper limit temperature being as high as that of the compound (A), the compound (B) has a lower melting point than the compound (A) and is compatible with other liquid crystal compounds. It has excellent characteristics such as
[0009]
However, the compound (B) is a so-called N-type liquid crystal having a small dielectric anisotropy, and the threshold voltage of the liquid crystal composition cannot be reduced.
JP-A-54-87688 discloses a general formula (C).
[0010]
[Formula 4]
Asymmetric azines that are cyanobenzene derivatives represented by the formula (wherein R a represents an alkyl group) have been reported. The compound (C) is a so-called P-type liquid crystal having a large dielectric anisotropy, and is effective even when a low threshold voltage is required. However, since the compound (C) has a cyano group, the viscosity increases and the response is not as good as the compounds (A) and (B). Therefore, it is not suitable for applications requiring high-speed response or applications where reliability is important.
[0012]
In order to reduce the viscosity while being a P-type liquid crystal, it is effective to use a halogen atom such as fluorine, a fluorine-substituted alkoxyl group such as a trifluoromethoxy group, or an alkyl group as a polar group. The only compound having such a polar group as an azine-based liquid crystal compound is described in JP-A No. 54-87688 as described above.
[0013]
[Chemical formula 5]
However, since the compound (D) has a methyl branching group present in the azine skeleton, the upper limit temperature of the nematic phase is as low as 75 ° C., and below 69 ° C., a smectic phase is developed and the viscosity further increases. Therefore, the compound is not suitable for high-speed response.
[0015]
Accordingly, there is a demand for an azine-based P-type liquid crystal compound that has a low viscosity, can be driven at a low voltage, can respond at high speed, and has a high nematic phase upper limit temperature.
[0016]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a new asymmetric azine P-type liquid crystal compound and to provide a liquid crystal composition capable of high-speed response and low-voltage driving using the same. .
[0017]
[Means for Solving the Problems]
In order to solve the above problems, the present invention
1. Formula (I)
[0018]
[Chemical 6]
(In the formula, R represents an alkyl group having 1 to 12 carbon atoms or an alkoxyl group, and Z represents a fluorine atom, a chlorine atom, —OCF 3 , —OCF 2 H, —CF 3, or —OCH 2 CF 3 . ) A compound represented by
2. 2. The compound according to 1 above, wherein in general formula (I), Z is a fluorine atom.
3. 2. The compound according to 1 above, wherein in the general formula (I), Z is —OCF 3 .
4). 4. The compound according to 1, 2 or 3, wherein in general formula (I), R is a linear alkyl group having 1 to 7 carbon atoms.
5). 2. A liquid crystal composition comprising the compound of general formula (I) according to 1 above.
Has been found as means for solving the above problems.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
An example of the present invention will be described below.
In general formula (I), R preferably has 1 to 7 carbon atoms, and more preferably a linear alkyl group. Z is preferably a fluorine atom or —OCF 3 .
[0021]
The compound of general formula (I) can be manufactured as follows.
That is, the general formula (II)
[0022]
[Chemical 7]
(Wherein R represents the same meaning as in general formula (I)) and hydrazone represented by general formula (III)
[0024]
[Chemical 8]
(Wherein Z represents the same meaning as in general formula (I)) and can be easily obtained by reacting with the benzaldehyde derivative represented by formula (I). In this case, a symmetrical azine such as formula (IV) or formula (V)
[Chemical 9]
(In the formula, R and Z represent the same meaning as in general formula (I).)
It is preferable to react in the presence of an amine in order to suppress the formation of.
As amines, secondary amines or tertiary amines are preferable, and tertiary amines are particularly preferable. Further, as the tertiary amine, trialkylamines such as triethylamine, trimethylamine and tributylamine, aromatic amines such as N, N-dimethylaniline and N, N-diethylaniline, cyclic amines such as pyridine, etc. are used. Particularly preferred are trialkylamines such as
[0028]
The amount of amine used is preferably from 0.1 to 20 moles, more preferably from 0.5 to 10 moles, based on the hydrazone of (II).
