JP4655317B2 - Liquid crystal composition and liquid crystal display element - Google Patents
Liquid crystal composition and liquid crystal display element Download PDFInfo
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- JP4655317B2 JP4655317B2 JP30682199A JP30682199A JP4655317B2 JP 4655317 B2 JP4655317 B2 JP 4655317B2 JP 30682199 A JP30682199 A JP 30682199A JP 30682199 A JP30682199 A JP 30682199A JP 4655317 B2 JP4655317 B2 JP 4655317B2
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 61
- 239000000203 mixture Substances 0.000 title claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 69
- 125000004432 carbon atom Chemical group C* 0.000 claims description 65
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- -1 2-methyl-1,4-phenylene group Chemical group 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 29
- 125000001153 fluoro group Chemical group F* 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 6
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical group C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011306 natural pitch Substances 0.000 description 1
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- Liquid Crystal Substances (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は電気光学的液晶表示材料として有用なネマチック液晶組成物及び、これを用いた液晶表示素子に関する。
【０００２】
【従来の技術】
液晶表示装置(LCD)は、電卓のディスプレイとして登場して以来、コンピューターの開発と歩みを同じくして、TN-LCD(捻れネマチック液晶表示装置)から、STN-LCDへと表示容量の拡大に対応してきた。STN-LCDは、シェファー(Scheffer)等［SID '85 Digest, 120頁(1985年)］、あるいは衣川等［SID '86 Digest, 122頁(1986年)］によって、開発され、ワードプロセッサ、パーソナルコンピュータなどの高情報処理用の表示に広く普及しはじめている。最近、STN-LCDでの応答特性を改善する目的でアクティブアドレッシング駆動方式が提案されている。(Proc.12th International Display Research Conference p.503 1992年)また、携帯用端末表示(Personal Digital Assistance)ではより広い温度域で良好な表示特性が要求されている。この様な液晶材料として粘性が低く、駆動電圧が低くなおかつ広い温度範囲に対して一定値を保持することや、あるいは種々の時分割に対応した周波数範囲で駆動電圧が変動しないことが要求されている。しかし、表示素子に組み込んだときの応答速度やコントラストなどはまだ十分とは言えず、現在も新しい液晶化合物あるいは液晶組成物の提案がなされている。
【０００３】
上述のようにTN-LCDやSTN-LCDの重要な特性改善課題の一つにコントラストの向上がある。LCDの急速な用途拡大に伴い、室内で使用されるだけでなく、コンピューターの携帯端末ディスプレイ、車載用計器、屋外使用計測機のディスプレイのように、温度条件の過酷な屋外で使用されることが増加してきた。LCDが置かれる環境の温度変化による表示コントラストの低下が問題になってきている。また、屋外での使用では高い信頼性も求められるようになってきた。
【０００４】
周囲の温度変化によるLCD表示品位の低下の原因は、様々な要因が上げられるが、ネマティック液晶の弾性定数・誘電率などの温度変化と添加したカイラル物質の固有ピッチの温度変化に起因する閾値電圧Vthの温度変化を押さえるため、カイラル物質の固有ピッチの温度変化を制御することにより、閾値電圧の温度依存性を改善する提案(特開昭55-38869)はすでに知られており、母体液晶とカイラル物質の組み合わせにより、その効果が変化する事や、カイラル量を増やすことにより、レスポンス等の表示特性に悪影響を及ぼすことが問題になっていた。
【０００５】
しかし、液晶中に含まれるイオン性物質の易動度の温度変化により電流値が増加するため、液晶にかかる実効値電圧がイオンにより消費され、コントラスト及び信頼性を低下させることに起因する改善策は知られていない。特に、その骨格中にエステル結合を有する化合物を多数含む液晶組成物で顕著であり、エステル結合を有する化合物を減らした液晶組成物が求められていた。
【０００６】
