JPH0597772A - Ester compound and liquid crystal composition and loquid crystal display element - Google Patents
Ester compound and liquid crystal composition and loquid crystal display elementInfo
- Publication number
- JPH0597772A JPH0597772A JP3259336A JP25933691A JPH0597772A JP H0597772 A JPH0597772 A JP H0597772A JP 3259336 A JP3259336 A JP 3259336A JP 25933691 A JP25933691 A JP 25933691A JP H0597772 A JPH0597772 A JP H0597772A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- compound
- crystal display
- ester compound
- crystal composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- -1 Ester compound Chemical class 0.000 title claims description 22
- 239000013078 crystal Substances 0.000 title description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 6
- LOQLDQJTSMKBJU-UHFFFAOYSA-N 4-(chloromethyl)benzonitrile Chemical compound ClCC1=CC=C(C#N)C=C1 LOQLDQJTSMKBJU-UHFFFAOYSA-N 0.000 abstract description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 4
- XAASLEJRGFPHEV-UHFFFAOYSA-N 4-cyanobenzyl alcohol Chemical compound OCC1=CC=C(C#N)C=C1 XAASLEJRGFPHEV-UHFFFAOYSA-N 0.000 abstract description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 abstract description 3
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FEPGKHZMVPLZTI-UHFFFAOYSA-N 4-(butoxymethyl)benzoic acid Chemical compound CCCCOCC1=CC=C(C(O)=O)C=C1 FEPGKHZMVPLZTI-UHFFFAOYSA-N 0.000 description 2
- CJTKPSRYDGQJRY-UHFFFAOYSA-N 4-(butoxymethyl)benzonitrile Chemical compound CCCCOCC1=CC=C(C#N)C=C1 CJTKPSRYDGQJRY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- NWRXEGKWQXAEHC-UHFFFAOYSA-N 2-(hydroxymethyl)benzonitrile Chemical compound OCC1=CC=CC=C1C#N NWRXEGKWQXAEHC-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 210000004027 cell Anatomy 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
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液晶表示素子に用いら
れる液晶組成物の成分として有用な新規のエステル化合
物及びそれを含有する液晶組成物及びその液晶組成物を
使用する液晶表示素子に関する。TECHNICAL FIELD The present invention relates to a novel ester compound useful as a component of a liquid crystal composition used for a liquid crystal display device, a liquid crystal composition containing the same, and a liquid crystal display device using the liquid crystal composition.
【０００２】[0002]
【従来の技術】液晶表示素子は電場印加により液晶分子
の配列が変化することで液晶セルの光学的性質が変化し
て光変調が生ずる液晶の電気光学効果を応用したもので
あり、その表示方式により動的散乱型（ＤＳ型）、捩れ
たネマチック型（ＴＮ型）、複屈折制御型（ＥＣＢ
型）、超捩れネマチック型（ＳＴＮ型）、超捩れ複屈折
型（ＳＢＥ型）などに分けられる。また、これらの液晶
表示素子を動作させる駆動方式にはスタティク駆動方
式、時分割駆動方式、アクティブマトリックス駆動方
式、二周波駆動方式などがある。2. Description of the Related Art A liquid crystal display element is an application of the electro-optical effect of liquid crystal in which the optical properties of a liquid crystal cell are changed by the change of the alignment of liquid crystal molecules by the application of an electric field, resulting in optical modulation. Dynamic scattering type (DS type), twisted nematic type (TN type), birefringence control type (ECB)
Type), super twisted nematic type (STN type), super twisted birefringent type (SBE type), and the like. Further, as a driving method for operating these liquid crystal display elements, there are a static driving method, a time division driving method, an active matrix driving method, a dual frequency driving method and the like.