These amines may be added to the system when reacting the hydrazone of (II) with the benzaldehyde of (III), but are added in the post-treatment step when preparing the hydrazone of (II). The hydrazone containing amine may be reacted with benzaldehyde (III). That is, the general formula (VI)
[0029]
[Chemical Formula 10]
(In the formula, R represents the same meaning as in general formula (I).) The benzaldehyde derivative represented by formula (I) is reacted with a large excess of hydrazine in a solvent such as ethanol to prepare hydrazone of (II), and the reaction After completion, an insoluble solvent such as dichloromethane is added, and washing with water is repeated to remove excess hydrazine. After most of the solvent is distilled off, an amine is added if necessary, and (III) benzaldehyde is added and reacted in a solvent such as ethanol. This reaction may be carried out under cooling or under heating, but usually it is preferably carried out at around room temperature. After completion of the reaction, an insoluble solvent such as dichloromethane is added in the same manner and repeated washing with water is carried out, and then the solvent is distilled off and purified by recrystallization from a solvent such as methanol. Moreover, it is also preferable to refine | purify using the column chromatography by basic alumina as needed.
[0031]
Examples of the azine derivatives of the general formula (I) thus produced are listed in Table 1 together with their phase transition temperatures.
[0032]
[Table 1]
In the table, Cr represents a crystalline phase, S represents an unidentified smectic phase, SA represents a smectic A phase, N represents a nematic phase, and I represents an isotropic liquid phase. The phase transition temperature represents “° C.”.
[0034]
As can be seen from Table 1, all the compounds of the general formula (I) of the present invention exhibit a high nematic phase upper limit temperature.
The excellent effect obtained by adding the compound of the general formula (I) to the conventional liquid crystal composition is apparent as follows.
[0035]
Host liquid crystal (H)
[0036]
Embedded image
(In the formula, “%” represents “% by weight”.)
Was prepared. This host liquid crystal (H) exhibits a nematic phase at 116.7 ° C. or lower, and its melting point is 11 ° C. This was sealed in a TN cell having a thickness of 4.5 μm to produce a liquid crystal element, and the response time was measured and found to be 21.5 ms. Here, the response time is a measured value when an electric field is applied in which the rise time and the fall time are equal. Further, the threshold voltage of this device was measured and found to be 1.88V.
[0038]
Next, host liquid crystal (H) 80% by weight and No. 1 in Table 1 were used. (I-2)
[0039]
Embedded image
A liquid crystal composition (M-2) comprising 20% by weight of the above compound was prepared. This (M-2) had a nematic phase upper limit temperature (T NI ) of 104 ° C., which was slightly lower than that of the host liquid crystal (H). The composition was allowed to stand at 0 ° C. for 24 hours, but no crystal precipitation or the like could be observed. Using this, an element was produced in the same manner, and the response time was measured. As a result, the speed was significantly increased to 14 milliseconds. Next, when the threshold voltage was measured, it was 2.07 V, which was slightly higher than that of the host liquid crystal (H).
[0041]
In contrast, it is an N-type azine derivative (B-1)
[0042]
Embedded image
A liquid crystal composition (MB) comprising 20% by weight and host liquid crystal (H) 80% by weight was prepared.
The nematic phase upper limit temperature (T NI ) of (MB) was 115.6 ° C., similar to the host liquid crystal (H), and slightly higher than (M-2). Next, a liquid crystal element was produced in the same manner and its response time was measured. As a result, it was considerably faster than the host liquid crystal (H), although it was slightly less than 15.3 milliseconds (M-2). However, when the threshold voltage of this element was measured, it was 2.54 V, which was significantly higher than that of the host liquid crystals (H) and (M-2).
[0044]
From the above, it can be seen that the compound of the present invention is very effective in greatly improving the response time without increasing the threshold voltage or decreasing the temperature range.