また、携帯端末ディスプレイ等に用いられる場合、その消費電力を抑えるために駆動電圧を下げることが行われているが。この様な用途に用いられるときの液晶組成物には低閾値電圧が求められる。しかし、駆動電圧を下げる材料(誘電率異方性の大きい)を組み合わせるとレスポンスに悪影響を及ぼし、この影響を避けるためには表示素子のセル厚を薄くする必要がある。セル厚を薄くするとリタデーションを一定にするためには屈折率の異方性の大きい材料を組み合わせる必要が生じる。すなわち、屈折率の異方性はビシクロヘキサン骨格<フェニルシクロヘキサン骨格<ビフェニル骨格の順であり、この順序がより好ましい液晶組成物の構成化合物となる。
【０００７】
【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、レスポンス、閾値電圧等の液晶諸特性を低下させることなく、電流値を抑制した信頼性の高い液晶組成物を提供すること、また、この液晶組成物を使用したコントラストの高い液晶表示素子を提供することにある。
【０００８】
【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、種々の液晶化合物を用いた液晶組成物を検討した結果以下の液晶組成物を見いだした。
【０００９】
発明1 第一成分として一般式(I)
【００１０】
【化９】
(式中、R1は炭素原子数1〜10のアルキル基を表す。)から選ばれる化合物を1種もしくは2種以上を含有し、第二成分として一般式(II)、(III)
【化１０】
【００１２】
発明2 一般式(I)の化合物の含有率が5〜40質量%の範囲で、さらに一般式(II)もしくは一般式(III)の化合物の中から選んだ1種もしくは2種以上を含有し、選んだ化合物の含有率がそれぞれ5〜95質量%の範囲であることを特徴とする発明1記載の液晶組成物。
【００１３】
発明3 一般式(II)の化合物として、環Aおよび環Bがトランス-1,4-シクロヘキシレン基であり、Z1、Z2が単結合の一般式(II-a)
【００１４】
【化１１】
(式中、R5、R6はR2、R3と同じ意味を表し、環Fは1,4-フェニレン基またはトランス-1,4-シクロヘキシレン基を表し、nは0もしくは1を表す。)から選ばれる1種もしくは2種以上の化合物を含有することを特徴とする発明1又は2記載の液晶組成物。
【００１６】
発明4 一般式(I)の含有率が5〜40質量%の範囲で、なおかつ第二成分として一般式(II-a)の化合物を1種もしくは2種以上を含有しその含有率が5〜95質量%の範囲であることを特徴とする発明3記載の液晶組成物。
【００１７】
発明5 一般式(III)の化合物として、環Dがトランス-1,4-シクロヘキシレン基であり、Z3、Z4が単結合であり、m=1の一般式(III-a)
【００１８】
【化１２】
(式中、R7は炭素原子数1〜8のアルキル基または、2〜8のアルケニル基を表し、環Gは1,4-フェニレン基またはトランス-1,4-シクロヘキシレン基を表し、X5はシアノ基、フッ素原子、トリフルオロメトキシ基、ジフルオロメトキシ基を表し、X4、X6はそれぞれ独立的に水素原子またはフッ素原子を表す。)から選ばれる1種もしくは2種以上の化合物を含有することを特徴とする発明1、2、3又は4記載の液晶組成物。
【００２０】
発明6 一般式(I)の含有率が5〜40質量%の範囲で、なおかつ一般式(III-a)の化合物を1種もしくは2種以上を含有し、その含有率が5〜95質量%の範囲であることを特徴とする発明5記載の液晶組成物。
【００２１】
発明7 一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(II-b)
【００２２】
【化１３】
(式中、R8、R9はそれぞれ独立的炭素原子数1〜8のアルキル基または炭素原子数2〜8のアルケニル基を表す。)から選ばれる1種もしくは2種以上の化合物を含有し、その含有率が5〜40質量%の範囲で、さらに一般式(II-c)
【００２４】
【化１４】
(式中、R10、R11はそれぞれ独立的に炭素原子数1〜8のアルキル基または炭素原子数2〜8のアルケニル基を表す。)から選ばれる1種もしくは2種以上の化合物を含有しその含有率が5〜60質量%の範囲であることを特徴とする発明1〜6記載の液晶組成物。
【００２６】
発明8 発明1記載の一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(III-a)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(II-b)もしくは一般式(II-c)の化合物を1種もしくは2種以上を含有し、その含有率が5〜60質量%の範囲であることを特徴とする発明1〜7記載の液晶組成物。
【００２７】
発明9 発明1記載の一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(III-a)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(II-b)及び一般式(II-c)の化合物を1種もしくは2種以上を含有し、その含有率がそれぞれ5〜40質量%の範囲であることを特徴とする発明1〜8記載の液晶組成物。
【００２８】
発明10 発明1〜9記載の一般式(III)もしくは(III-a)として一般式(III-b)
【００２９】
【化１５】
(式中、R12は炭素原子数1〜16のアルキル基または炭素原子数2〜8のアルケニル基を表す。)から選ばれる1種もしくは2種以上の化合物を含有しその含有率が5〜40質量%の範囲であることを特徴とする発明1〜9記載の液晶組成物。
【００３１】
発明11 発明1〜9記載の一般式(III)もしくは(III-a)として一般式(III-c)
【００３２】
【化１６】
(式中、R12は炭素原子数1〜16のアルキル基または炭素原子数2〜8のアルケニル基を表す。)から選ばれる1種もしくは2種以上の化合物を含有しその含有率が5〜40質量%の範囲であることを特徴とする発明1〜9記載の液晶組成物。
【００３４】
発明12 発明1〜11のいずれかに記載の液晶組成物を用いた液晶表示素子。