【０００３】液晶表示素子はＬＥＤ、ＥＬ、ＣＲＴ等の
表示素子と比較して （１）小型、薄型化が容易にできる。 （２）駆動電圧が低く、また消費電力が非常に小さい。 （３）ＬＳＩとの相性が良く、駆動回路の簡単化ができ
る。 （４）受光型素子であるため直射日光下でも見やすく、
また長時間使用しても目が疲れにくい。 等の特徴を有するため、これらの特徴を生かして主とし
てＴＮ型の液晶表示素子がウォッチ、電卓、オーディオ
機器、ゲーム、自動車のダッシュボード、カメラ、電話
器、家庭用電気製品、その他各種計測器の表示用として
応く使用されてきた。最近ではＳＴＮ型の液晶表示素子
がパーソナルコンピューターやワードプロセッサーのデ
ィスプレイに、アクティブマトリックス駆動のＴＮ型液
晶表示素子がカラーテレビに応用されつつあり、近い将
来においてＣＲＴに代る表示素子として注目を集めてい
る。Liquid crystal display elements can be easily made smaller and thinner than display elements such as LEDs, EL, and CRTs. (2) The driving voltage is low and the power consumption is very small. (3) Compatibility with LSI is good, and the drive circuit can be simplified. (4) Since it is a light receiving element, it is easy to see even in direct sunlight,
Also, eyes do not get tired easily even after long use. Due to these features, TN type liquid crystal display elements are mainly used for watches, calculators, audio devices, games, automobile dashboards, cameras, telephones, household electric appliances, and other various measuring instruments. It has been used as a display. Recently, STN type liquid crystal display elements are being applied to displays of personal computers and word processors, and active matrix driven TN type liquid crystal display elements are being applied to color televisions, and they are drawing attention as display elements to replace CRTs in the near future. ..
【０００４】このように液晶表示素子は様々な分野で用
いられているためそれらに使用される液晶材料に要求さ
れる特性は表示方式、駆動方式、応用分野等の組み合せ
により種々変化するが、次に挙げた諸特性はＴＮ型やＳ
ＴＮ型の液晶表示素子等においては必要不可欠である。 （１）着色がなく、熱、光、電気的、化学的に安定であ
ること。 （２）実用温度範囲が室温付近にあり、しかもできるか
ぎり広いこと。 （３）電圧−光透過率特性（Ｖ−ＩO 特性）のしきい値
電圧（Ｖｔｈ）が低く、かつその温度依存性が小さいこ
と。 （４）Ｖ−ＩO 特性の急峻性が良好なこと。 （５）Ｖ−ＩO 特性の視角依存性が小さいこと。 （６）電気光学的な応答速度が速いこと。Since the liquid crystal display device is used in various fields as described above, the characteristics required for the liquid crystal material used for them vary variously depending on the combination of the display system, the driving system and the application field. The characteristics listed in are TN type and S
It is indispensable in TN type liquid crystal display devices and the like. (1) It is not colored and is stable to heat, light, electricity, and chemicals. (2) The practical temperature range should be around room temperature, and as wide as possible. (3) The threshold voltage (Vth) of the voltage-light transmittance characteristic (VI- O characteristic) is low and its temperature dependence is small. (4) The steepness of V- IO characteristics is good. (5) The visual angle dependence of the V- IO characteristics is small. (6) The electro-optical response speed is fast.
【０００５】[0005]
【発明が解決しようとする課題】これらの諸特性のうち
で（１）を満足する液晶化合物は多数知られているが、
（２）以下の特性を単一成分で満足するような液晶化合
物は現在のところ知られていない。そこで、（２）以下
の特性を充たす方法として複数の液晶化合物又はその類
化合物を混合した液晶組成物を用いているのが実状であ
る。Many liquid crystal compounds satisfying (1) among these characteristics are known.
(2) A liquid crystal compound satisfying the following characteristics with a single component is not known at present. Therefore, as a method for satisfying (2) the following characteristics, a liquid crystal composition in which a plurality of liquid crystal compounds or a similar compound is mixed is actually used.
【０００６】液晶組成物に求められる特性のなかで、し
きい値電圧（Ｖｔｈ）は例えばＴＮ型の液晶表示素子の
場合には次式で表わされる。Among the characteristics required for the liquid crystal composition, the threshold voltage (Vth) is expressed by the following equation in the case of a TN type liquid crystal display device, for example.
【数１】 （ここで、ｄは液晶層の厚み、Ｋ11，Ｋ22，Ｋ33はそれ
ぞれスプレー、ツイスト、ベンドの弾性定数、ε0 は真
空誘電率、△εは誘電異方性を示す）したがって、Ｖｔ
ｈを下げるには弾性定数が小さく、誘電異方性が大きい
化合物を液晶組成物に添加すれば良いことがわかる。[Equation 1] (Here, d is the thickness of the liquid crystal layer, K 11 , K 22 , and K 33 are the elastic constants of spray, twist, and bend, ε 0 is the vacuum dielectric constant, and Δε is the dielectric anisotropy.) Therefore, Vt
It can be seen that a compound having a small elastic constant and a large dielectric anisotropy may be added to the liquid crystal composition to decrease h.