[0045]
【Example】
The following examples further illustrate the present invention. However, the present invention is not limited to these examples.
[0046]
The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and infrared absorption spectrum (IR), and the phase transition temperature was measured with a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter ( DSC). Further, “%” in the composition represents “% by weight”.
Example 1 Synthesis of 1- (4-fluorobenzylidene) -2- (4-propylbenzylidene) hydrazine (Compound No. (I-2) in Table 1)
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To 140 g of hydrazine monohydrate, 50 g of 4-propylbenzaldehyde was dissolved in 250 mL of ethanol, and the mixture was stirred at room temperature for 1 hour. After adding 400 mL of dichloromethane, it was washed 3 times with 300 mL of saturated aqueous sodium hydrogen carbonate solution. 15 mL of triethylamine was added to the organic layer, and dehydrated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, 15 mL of triethylamine was added, 250 mL of ethanol and 43 g of 4-fluorobenzaldehyde were added, and the mixture was further stirred at room temperature for 6 hours. After adding 400 mL of dichloromethane and washing with 300 mL of saturated aqueous sodium hydrogen carbonate solution, the solvent was distilled off under reduced pressure. The residue was purified using alumina (basic) column chromatography (dichloromethane) and further recrystallized from methanol to obtain 26.9 g of 1- (4-fluorobenzylidene) -2- (4-propylbenzylidene) hydrazine. It was. This compound had a melting point of 70.5 ° C. and exhibited a nematic phase up to 96.5 ° C.
[0049]
In the above, instead of 4-propylbenzaldehyde, by using 4-methylbenzaldehyde, 4-ethylbenzaldehyde, 4-butylbenzaldehyde, 4-pentylbenzaldehyde, 4-heptylbenzaldehyde, or 4-methoxybenzaldehyde, A compound was obtained.
[0050]
1- (4-Fluorobenzylidene) -2- (4-methylbenzylidene) hydrazine 1- (4-Fluorobenzylidene) -2- (4-ethylbenzylidene) hydrazine (Compound No. (I-1) in Table 1) )
1- (4-Fluorobenzylidene) -2- (4-butylbenzylidene) hydrazine (No. (I-3) compound in Table 1)
1- (4-Fluorobenzylidene) -2- (4-pentylbenzylidene) hydrazine 1- (4-fluorobenzylidene) -2- (4-heptylbenzylidene) hydrazine 1- (4-fluorobenzylidene) -2- (4- Methoxybenzylidene) hydrazine (Example 2) Synthesis of 1- (4-trifluoromethoxybenzylidene) -2- (4-propylbenzylidene) hydrazine (compound No. (I-4) in Table 1)
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1- (4-trifluoromethoxybenzylidene) -2- (4-propylbenzylidene) was used in the same manner as in Example 1 except that 4-trifluoromethoxybenzene was used instead of 4-fluorobenzaldehyde in Example 1. Hydrazine was obtained. The phase transition temperatures of this compound are summarized in Table 1.
[0053]
Similarly, the following compounds were obtained.