【００３５】
発明13 発明1〜11のいずれかに記載の液晶組成物を用いた、ねじれ角が220°〜270°であることを特徴とする超捩れネマチック(STN)液晶表示素子。
【００３６】
【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。発明1において、第一成分として一般式(I)から選ばれる化合物を1種もしくは2種以上を含有するが、1種もしくは2種が好ましい。また、式中R1は炭素原子数2〜16のアルケニル基もしくは炭素原子数3〜16のアルケニルオキシ基を表すが、炭素原子数2〜16のアルケニル基が好ましく、炭素原子数2〜8のアルケニル基がより好ましく、以下式(a)〜(e)の構造がさらに好ましく、
【００３７】
【化１７】
(構造式は右端で環に連結しているものとする。)その中でも(e)が特に好ましい。さらに、第二成分として一般式(II)、(III)から選ばれる化合物を1種もしくは2種以上を含有するが、3種以上が好ましく、3種〜20種がさらに好ましく、5種〜15種が特に好ましく、その中に一般式(II)の化合物を少なくとも2種以上含むことがより好ましい。この液晶組成物はネマチック相上限温度が75℃以上であることを特徴とするが、80℃以上が好ましく、85℃以上が特に好ましい。また、Δnは0.07〜0.24の範囲であることを特徴とするが、0.08〜0.22が好ましい。R2、R3、R4はそれぞれ独立的にフッ素置換されていても良い炭素原子数1〜16のアルキル基またはアルコキシル基、炭素原子数2〜16のアルケニル基、炭素原子数3〜16のアルケニルオキシ基、または炭素原子数1〜10のアルコキシル基で置換された炭素原子数1〜12のアルキル基を表すが、炭素原子数1〜16のアルキル基、炭素原子数2〜16のアルケニル基が好ましく、炭素原子数1〜8のアルキル基、炭素原子数2〜8のアルケニル基がより好ましく、1〜5のアルキル基もしくはアルケニル基として式(a)〜(e)が特に好ましい。環A、環B、環C、環D及び環Eはそれぞれ独立的にフッ素原子により置換されていてもよい1,4-フェニレン基、2-メチル-1,4-フェニレン基、3-メチル-1,4-フェニレン基、ナフタレン-2,6-ジイル基、フェナントレン-2,7-ジイル基、フルオレン-2,7-ジイル基、トランス-1,4-シクロヘキシレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基、トランス-1,3ジオキサン-2,5-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基またはピリダジン-2,5-ジイル基を表すが、1,4-フェニレン基、トランス-1,4-シクロヘキシレン基が好ましく、環A、環B、環D、環Eにおいてはトランス-1,4-シクロヘキシレン基がより好ましく、環Cにおいては1,4-フェニレン基より好ましい。l、mはそれぞれ独立的に0、1もしくは2を表すが、0もしくは1が好ましい。Z1、Z2、Z3、Z4はそれぞれ独立的に単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-または-C≡C-表すが、Z1、Z2においては単結合もしくは-CH2CH2-が好ましく、単結合がより好ましい。Z3、Z4においては単結合もしくは-C≡C-が好ましく、単結合がより好ましい。X2はシアノ基、フッ素原子、塩素原子、トリフルオロメトキシ基、トリフルオロメチル基、ジフルオロメトキシ基、水素原子、3,3,3-トリフルオロエトキシ基、R'または-OR'を表し、R'は炭素原子数1〜12の直鎖状アルキル基または、2〜12の直鎖状アルケニル基を表すが、シアノ基、フッ素原子、トリフルオロメトキシ基、ジフルオロメトキシ基が好ましく、フッ素原子、トリフルオロメトキシ基、ジフルオロメトキシ基がより好ましく、フッ素原子が特に好ましい。X1、X3は水素原子、フッ素原子または塩素原子を表すが、水素原子、フッ素原子が好ましく、フッ素原子が特に好ましい。
【００３９】
発明2において、一般式(I)の含有率は5〜40質量%であるが、5〜25質量%が好ましく、5〜20質量%が特に好ましく、一般式(II)もしくは一般式(III)の含有率は5〜95質量%であるが、15〜85質量%が好ましく、25〜85質量%が特に好ましい。
【００４０】
発明4において、一般式(I)の化合物を1種もしくは2種以上を含有しその含有率が5〜40質量%の範囲で、なおかつ一般式(II-a)の化合物を1種もしくは2種以上を含有しその含有率が5〜95質量%の範囲であるが、一般式(I)の化合物を1種もしくは2種含有しその含有率が5〜25質量%が好ましく、5〜20質量%が特に好ましく、一般式(II-a)の化合物を2種以上含有しその含有率が5〜95質量%であることが好ましく、15〜85質量%が好ましく、25〜85質量%が特に好ましい。
【００４１】
発明6において、一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ第二成分として一般式(III-a)の化合物を1種もしくは2種以上を含有し、その含有率が5〜95質量%の範囲であるが、一般式(I)の化合物を1種もしくは2種含有しその含有率が5〜25質量%が好ましく、5〜15質量%が特に好ましく、一般式(III-a)の化合物を2種以上含有しその含有率が5〜95質量%であることが好ましく、15〜85質量%が好ましく、25〜85質量%が特に好ましい。
【００４２】
発明7において、一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(II-b)から選ばれる1種もしくは2種以上の化合物を含有し、その含有率が5〜40質量%の範囲であるが5〜25質量%が好ましい、さらに一般式(II-c)から選ばれる1種もしくは2種以上の化合物を含有しその含有率が5〜60質量%の範囲であるが、5〜50質量%が好ましく5〜40質量%であることがより好ましい。式中R8、R9、R10、R11はそれぞれ独立的に炭素原子数1〜8のアルキル基または炭素原子数2〜8のアルケニル基を表すが、1〜5のアルキル基もしくはアルケニル基として式(a)〜(e)が特に好ましい。