【０００７】そこで、本発明の目的は誘電異方性が正で
大きい化合物を提供することである。また、本発明の他
の目的はその化合物を含有する誘電異方性が正で大きな
液晶組成物を提供することである。さらに、本発明の他
の目的はその液晶組成物を用いることにより駆動電圧の
低い液晶表示素子を提供することである。Therefore, an object of the present invention is to provide a compound having a large positive dielectric anisotropy. Another object of the present invention is to provide a liquid crystal composition containing the compound and having a large positive dielectric anisotropy. Still another object of the present invention is to provide a liquid crystal display device having a low driving voltage by using the liquid crystal composition.
【０００８】[0008]
【課題を解決するための手段】本発明のエステル化合物
は、一般式The ester compound of the present invention has the general formula
【化４】 （ここで、Ｒは炭素原子数が１〜８のアルカリ基、Ｘは
Ｈ又はＦを示す）で表わされるエステル化合物である。[Chemical 4] (Wherein R is an alkali group having 1 to 8 carbon atoms, X is H or F), and is an ester compound.
【０００９】また、本発明の液晶組成物は前記エステル
化合物を少なくとも一種類含有することを特徴とする。The liquid crystal composition of the present invention is characterized by containing at least one kind of the ester compound.
【００１０】また、本発明の液晶表示素子は、前記エス
テル化合物を少なくとも一種類含有する前記液晶組成物
を使用することを特徴とする。The liquid crystal display device of the present invention is characterized by using the liquid crystal composition containing at least one kind of the ester compound.
【００１１】本発明のエステル化合物は、例えば表１に
示すスキームにより製造することができる。The ester compound of the present invention can be produced, for example, by the scheme shown in Table 1.
【表１】 （ここで、Ｒは炭素原子数が１〜８のアルキル基、Ｘは
Ｈ又はＦを示す。）即ち、ステップ（１）においては４
−シアノベンズアルデヒド（Ｂ）をエタノール中で水素
化ホウ素ナトリウムを用いて還元して４−ヒドロキシメ
チルベンゾニトリル（Ｃ）を得る。ステップ（２）にお
いては化合物（Ｃ）をクロロホルム中で塩化チオニルを
用いて塩素化して４−クロロメチルベンゾニトリル
（Ｄ）を得る。ステップ（３）においては化合物（Ｄ）
を相当するナトリウムアルコラートを用いてアルコキシ
化して４−アルコキシメチルベンゾニトリル（Ｅ）を得
る。ステップ（４）においては化合物（Ｅ）をエチレン
グリコール中でＫＯＨと水を用いて加水分解して４−ア
ルコキシメチル安息香酸（Ｆ）を得る。ステップ（５）
においては化合物（Ｆ）と化合物（Ｇ）をテトラヒドロ
フラン中でトリフェニルホスフィンとジエチルアゾカル
ボキシレートを用いてエステル化して本発明のエステル
化合物（Ａ）を得る。[Table 1] (Here, R represents an alkyl group having 1 to 8 carbon atoms, X represents H or F.) That is, 4 in step (1).
-Cyanobenzaldehyde (B) is reduced in ethanol with sodium borohydride to give 4-hydroxymethylbenzonitrile (C). In step (2), compound (C) is chlorinated in chloroform with thionyl chloride to give 4-chloromethylbenzonitrile (D). Compound (D) in step (3)
Is alkoxylated with the corresponding sodium alcoholate to give 4-alkoxymethylbenzonitrile (E). In step (4), compound (E) is hydrolyzed in ethylene glycol with KOH and water to give 4-alkoxymethylbenzoic acid (F). Step (5)
In, the compound (F) and the compound (G) are esterified in tetrahydrofuran with triphenylphosphine and diethylazocarboxylate to obtain the ester compound (A) of the present invention.