1- (4-trifluoromethoxybenzylidene) -2- (4-methylbenzylidene) hydrazine 1- (4-trifluoromethoxybenzylidene) -2- (4-ethylbenzylidene) hydrazine 1- (4-trifluoromethoxybenzylidene) 2- (4-Butylbenzylidene) hydrazine 1- (4-trifluoromethoxybenzylidene) -2- (4-pentylbenzylidene) hydrazine 1- (4-trifluoromethoxybenzylidene) -2- (4-heptylbenzylidene) hydrazine 1- (4-trifluoromethoxybenzylidene) -2- (4-methoxybenzylidene) hydrazine 1- (4-trifluoromethylbenzylidene) -2- (4-methylbenzylidene) hydrazine 1- (4-trifluoromethylbenzylidene) -2- (4-Ethyl Nylidene) hydrazine 1- (4-trifluoromethylbenzylidene) -2- (4-propylbenzylidene) hydrazine 1- (4-trifluoromethylbenzylidene) -2- (4-butylbenzylidene) hydrazine 1- (4-trifluoro) Methylbenzylidene) -2- (4-pentylbenzylidene) hydrazine 1- (4-trifluoromethylbenzylidene) -2- (4-heptylbenzylidene) hydrazine 1- (4-trifluoromethylbenzylidene) -2- (4-methoxy Benzylidene) hydrazine 1- (4-difluoromethoxybenzylidene) -2- (4-methylbenzylidene) hydrazine 1- (4-difluoromethoxybenzylidene) -2- (4-ethylbenzylidene) hydrazine 1- (4-difluoromethoxybenzylidene) -2 (4-propylbenzylidene) hydrazine 1- (4-difluoromethoxybenzylidene) -2- (4-butylbenzylidene) hydrazine 1- (4-difluoromethoxybenzylidene) -2- (4-pentylbenzylidene) hydrazine 1- (4- Difluoromethoxybenzylidene) -2- (4-heptylbenzylidene) hydrazine 1- (4-difluoromethoxybenzylidene) -2- (4-methoxybenzylidene) hydrazine 1- [4- (2,2,2-trifluoroethoxy) benzylidene ] -2- (4-Methylbenzylidene) hydrazine 1- [4- (2,2,2-trifluoroethoxy) benzylidene] -2- (4-ethylbenzylidene) hydrazine 1- [4- (2,2,2) -Trifluoroethoxy) benzylidene] -2- (4-propylbenzene) Nylidene) hydrazine 1- [4- (2,2,2-trifluoroethoxy) benzylidene] -2- (4-butylbenzylidene) hydrazine 1- [4- (2,2,2-trifluoroethoxy) benzylidene]- 2- (4-Pentylbenzylidene) hydrazine 1- [4- (2,2,2-trifluoroethoxy) benzylidene] -2- (4-heptylbenzylidene) hydrazine 1- [4- (2,2,2-tri Fluoroethoxy) benzylidene] -2- (4-methoxybenzylidene) hydrazine (Example 3) Preparation of liquid crystal composition (1)
Host liquid crystal (H)
[0054]
Embedded image
Shows a nematic phase below 116.7 ° C., and its melting point is 11 ° C. This was filled in a 4.5 μm thick TN cell to produce a liquid crystal device, and the measured response time was 21.5 ms. (At the time of voltage application in which the fall time and the rise time are equal) The threshold voltage of this element was 1.88V.
[0056]
When a liquid crystal composition (M-2) comprising 80% of the host liquid crystal (H) and 20% of the compound (I-2) obtained in Example 1 was prepared, the nematic phase upper limit temperature (T NI ) was 104 ° C. And did not drop much. Similarly, when a liquid crystal element was manufactured and its response time was measured, it was found that the speed was significantly increased to 14.0 milliseconds. Further, the threshold voltage of this element was 2.07 V, and it did not increase so much.
[0057]
This composition was allowed to stand at 0 ° C. for 24 hours, but no crystal deposition was observed.
(Example 4) Preparation of liquid crystal composition (2)
A liquid crystal composition (M-4) comprising 80% of the host liquid crystal (H) and 20% of the compound (I-4) obtained in Example 2 was prepared. This (M-4) had a nematic phase upper limit temperature (T NI ) of 98 ° C., which was slightly lower than (M-2). Similarly, a liquid crystal element was manufactured and its response time was measured to be 15.8 milliseconds, which is slightly slower than (M-2), but it can be significantly improved compared to the host liquid crystal (H). It was. Similarly, when a device was produced and the threshold voltage was measured, it was 1.85 V, which was lower than (M-2).
[0058]
This composition was allowed to stand at 0 ° C. for 24 hours, but no crystal deposition was observed.
(Comparative example)
80% of the host liquid crystal (H) and N-type azine derivative (B-1)
[0059]
Embedded image
A liquid crystal composition (MB) comprising 20% of the above compound was prepared.