【００４３】
発明8において、発明1記載の一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(III-a)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(II-b)もしくは一般式(II-c)の化合物を1種もしくは2種以上を含有し、その含有率が5〜60質量%の範囲であるが、一般式(I)の化合物を1種もしくは2種含有しその含有率が5〜20質量%の範囲であることが好ましく、一般式(III-a)の含有率が5〜35質量%の範囲であることが好ましく、5〜25質量%の範囲であることがより好ましく、一般式(II-b)もしくは一般式(II-c)の含有率が5〜55質量%の範囲であることが好ましく、5〜45質量%の範囲であることがより好ましい。
【００４４】
発明9において、発明1記載の一般式(I)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(III-a)の化合物を1種もしくは2種以上を含有し、その含有率が5〜40質量%の範囲で、なおかつ一般式(II-b)及び一般式(II-c)の化合物を1種もしくは2種以上を含有し、その含有率がそれぞれ5〜40質量%の範囲であるが、一般式(I)の化合物を1種もしくは2種含有しその含有率が5〜20質量%の範囲であることが好ましく、一般式(II-b)及び一般式(II-c)の化合物をそれぞれ1種以上含有しその含有率が5〜20質量%の範囲であり、一般式(III-a)の化合物を2種以上含有しその含有率が5〜25質量%の範囲であることが好ましい。
【００４５】
発明10において、発明1記載の一般式(III)もしくは一般式(III-a)として、一般式(III-b)から選ばれる1種もしくは2種以上の化合物を含有しその含有率が5〜40質量%の範囲であるが、一般式(III-b)の化合物を1〜10種含有しその含有率が5〜35質量%の範囲であることが好ましく、1〜5種を含有しその含有率が5〜30質量%の範囲であることがより好ましい。式中R12は炭素原子数1〜8のアルキル基または炭素原子数2〜8のアルケニル基を表すが、1〜5のアルキル基もしくはアルケニル基として式(a)〜(e)が特に好ましい。
【００４６】
発明11において、発明1記載の一般式(III)もしくは一般式(III-a)として、一般式(III-c)から選ばれる1種もしくは2種以上の化合物を含有しその含有率が5〜40質量%の範囲であるが、一般式(III-c)の化合物を1〜10種含有しその含有率が5〜35質量%の範囲であることが好ましく、1〜5種を含有しその含有率が5〜30質量%の範囲であることがより好ましい。式中R12は炭素原子数1〜8のアルキル基または炭素原子数2〜8のアルケニル基を表すが、1〜5のアルキル基もしくはアルケニル基として式(a)〜(e)が特に好ましい。
【００４７】
上記ネマチック液晶組成物はTN-LCDやSTN-LCDに有用であるがSTN-LCDに特に有用である。また、透過型あるいは反射型の液晶表示素子に用いることができる。本発明の液晶組成物は、上記一般式(I)〜(III-c)で表される化合物以外に、通常のネマチック液晶、スメクチック液晶、コレステリック液晶などを含有していてもよい。
【００４８】
【実施例】
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。
【００４９】
実施例中、測定した特性は以下の通りである。
STN-LCD表示素子の作成は以下のように行った。ネマチック液晶組成物にカイラル物質「S-811」(メルク社製)を添加して混合液晶を調製し、対向する平面透明電極上に「サンエバー610」(日産化学社製)の有機膜をラビングして配向膜を形成したツイスト角240度のSTN-LCD表示用セルに注入した。なお、カイラル物質はカイラル物質の添加による混合液晶の固有らせんピッチＰと表示用セルのセル厚dが、Δn・d=0.85、d/P=0.50となるように添加した。
【００５１】
化合物記載に下記の略号を使用する。
ネマチック液晶組成物No.1
【００５２】
【化１８】
を調製し、この組成物の諸特性を測定した結果を比較例1と共に表1に示す。
【００５４】
【表１】
表1に示すように、実施例1の液晶組成物は、比較例1の組成物に比べ電流値を大幅に抑制しているうえにコントラストも改善している。
ここで作製したSTN-LCDを用いて、優れた表示特性を示す液晶表示装置を作成することができた。
(実施例2、比較例2)
ネマチック液晶組成物No.2を調製し(実施例2)諸特性を測定した、また比較の組成物として本発明外の組成物組成物の組成及び特性データ(比較例2)と共に表2に示した。
【００５６】
【表２】
表2に示すように、実施例2の液晶組成物もまた、比較例2の組成物に比べ電流値を大幅に抑制し、コントラストも改善している。
ここで作製したSTN-LCDを用いて、優れた表示特性を示す液晶表示装置を作成することができた。
【００５８】
【発明の効果】
本発明の液晶材料の組み合わせによって、電流値が抑制された誘電率異方性の高い液晶組成物が得られた。また、この組成物を液晶表示素子として用いた場合、コントラスト及び信頼性が高く優れたものであった。この液晶ディスプレイはSTNおよびTN-LCDとして非常に実用的である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a nematic liquid crystal composition useful as an electro-optical liquid crystal display material and a liquid crystal display element using the same.