【００１２】このようにして得られるエステル化合物
（Ａ）は電気化学的に安定であり他の液晶化合物との相
容性が良好であり、誘電異方性の値が正で大きく、特に
フッソ原子が２個置換した化合物は４位にシアノ基が置
換したものと同程度の大きな誘電異方性を持ち、しか
も、それよりも電気化学的に安定であり複屈折も小さい
特徴を有する。The ester compound (A) thus obtained is electrochemically stable, has good compatibility with other liquid crystal compounds, and has a large positive dielectric anisotropy value. The compound in which 2 is substituted has the same large dielectric anisotropy as that in which the cyano group is substituted at the 4-position, and is electrochemically stable and has a small birefringence.
【００１３】したがって、エステル化合物（Ａ）を従来
の液晶組成物に混合することにより電気化学的な安定性
を損なうことなく誘電異方性を正で大きくすることがで
きる。この場合にエステル化合物（Ａ）を添加する母液
晶の成分としては従来の液晶化合物の全てが利用可能で
あるが、特に有用な液晶化合物を表２に挙げた。Therefore, by mixing the ester compound (A) with the conventional liquid crystal composition, the dielectric anisotropy can be made positive and large without impairing the electrochemical stability. In this case, all the conventional liquid crystal compounds can be used as the component of the mother liquid crystal to which the ester compound (A) is added, and particularly useful liquid crystal compounds are listed in Table 2.
【表２】 これらの化合物を混合した母液晶にエステル化合物
（Ａ）を添加できる割合は１〜５０重量％の範囲である
が、より実用的には３〜３０重量％の範囲が好ましい。[Table 2] The proportion in which the ester compound (A) can be added to the mother liquid crystal in which these compounds are mixed is in the range of 1 to 50% by weight, but more practically it is preferably in the range of 3 to 30% by weight.
【００１４】また、エステル化合物（Ａ）を添加した液
晶組成物をＴＮ型又はＳＴＮ型の液晶表示素子に使用す
ると駆動電圧を下げることが可能となり、特に高時分割
駆動の液晶表示素子においてはＩＣに高耐圧を必要とし
ないため有用である。本発明の液晶表示素子の構造は図
１に示した通りであり、詳しくは実施例に示した。Further, when the liquid crystal composition containing the ester compound (A) is used in a TN type or STN type liquid crystal display element, the driving voltage can be lowered, and especially in a high time division driving liquid crystal display element, IC It is useful because it does not require high withstand voltage. The structure of the liquid crystal display element of the present invention is as shown in FIG. 1, and details are shown in the examples.
【００１５】[0015]
【実施例】以下、実施例により本発明の化合物の製造お
よび液晶組成物および液晶表示素子を更に詳しく説明す
る。EXAMPLES The production of compounds of the present invention and liquid crystal compositions and liquid crystal display devices will be described in more detail below with reference to examples.
【００１６】［実施例１］ （化合物の製造） ４−フルオロフェニル ４′−ブトキシメチルベンゾエ
ートの製造方法。[Example 1] (Production of compound) A method for producing 4-fluorophenyl 4'-butoxymethylbenzoate.
【００１７】ステップ１ ４−シアノベンズアルデヒド
１９７ｇ（１．５モル）を無水エタノール７５０ｃｍ3
に溶解し、撹拌しながらＮａＢＨ4 の粉末を少しずつ加
えた。その後室温で５時間撹拌し、エタノールを留去し
た。残渣をエーテルに溶解し、飽和食塩水で洗浄後エー
テルを留去した。残渣をメタノールから再結晶して４−
ヒドロキシメチルベンゾニトリル１７９ｇを得た。 Step 1 197 g (1.5 mol) of 4-cyanobenzaldehyde was added to 750 cm 3 of absolute ethanol.
And powder of NaBH 4 was added little by little while stirring. Then, the mixture was stirred at room temperature for 5 hours, and ethanol was distilled off. The residue was dissolved in ether, washed with saturated brine and the ether was distilled off. The residue was recrystallized from methanol and 4-
179 g of hydroxymethylbenzonitrile was obtained.
【００１８】ステップ２ ４−ヒドロキシメチルベンゾ
ニトリル１７９ｇをクロロホルム２００ｃｍ3 に溶解
し、氷水冷却撹拌下にＳＯＣｌ2 ３２０ｇを滴下した。
その後撹拌しながら２時間還流した。過剰なＳＯＣｌ2
を留去し、残渣を減圧蒸留（ｂ．ｐ．８７℃／２ｍｍＨ
ｇ）して４−クロロメチルベンゾニトリル２００ｇを得
た。 Step 2 179 g of 4-hydroxymethylbenzonitrile was dissolved in 200 cm 3 of chloroform, and 320 g of SOCl 2 was added dropwise with stirring while cooling with ice water.