The nematic phase upper limit temperature (T NI ) of (MB) was 115.6 ° C., similar to the host liquid crystal (H), and slightly higher than (M-2) and (M-4). Next, a liquid crystal element was produced in the same manner and its response time was measured. As a result, it was 15.3 ms, which was slightly faster than the host liquid crystal (H), although it was slightly less than (M-2). . However, when the threshold voltage of this element was measured, it was 2.54 V, which was significantly higher than (H), (M-2) or (M-4).
[0061]
From the above, it can be seen that the compound of the present invention is very effective in greatly improving the response time without increasing the threshold voltage or decreasing the temperature range.
[0062]
【The invention's effect】
The novel liquid crystal compound which is an asymmetric P-type azine derivative represented by the general formula (I) provided by the present invention is chemically stable to heat, light, etc., has excellent liquid crystallinity, and is industrially easy. Can be manufactured. The obtained compound of the general formula (I) is excellent in compatibility with the conventional liquid crystal compound or liquid crystal composition, and the addition can greatly improve the response time of the liquid crystal composition. Moreover, the threshold voltage is hardly increased.
[0063]
Therefore, it is very practical as a component of a liquid crystal material for a liquid crystal display element that has a wide temperature range and can be driven at a low voltage and can respond at high speed.
Claims (5)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22121296A JP3882948B2 (en) | 1996-08-22 | 1996-08-22 | Asymmetric azines |
| EP97114465A EP0825176B1 (en) | 1996-08-22 | 1997-08-21 | Azine derivative, process for the preparation thereof, nematic liquid crystal composition and liquid crystal display system comprising same |
| SG1997003016A SG67415A1 (en) | 1996-08-22 | 1997-08-21 | Azine derivative process for the preparation thereof nematic liquid crystal composition and liquid crystal display system comprising same |
| DE69708231T DE69708231T2 (en) | 1996-08-22 | 1997-08-21 | Azine derivative, process for its preparation, nematic liquid crystalline composition containing the same and liquid crystalline display device containing the same |
| CNB971177104A CN1199938C (en) | 1996-08-22 | 1997-08-21 | Azine compound, process for preparation thereof, nematic liquid crystal composition and use in liquid crystal display system |
| US08/916,026 US6010642A (en) | 1996-08-22 | 1997-08-21 | Azine derivative, process for the preparation thereof, nematic liquid crystal composition and liquid crystal display system comprising same |
| TW086112162A TW402632B (en) | 1996-08-22 | 1997-08-22 | Azine derivative, process for the preparation thereof, nematic liquid crystal composition and liquid crystal display system comprising same |
| HK98110969A HK1010188A1 (en) | 1996-08-22 | 1998-09-25 | Azine derivative, process for preparation thereof,nematic liquid crystal composition and liquid crystal display system comprising same. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22121296A JP3882948B2 (en) | 1996-08-22 | 1996-08-22 | Asymmetric azines |
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| Publication Number | Publication Date |
|---|---|
| JPH1059918A JPH1059918A (en) | 1998-03-03 |
| JP3882948B2 true JP3882948B2 (en) | 2007-02-21 |
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| JP22121296A Expired - Fee Related JP3882948B2 (en) | 1996-08-22 | 1996-08-22 | Asymmetric azines |
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| JP4876314B2 (en) * | 2001-01-23 | 2012-02-15 | Ｄｉｃ株式会社 | Liquid crystal composition and liquid crystal display element |
| JP4512975B2 (en) * | 2003-10-31 | 2010-07-28 | Ｄｉｃ株式会社 | Liquid crystal composition and liquid crystal display element |
| JP6024950B2 (en) * | 2012-07-03 | 2016-11-16 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| CN113583684A (en) * | 2021-09-07 | 2021-11-02 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition and liquid crystal display device |
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| JPH1059918A (en) | 1998-03-03 |
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