[0002]
[Prior art]
The liquid crystal display (LCD) has been used as a calculator display, and it has been the same as the development of computers to support the expansion of display capacity from TN-LCD (twisted nematic liquid crystal display) to STN-LCD. I have done it. STN-LCD was developed by Scheffer et al. [SID '85 Digest, 120 pages (1985)] or Kinukawa et al. It has begun to spread widely in the display for high information processing. Recently, an active addressing drive system has been proposed for the purpose of improving the response characteristics of STN-LCD. (Proc. 12th International Display Research Conference p.503 1992) In addition, in portable terminal display (Personal Digital Assistance), good display characteristics are required in a wider temperature range. As such a liquid crystal material, it is required that the viscosity is low, the driving voltage is low and a constant value is maintained over a wide temperature range, or that the driving voltage does not fluctuate in a frequency range corresponding to various time divisions. Yes. However, the response speed and contrast when incorporated in a display element are still not sufficient, and new liquid crystal compounds or liquid crystal compositions have been proposed.
[0003]
As described above, one of the important characteristics improvement issues of TN-LCD and STN-LCD is the improvement of contrast. With the rapid expansion of LCD applications, it is not only used indoors but also used outdoors with severe temperature conditions, such as computer mobile terminal displays, in-vehicle instruments, and displays used outdoors. It has increased. A decrease in display contrast due to temperature changes in the environment where the LCD is placed has become a problem. In addition, high reliability has been required for outdoor use.
[0004]
There are various causes for the deterioration of LCD display quality due to ambient temperature changes, but the threshold voltage is caused by temperature changes such as the elastic constant and dielectric constant of the nematic liquid crystal and the temperature change of the intrinsic pitch of the added chiral substance. In order to suppress the temperature change of Vth, a proposal for improving the temperature dependency of the threshold voltage by controlling the temperature change of the natural pitch of the chiral substance (Japanese Patent Laid-Open No. 55-38869) is already known. It has been a problem that the effect changes depending on the combination of chiral substances, and that the display characteristics such as response are adversely affected by increasing the amount of chiral substances.
[0005]
However, since the current value increases due to the temperature change of the mobility of the ionic substance contained in the liquid crystal, the effective value voltage applied to the liquid crystal is consumed by the ions, and the improvement measures are caused by lowering the contrast and reliability. Is not known. In particular, a liquid crystal composition containing a large number of compounds having an ester bond in its skeleton is remarkable, and a liquid crystal composition having a reduced number of compounds having an ester bond has been demanded.
[0006]
In addition, when used in a portable terminal display or the like, the drive voltage is lowered in order to reduce the power consumption. A low threshold voltage is required for the liquid crystal composition when used in such applications. However, when a material that lowers the driving voltage (having a large dielectric anisotropy) is combined, the response is adversely affected. To avoid this influence, it is necessary to reduce the cell thickness of the display element. When the cell thickness is reduced, it is necessary to combine materials having a large refractive index anisotropy in order to make the retardation constant. That is, the anisotropy of the refractive index is in the order of bicyclohexane skeleton <phenylcyclohexane skeleton <biphenyl skeleton, and this order is a more preferable constituent compound of the liquid crystal composition.
[0007]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a highly reliable liquid crystal composition in which the current value is suppressed without deteriorating various liquid crystal characteristics such as response and threshold voltage, and to use this liquid crystal composition An object of the present invention is to provide a liquid crystal display element having high contrast.
[0008]
[Means for Solving the Problems]
The present invention has found the following liquid crystal compositions as a result of studying liquid crystal compositions using various liquid crystal compounds in order to solve the above problems.
[0009]
Invention 1 General formula (I) as the first component
[0010]
[Chemical 9]
(Wherein R 1 represents an alkyl group having 1 to 10 carbon atoms), containing one or more compounds selected from general formulas (II) and (III) as the second component
Embedded image
[0012]
Invention 2 The content of the compound of general formula (I) is in the range of 5 to 40% by mass, and further contains one or more selected from compounds of general formula (II) or general formula (III). The liquid crystal composition according to invention 1, wherein the content of the selected compound is in the range of 5 to 95% by mass.
[0013]
Invention 3 As a compound of general formula (II), ring A and ring B are trans-1,4-cyclohexylene groups, and Z 1 and Z 2 are single bonds.