Then, the mixture was refluxed for 2 hours with stirring. Excess SOCl 2
Was distilled off, and the residue was distilled under reduced pressure (bp 87 ° C./2 mmH
g) to give 200 g of 4-chloromethylbenzonitrile.
【００１９】ステップ３ ブタノール１２４ｃｍ3 にＮ
ａ２０ｇを溶解し４−クロロメチルベンゾニトリル３
０．３ｇを一度に加えて７時間還流した。反応液にクロ
ロホルム５００ｃｍ3 を加えて水で洗浄し、クロロホル
ムを留去した。残った油状物を減圧蒸留（ｂ．ｐ．１２
１℃／１ｍｍＨｇ）して４−ブトキシメチルベンゾニト
リル３３．６ｇを得た。 Step 3 Butanol 124 cm 3 N
Dissolve 20 g of 4-chloromethylbenzonitrile 3
0.3 g was added at once and refluxed for 7 hours. Chloroform (500 cm 3) was added to the reaction solution and the mixture was washed with water, and chloroform was distilled off. The residual oily substance was distilled under reduced pressure (bp.
(1 ° C./1 mmHg) to obtain 33.6 g of 4-butoxymethylbenzonitrile.
【００２０】ステップ４ ４−ブトキシメチルベンゾニ
トリル３３．６ｇ、ＫＯＨ５８ｇ，水３２ｃｍ3 、エチ
レングリコール１８０ｃｍ3 を撹拌しながら１５時間還
流した。反応液を１０％塩酸５００ｃｍ3 に注ぎ、析出
した結晶を濾過し、水で充分洗浄した。結晶を含水メタ
ノールから再結晶して４−ブトキシメチル安息香酸３１
ｇを得た。 Step 4 4-butoxymethylbenzonitrile (33.6 g), KOH (58 g), water (32 cm 3) and ethylene glycol (180 cm 3) were refluxed for 15 hours while stirring. The reaction solution was poured into 500 cm 3 of 10% hydrochloric acid, and the precipitated crystals were filtered and thoroughly washed with water. The crystals were recrystallized from water-containing methanol to give 4-butoxymethylbenzoic acid 31.
g was obtained.
【００２１】ステップ５ ４−ブトキシメチル安息香酸
３．１ｇ、４−フルオロフェノール１．７ｇ、トリフェ
ニルホスフィン４．８ｇをテトラヒドロフラン５０ｃｍ
3 に溶解し、撹拌しながらジエチル アゾカルボキシレ
ート３．１ｇを滴下した。その後室温で１晩撹拌した。
テトラヒドロフランを留去し、残渣を含水メタノールか
ら再結晶して４−フルオロフェニル ４′−ブトキシメ
チルベンゾエート３．４ｇを得た。 Step 5 4-butoxymethylbenzoic acid 3.1 g, 4-fluorophenol 1.7 g, and triphenylphosphine 4.8 g were added to tetrahydrofuran 50 cm.
It was dissolved in 3 and 3.1 g of diethyl azocarboxylate was added dropwise with stirring. Then, the mixture was stirred at room temperature overnight.
Tetrahydrofuran was distilled off and the residue was recrystallized from water-containing methanol to obtain 3.4 g of 4-fluorophenyl 4'-butoxymethylbenzoate.
【００２２】この化合物の相転移温度をＤＳＣ（昇降温
速度５℃／ｍｉｎ）を用いて測定した結果は次のとおり
であった。The phase transition temperature of this compound was measured by using DSC (rate of temperature increase / decrease: 5 ° C./min) and the results were as follows.
【００２３】Ｃ−Ｓ ２６．９℃ Ｓ−Ｉ ５３．４℃ 以下、同様な製造方法により次の化合物を製造した。C-S 26.9 ° C. S-I 53.4 ° C. The following compounds were produced by the same production method.
