JP2872260B2 - Ferroelectric liquid crystal device - Google Patents
Ferroelectric liquid crystal deviceInfo
- Publication number
- JP2872260B2 JP2872260B2 JP1064775A JP6477589A JP2872260B2 JP 2872260 B2 JP2872260 B2 JP 2872260B2 JP 1064775 A JP1064775 A JP 1064775A JP 6477589 A JP6477589 A JP 6477589A JP 2872260 B2 JP2872260 B2 JP 2872260B2
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- liquid crystal
- crystal composition
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- general formula
- compound
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- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 title claims description 42
- 239000004973 liquid crystal related substance Substances 0.000 claims description 203
- 239000000203 mixture Substances 0.000 claims description 135
- 150000001875 compounds Chemical class 0.000 claims description 72
- 239000000758 substrate Substances 0.000 claims description 15
- 230000000087 stabilizing effect Effects 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
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- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
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- 229910052717 sulfur Inorganic materials 0.000 claims description 2
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- 230000004044 response Effects 0.000 description 34
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- 239000004990 Smectic liquid crystal Substances 0.000 description 9
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- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- NMZPWKRKMBJEOZ-UHFFFAOYSA-N 4-propylcyclohexane-1-carbonyl chloride Chemical compound CCCC1CCC(C(Cl)=O)CC1 NMZPWKRKMBJEOZ-UHFFFAOYSA-N 0.000 description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- WURPXOIGGSYBFF-UHFFFAOYSA-N 4-(5-butan-2-yl-1,3,4-thiadiazol-2-yl)phenol Chemical compound CC(CC)C=1SC(=NN1)C1=CC=C(C=C1)O WURPXOIGGSYBFF-UHFFFAOYSA-N 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- PPWKQEDYUMJFNK-XYPYZODXSA-N CCCCC[C@H]1CC[C@H](C(Cl)=O)CC1 Chemical compound CCCCC[C@H]1CC[C@H](C(Cl)=O)CC1 PPWKQEDYUMJFNK-XYPYZODXSA-N 0.000 description 1
- RVLAXPQGTRTHEV-XYPYZODXSA-N CCCCC[C@H]1CC[C@H](C(O)=O)CC1 Chemical compound CCCCC[C@H]1CC[C@H](C(O)=O)CC1 RVLAXPQGTRTHEV-XYPYZODXSA-N 0.000 description 1
- KBJAZDKVSZDVDM-SHTZXODSSA-N CCC[C@H]1CC[C@H](CCC(C=C2)=CC=C2S(O)(=O)=O)CC1 Chemical compound CCC[C@H]1CC[C@H](CCC(C=C2)=CC=C2S(O)(=O)=O)CC1 KBJAZDKVSZDVDM-SHTZXODSSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 108010021119 Trichosanthin Proteins 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Landscapes
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】 〔従来の技術〕 クラーク・ラガアウオルによって1980年に提唱され
た、強誘電性液晶表示方式,SSFLC（Surface-Stabilized
-ferroelectric-Liquidcrystal）方式においては、強誘
電液晶（以下FLC）自身の有するらせんピツチl0を上下
基板界面の効果を用いて、解くことに主眼を有する。DETAILED DESCRIPTION OF THE INVENTION [Prior Art] A ferroelectric liquid crystal display system, SSFLC (Surface-Stabilized), proposed in 1980 by Clark Ragaauol.
In -ferroelectric-Liquidcrystal) method, it has a focus on helical pitch l 0 having a ferroelectric liquid crystal (hereinafter FLC) itself with the effect of the upper and lower substrate interface, solving it in.
上下基板間隔（セル厚）を前記らせんピツチl0を解く
膜厚以下に設定し、 さらに、基板界面に対して液晶分子が平行に配向を取
るように設定しておくと、FLCのスメクチツク相におけ
る層方向は基板に垂直に形成される。In setting the upper and lower substrate gap (cell thickness) below the thickness solving the helical pitch l 0, further, the liquid crystal molecules to the substrate surface is set so as to take a parallel orientation, FLC of smectic phase The layer direction is formed perpendicular to the substrate.