[0014]
Embedded image
(Wherein R 5 and R 6 represent the same meaning as R 2 and R 3 , ring F represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and n represents 0 or 1) 3. A liquid crystal composition according to invention 1 or 2, which comprises one or more compounds selected from
[0016]
Invention 4 The content of the general formula (I) is in the range of 5 to 40% by mass, and the compound of the general formula (II-a) as the second component contains one or more kinds, and the content is 5 to 5%. The liquid crystal composition according to invention 3, which is in the range of 95% by mass.
[0017]
Invention 5 As a compound of general formula (III), ring D is a trans-1,4-cyclohexylene group, Z 3 and Z 4 are single bonds, and m = 1, general formula (III-a)
[0018]
Embedded image
(Wherein R 7 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, ring G represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and 5 represents a cyano group, a fluorine atom, a trifluoromethoxy group, or a difluoromethoxy group, and X 4 and X 6 each independently represent a hydrogen atom or a fluorine atom.) 5. A liquid crystal composition according to invention 1, 2, 3 or 4, characterized by containing.
[0020]
Invention 6 The content of the general formula (I) is in the range of 5 to 40% by mass, and contains one or more compounds of the general formula (III-a), and the content is 5 to 95% by mass. 6. The liquid crystal composition according to invention 5, wherein
[0021]
Invention 7 One or more compounds of the general formula (I) are contained, the content thereof is in the range of 5 to 40% by mass, and the general formula (II-b)
[0022]
Embedded image
(Wherein R 8 and R 9 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms), and contains one or more compounds selected from the group consisting of In addition, the content is in the range of 5 to 40% by mass, further the general formula (II-c)
[0024]
Embedded image
(In the formula, each of R 10 and R 11 independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.) Contains one or more compounds selected from And the content rate is the range of 5-60 mass%, The liquid crystal composition of invention 1-6 characterized by the above-mentioned.
[0026]
Invention 8 One or more compounds of the general formula (I) described in the invention 1 are contained, the content thereof is in the range of 5 to 40% by mass, and one compound of the general formula (III-a) is used. Alternatively, it contains two or more, the content is in the range of 5-40% by mass, and contains one or more compounds of the general formula (II-b) or general formula (II-c), The liquid crystal composition according to any one of inventions 1 to 7, wherein the content is in the range of 5 to 60% by mass.
[0027]
Invention 9 One or more compounds of the general formula (I) described in the invention 1 are contained, the content thereof is in the range of 5 to 40% by mass, and one compound of the general formula (III-a) is used. Or containing two or more, the content is in the range of 5 to 40% by mass, and contains one or more compounds of general formula (II-b) and general formula (II-c), The liquid crystal composition according to any one of inventions 1 to 8, wherein the content is in the range of 5 to 40% by mass.
[0028]
Invention 10 General formula (III-b) as general formula (III) or (III-a) according to inventions 1 to 9
[0029]
Embedded image
(Wherein R 12 represents an alkyl group having 1 to 16 carbon atoms or an alkenyl group having 2 to 8 carbon atoms), and the content thereof is 5 to 5 The liquid crystal composition according to any one of inventions 1 to 9, which is in the range of 40% by mass.
[0031]
Invention 11 General formula (III-c) as general formula (III) or (III-a) according to inventions 1 to 9
[0032]
Embedded image
(Wherein R 12 represents an alkyl group having 1 to 16 carbon atoms or an alkenyl group having 2 to 8 carbon atoms), and the content thereof is 5 to 5 The liquid crystal composition according to any one of inventions 1 to 9, which is in the range of 40% by mass.
[0034]
Invention 12 A liquid crystal display device using the liquid crystal composition according to any one of Inventions 1 to 11.
[0035]
Invention 13 A super twisted nematic (STN) liquid crystal display element using the liquid crystal composition according to any one of Inventions 1 to 11 and having a twist angle of 220 ° to 270 °.