【００２４】４−フルオロフェニル ４′−メトキシメ
チルベンゾエート Ｃ−Ｉ ６９．０℃ ４−フルオロフェニル ４′−エトキシメチルベンゾエ
ート Ｃ−Ｉ ７１．０℃ ４−フルオロフェニル ４′−プロポキシメチルベンゾ
エート Ｃ−Ｉ ５７．６℃ ３，４−ジフルオロフェニル ４′−メトキシメチルベ
ンゾエート Ｃ−Ｉ １１２．７℃ ３，４−ジフルオロフェニル ４′−エトキシメチルベ
ンゾエート Ｃ−Ｉ ６０．２℃ Ｓ−Ｉ ２９．０℃ ３，４−ジフルオロフェニル ４′−プロポキシメチル
ベンゾエート Ｃ−Ｉ ４０．７℃ ３，４−ジフルオロフェニル ４′−ブトキシメチルベ
ンゾエート Ｃ−Ｓ ２９．８℃ Ｓ−Ｉ ４２．７℃ ［実施例２］ （結晶組成物） 市販の液晶組成物ＺＬＩ−１５６５（メルク社製）の９
０重量％に本発明の化合物４−フルオロフェニル ４′
−ブトキシメチルベンゾエートおよび３，４−ジフルオ
ロフェニル ４′−ブトキシメチルベンゾエートを各々
１０重量％混合した液晶組成物ＡおよびＢ、また比較例
としてＺＬＩ−１５６５自体のネマチック一等方性液体
相転移温度（Ｎ−Ｉ点）および複屈折（△ｎ）を測定し
た。以上の結果を表３に示した。 ［実施例３］ （液晶表示素子） 図１に示すようにガラス基板１および２の対向する内面
上にＩＴＯからなる透明電極３を形成し、この上側にポ
リイミドからなる配向剤を塗布し、この表面を綿布でラ
ビング処理して配向制御層４を形成した。さらに、ガラ
ス基板１と２をギャップ剤を含有するシール剤６を介し
て対向配置させ、その空間に実施例２の液晶組成物を注
入した。なお、セルギャップは９μｍでチルト角は９０
度のＴＮ型の液晶セルとし、２０℃において交流スタテ
ィック駆動方式を用いて電圧−光透過率特性のしきい値
電圧（Ｖｔｈ）、視角特性（α）および急峻性（β）を
測定した。以上の結果を表３に示した。4-Fluorophenyl 4'-methoxymethyl benzoate C-I 69.0 ° C. 4-Fluorophenyl 4'-ethoxymethyl benzoate C-I 71.0 ° C. 4-Fluorophenyl 4'-propoxymethyl benzoate C-I 57.6 ° C. 3,4-Difluorophenyl 4′-methoxymethyl benzoate C-I 112.7 ° C. 3,4-Difluorophenyl 4′-ethoxymethyl benzoate C-I 60.2 ° C. S-I 29.0 ° C. 3 , 4-Difluorophenyl 4'-propoxymethylbenzoate C-I 40.7 ° C 3,4-difluorophenyl 4'-butoxymethylbenzoate C-S 29.8 ° C S-I 42.7 ° C [Example 2] ( Crystal composition) 9 of commercially available liquid crystal composition ZLI-1565 (manufactured by Merck)
0% by weight of the compound of the present invention 4-fluorophenyl 4 '
-Butoxymethyl benzoate and 3,4-difluorophenyl 4'-butoxymethyl benzoate were mixed in liquid crystal compositions A and B, respectively, and as a comparative example, ZLI-1565 itself had a nematic isotropic liquid phase transition temperature ( The NI point) and the birefringence (Δn) were measured. The above results are shown in Table 3. Example 3 (Liquid Crystal Display Element) As shown in FIG. 1, transparent electrodes 3 made of ITO are formed on the inner surfaces of the glass substrates 1 and 2 facing each other, and an aligning agent made of polyimide is applied on the upper side of the transparent electrodes 3. The surface was rubbed with a cotton cloth to form an orientation control layer 4. Further, the glass substrates 1 and 2 were opposed to each other with a sealing agent 6 containing a gap agent interposed therebetween, and the liquid crystal composition of Example 2 was injected into the space. The cell gap is 9 μm and the tilt angle is 90
And a threshold voltage (Vth), a viewing angle characteristic (α) and a steepness (β) of a voltage-light transmittance characteristic were measured at 20 ° C. by using an AC static driving method. The above results are shown in Table 3.