[0036]
DETAILED DESCRIPTION OF THE INVENTION
An example of the present invention will be described below. In the invention 1, the first component contains one or more compounds selected from the general formula (I), but one or two compounds are preferable. In the formula, R 1 represents an alkenyl group having 2 to 16 carbon atoms or an alkenyloxy group having 3 to 16 carbon atoms, preferably an alkenyl group having 2 to 16 carbon atoms, and having 2 to 8 carbon atoms. Alkenyl groups are more preferred, structures of the following formulas (a) to (e) are more preferred,
[0037]
Embedded image
(The structural formula is connected to the ring at the right end.) Among these, (e) is particularly preferred. Furthermore, it contains one or more compounds selected from general formulas (II) and (III) as the second component, preferably 3 or more, more preferably 3 to 20 and more preferably 5 to 15 Species are particularly preferred, and it is more preferred that at least two kinds of compounds of the general formula (II) are contained therein. The liquid crystal composition has a nematic phase upper limit temperature of 75 ° C. or higher, preferably 80 ° C. or higher, particularly preferably 85 ° C. or higher. Further, Δn is characterized by being in the range of 0.07 to 0.24, preferably 0.08 to 0.22. R 2 , R 3 , and R 4 each independently may be fluorine-substituted alkyl group or alkoxyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, or 3 to 16 carbon atoms Represents an alkenyloxy group or an alkyl group having 1 to 12 carbon atoms substituted with an alkoxyl group having 1 to 10 carbon atoms, but an alkyl group having 1 to 16 carbon atoms or an alkenyl group having 2 to 16 carbon atoms Are more preferable, an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 2 to 8 carbon atoms are more preferable, and formulas (a) to (e) are particularly preferable as an alkyl group or alkenyl group having 1 to 5 carbon atoms. Ring A, Ring B, Ring C, Ring D and Ring E are each independently a 1,4-phenylene group, 2-methyl-1,4-phenylene group, 3-methyl- 1,4-phenylene group, naphthalene-2,6-diyl group, phenanthrene-2,7-diyl group, fluorene-2,7-diyl group, trans-1,4-cyclohexylene group, 1,2,3, 4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2, 5-diyl group, pyrazine-2,5-diyl group or pyridazine-2,5-diyl group, preferably 1,4-phenylene group or trans-1,4-cyclohexylene group, ring A, ring B In Ring D and Ring E, a trans-1,4-cyclohexylene group is more preferable, and in Ring C, a 1,4-phenylene group is more preferable. l and m each independently represents 0, 1 or 2, with 0 or 1 being preferred. Z 1 , Z 2 , Z 3 and Z 4 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O— or —C≡C— As shown, in Z 1 and Z 2 , a single bond or —CH 2 CH 2 — is preferable, and a single bond is more preferable. In Z 3 and Z 4 , a single bond or —C≡C— is preferable, and a single bond is more preferable. X 2 represents a cyano group, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, a hydrogen atom, a 3,3,3-trifluoroethoxy group, R ′ or —OR ′, and R 'Represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkenyl group having 2 to 12 carbon atoms, and is preferably a cyano group, a fluorine atom, a trifluoromethoxy group, or a difluoromethoxy group. A fluoromethoxy group and a difluoromethoxy group are more preferable, and a fluorine atom is particularly preferable. X 1 and X 3 represent a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, and particularly preferably a fluorine atom.
[0039]
In the invention 2, the content of the general formula (I) is 5 to 40% by mass, preferably 5 to 25% by mass, particularly preferably 5 to 20% by mass, the general formula (II) or the general formula (III). The content of is from 5 to 95 mass%, preferably from 15 to 85 mass%, particularly preferably from 25 to 85 mass%.
[0040]
In the invention 4, the compound of the general formula (I) contains one or more compounds, the content thereof is in the range of 5 to 40% by mass, and one or two compounds of the general formula (II-a) The content is in the range of 5 to 95% by mass, but one or two compounds of the general formula (I) are contained, and the content is preferably 5 to 25% by mass, and 5 to 20% by mass. % Is particularly preferred, containing two or more compounds of the general formula (II-a), the content of which is preferably 5 to 95% by weight, preferably 15 to 85% by weight, particularly 25 to 85% by weight preferable.
[0041]
In the invention 6, the compound of the general formula (I) contains one or more compounds of the general formula (I), the content is in the range of 5 to 40% by mass, and the compound of the general formula (III-a) as the second component 1 or 2 or more types, the content is in the range of 5 to 95% by mass, but contains one or two compounds of the general formula (I), the content is 5 to 25% by mass Preferably, 5 to 15% by mass is particularly preferable, it contains two or more compounds of the general formula (III-a), the content is preferably 5 to 95% by mass, preferably 15 to 85% by mass, 25 ˜85% by weight is particularly preferred.
[0042]
In the invention 7, one or two or more compounds selected from the general formula (II-b) are contained in the range of 5 to 40% by mass of the compound of the general formula (I). One or more compounds selected from the general formula (II-c), wherein the content is in the range of 5 to 40% by mass, preferably 5 to 25% by mass. The content is in the range of 5 to 60% by mass, preferably 5 to 50% by mass, and more preferably 5 to 40% by mass. In the formula, R 8 , R 9 , R 10 and R 11 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, but an alkyl group or alkenyl group having 1 to 5 carbon atoms. Are particularly preferred as formulas (a) to (e).
[0043]
In the invention 8, the compound of the general formula (I) described in the invention 1 contains one or more compounds, the content thereof is in the range of 5 to 40% by mass, and the compound of the general formula (III-a) Contains 1 or 2 or more types, the content is in the range of 5 to 40% by mass, and contains one or more compounds of general formula (II-b) or general formula (II-c) The content is in the range of 5 to 60% by mass, but preferably contains one or two compounds of the general formula (I) and the content is in the range of 5 to 20% by mass. The content of the formula (III-a) is preferably in the range of 5 to 35 mass%, more preferably in the range of 5 to 25 mass%, and the general formula (II-b) or the general formula (II- The content of c) is preferably in the range of 5 to 55% by mass, and more preferably in the range of 5 to 45% by mass.
[0044]
In the invention 9, the compound of the general formula (I) described in the invention 1 contains one or more compounds, the content thereof is in the range of 5 to 40% by mass, and the compound of the general formula (III-a) Contains 1 or 2 or more types, the content is in the range of 5-40% by mass, and contains one or more compounds of general formula (II-b) and general formula (II-c) And, the content of each is in the range of 5 to 40% by mass, but preferably contains one or two compounds of general formula (I) and the content is in the range of 5 to 20% by mass, Each contains at least one compound of general formula (II-b) and general formula (II-c), the content of which is in the range of 5 to 20% by mass, and two compounds of general formula (III-a) It is preferable that the content is 5% to 25% by mass.
[0045]
In the invention 10, the general formula (III) or the general formula (III-a) described in the invention 1 contains one or more compounds selected from the general formula (III-b), and the content thereof is 5 to 5 Although it is in the range of 40% by mass, it is preferable that the compound of the general formula (III-b) is contained in 1 to 10 types and the content thereof is in the range of 5 to 35% by mass, and contains 1 to 5 types. The content is more preferably in the range of 5 to 30% by mass. In the formula, R 12 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and the formulas (a) to (e) are particularly preferable as the alkyl group or alkenyl group having 1 to 5 carbon atoms.
[0046]
In Invention 11, as General Formula (III) or General Formula (III-a) described in Invention 1, it contains one or more compounds selected from General Formula (III-c), and the content thereof is 5 to 5 Although it is in the range of 40% by mass, it is preferable that 1 to 10 types of the compound of the general formula (III-c) are contained and the content thereof is in the range of 5 to 35% by mass, and 1 to 5 types are contained. The content is more preferably in the range of 5 to 30% by mass. In the formula, R 12 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and the formulas (a) to (e) are particularly preferable as the alkyl group or alkenyl group having 1 to 5 carbon atoms.
[0047]
The nematic liquid crystal composition is useful for TN-LCD and STN-LCD, but is particularly useful for STN-LCD. Further, it can be used for a transmissive or reflective liquid crystal display element. The liquid crystal composition of the present invention may contain ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals and the like in addition to the compounds represented by the above general formulas (I) to (III-c).
[0048]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
[0049]
In the examples, the measured characteristics are as follows.
The STN-LCD display element was created as follows. A chiral substance `` S-811 '' (Merck) was added to the nematic liquid crystal composition to prepare a mixed liquid crystal, and an organic film of `` Sunever 610 '' (Nissan Chemical) was rubbed on the opposing flat transparent electrode. Then, it was injected into an STN-LCD display cell having a twist angle of 240 degrees on which an orientation film was formed. The chiral material was added so that the intrinsic helical pitch P of the mixed liquid crystal and the cell thickness d of the display cell were Δn · d = 0.85 and d / P = 0.50.
[0051]
The following abbreviations are used in compound descriptions.
Nematic liquid crystal composition No.1
[0052]
Embedded image
Table 1 together with Comparative Example 1 shows the results of measuring the various properties of this composition.
[0054]
[Table 1]
As shown in Table 1, the liquid crystal composition of Example 1 significantly reduced the current value and improved the contrast as compared with the composition of Comparative Example 1.
Using the STN-LCD produced here, a liquid crystal display device having excellent display characteristics could be produced.
(Example 2, Comparative Example 2)
A nematic liquid crystal composition No. 2 was prepared (Example 2) and various properties were measured. It was.
[0056]
[Table 2]
As shown in Table 2, the liquid crystal composition of Example 2 also significantly suppressed the current value and improved the contrast as compared with the composition of Comparative Example 2.
Using the STN-LCD produced here, a liquid crystal display device having excellent display characteristics could be produced.
[0058]
【The invention's effect】
By the combination of the liquid crystal materials of the present invention, a liquid crystal composition having a high dielectric anisotropy with a suppressed current value was obtained. Moreover, when this composition was used as a liquid crystal display device, it was excellent in contrast and reliability. This liquid crystal display is very practical as STN and TN-LCD.
Claims (10)
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| JPH09118882A (en) * | 1995-10-24 | 1997-05-06 | Seiko Epson Corp | Liquid crystal composition and liquid crystal display element using the composition |
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| JP3698174B2 (en) * | 1994-07-15 | 2005-09-21 | セイコーエプソン株式会社 | Liquid crystal composition and liquid crystal display device using the same |
| JPH09101507A (en) * | 1995-10-03 | 1997-04-15 | Seiko Epson Corp | Production of liquid crystal electro-optic element |
| JPH09138412A (en) * | 1995-11-16 | 1997-05-27 | Seiko Epson Corp | High polymer dispersion type liquid crystal display element and its production |
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