【００２５】なお、本実施例においてはＴＮ型の液晶セ
ルを用いて測定したが、ＳＴＮ型の液晶セルを用いた場
合にも同様な効果が得られることを実験により確認し
た。In this example, the measurement was performed using a TN type liquid crystal cell, but it was confirmed by experiments that the same effect can be obtained when an STN type liquid crystal cell is used.
【表３】 [Table 3]
【００２６】[0026]
【発明の効果】以上、実施例により詳述したように、本
発明のエステル化合物は誘電異方性が正で大きな値を有
することがわかった。また、この化合物を従来の液晶組
成物に添加することにより誘電異方性が正で大きく、電
気化学的に安定な液晶組成物が得られることが確認でき
た。さらに、その液晶組成物をＴＮ型又はＳＴＮ型等の
液晶表示素子に使用するとしきい値電圧が低い液晶表示
素子が得られることが確認できた。As described above in detail with reference to Examples, it was found that the ester compound of the present invention has a positive and large dielectric anisotropy. Further, it was confirmed that by adding this compound to a conventional liquid crystal composition, a liquid crystal composition having a positive and large dielectric anisotropy and being electrochemically stable can be obtained. Furthermore, it was confirmed that when the liquid crystal composition was used for a TN type or STN type liquid crystal display element, a liquid crystal display element having a low threshold voltage was obtained.
【００２７】これらの点で本発明の化合物およびこれを
含有する液晶組成物はＴＮ型やＳＴＮ型の液晶表示素子
にとり極めて有用であり、特にＳＴＮ型の液晶表示素子
においてはＩＣの耐圧に対する負担を大いに軽減でき
る。From these points, the compound of the present invention and the liquid crystal composition containing the compound are extremely useful for TN-type and STN-type liquid crystal display elements, and particularly in the STN-type liquid crystal display element, the burden on the withstand voltage of the IC is increased. It can be greatly reduced.
【図１】本発明の実施例３において作製したＴＮ型液晶
表示素子の断面を示す図。FIG. 1 is a diagram showing a cross section of a TN type liquid crystal display element manufactured in Example 3 of the present invention.
１，２ ガラス基板 ３ 透明電極 ４ 配向制御層 ５ 偏光板 ６ シール剤 1, 2 glass substrate 3 transparent electrode 4 orientation control layer 5 polarizing plate 6 sealant
───────────────────────────────────────────────────── フロントページの続き (72)発明者 湯田坂 美穂 長野県諏訪市大和３丁目３番５号 セイコ ーエプソン株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Miho Yuzaka 3-3-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation
Claims (3)
Ｈ又はＦを示す）で表わされることを特徴とするエステ
ル化合物。1. A general formula: (Wherein R represents an alkyl group having 1 to 8 carbon atoms, X represents H or F), and an ester compound.
Ｈ又はＦを示す）で表わされるエステル化合物を少なく
とも一種類含有することを特徴とする液晶組成物。2. A general formula: (Here, R represents an alkyl group having 1 to 8 carbon atoms, X represents H or F), and at least one kind of ester compound is contained in the liquid crystal composition.
Ｈ又はＦを示す）で表わされるエステル化合物を少なく
とも一種類含有する液晶組成物を使用することを特徴と
する液晶表示素子。3. A general formula: (Wherein R is an alkyl group having 1 to 8 carbon atoms, X is H or F), and a liquid crystal composition containing at least one ester compound is used. ..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3259336A JPH0597772A (en) | 1991-10-07 | 1991-10-07 | Ester compound and liquid crystal composition and loquid crystal display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3259336A JPH0597772A (en) | 1991-10-07 | 1991-10-07 | Ester compound and liquid crystal composition and loquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0597772A true JPH0597772A (en) | 1993-04-20 |
Family
ID=17332690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3259336A Pending JPH0597772A (en) | 1991-10-07 | 1991-10-07 | Ester compound and liquid crystal composition and loquid crystal display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0597772A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0738709A3 (en) * | 1995-02-22 | 1997-07-16 | Chisso Corp | Ester derivate, liquid crystal composition and liquid crystal display element |
-
1991
- 1991-10-07 JP JP3259336A patent/JPH0597772A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0738709A3 (en) * | 1995-02-22 | 1997-07-16 | Chisso Corp | Ester derivate, liquid crystal composition and liquid crystal display element |
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