さらに、すくなくとも一方の基板上の分子の配向方向
を規制しておけば、セル全面に渡って層方向を一定に形
成することができる。Furthermore, if the orientation direction of the molecules on at least one substrate is regulated, the layer direction can be formed to be constant over the entire surface of the cell.
以上のような段階的な分子制御によって形成された配
向状態をマクロに見ると、セル面内において安定なFLC
分子長軸方向（）は２方向に限定される。FLCデイス
プレイはこの２方向（の平均的方向）が偏光子によっ
て分別可能な点を表示素子に応用しようとするものであ
る。Macroscopic observation of the alignment state formed by the stepwise molecular control described above shows that FLC is stable in the cell plane.
The molecular long axis direction () is limited to two directions. The FLC display intends to apply a point that these two directions (average directions) can be distinguished by a polarizer to a display element.
上記の安定に２方向間をスイツチングする基本的なメ
カニズムはFLCがスメクチツクC*相において示す強誘電
性を利用する。The basic mechanism for stable switching between the two directions utilizes the ferroelectricity exhibited by the FLC in the smectic C * phase.
FLCは層に平行な面内に分子のダイポール・モーメン
ト を有し、セルの基板間をダイポール・モーメント を多少方向を変えながらも連続的につながり、平均的に
は下基板から上基板へ、もしくはその逆の方向へ自発分
極（Ps）を形成して存在している。FLC is the dipole moment of a molecule in a plane parallel to the layer And a dipole moment between the cell substrates Are connected continuously while slightly changing the direction, and on average, spontaneous polarization (Ps) is formed in the direction from the lower substrate to the upper substrate or in the opposite direction.
自発分極（Ps）の方向（上から下か、下から上）のそ
れぞれが、前述の分子長軸（）いずれかと一致してい
るため、電界によるスイツチングが可能となっている。Since each of the directions of the spontaneous polarization (Ps) (from top to bottom or from bottom to top) coincides with one of the above-mentioned molecular long axes (), switching by an electric field is possible.
詳しくは外部よりFLC層に電界を印加させると層内の
ダイポール・モーメント は全てその電場方向に揃い（U1）電界を切ると、しばら
くの緩和を経て（１μｓ〜2ms位、FLCによって異なる）
（S2）という状態に落つく、U1はS2より分子の秩序度が
高く、光学的には一軸性の良い状態であり（ユニホーム
状態）、S2はFLCのダイポールが多少ねじれるために、
軸性はU1より劣るが（ツイステツド状態）が自発分極の
方向が一致している状態である。同様に外部電界の極性
が逆になればU2,S2という状態が存在する。S1,S2同様に
U1,U2の２状態間を電界の極性によって選択出来ること
になる（双安定性）。Specifically, when an electric field is applied to the FLC layer from outside, the dipole moment in the layer Are all aligned in the direction of the electric field (U1) When the electric field is cut off, after some relaxation (about 1 μs to 2 ms, depending on FLC)
(S2), U1 has a higher molecular order than S2 and is optically better uniaxial (uniform state), and S2 has a slightly twisted FLC dipole,
Although the axis is inferior to U1 (twisted state), the direction of spontaneous polarization is the same. Similarly, if the polarity of the external electric field is reversed, the states U2 and S2 exist. S1 and S2 as well
The two states U1 and U2 can be selected by the polarity of the electric field (bistability).
以上のような双安定性を有する特徴に加えて、強誘電
液晶は高速応答性であるという優れた特徴を持つ。それ
は強誘電液晶の持つ自発分極と印加電場が直接作用して
配向状態の転移を誘起するためであり、誘電率異方性と
電場の作用による従来のTN型素子の応答速度より３〜４
オーダー速い。In addition to the characteristic having bistability as described above, the ferroelectric liquid crystal has an excellent characteristic of high-speed response. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied electric field act directly to induce a transition of the alignment state, which is 3 to 4 times higher than the response speed of the conventional TN type device due to the dielectric anisotropy and the action of the electric field.
Order fast.
このように強誘電液晶はきわめて優れた特性を潜在的
に有しており、このような性質を利用することにより、
高速光学光シヤツターや、高密度、大画面デイスプレイ
への応用が期待される。このため強誘電性を持つ液晶材
料に関しては広く研究がなされているが、現在までに開
発された強誘電性液晶材料は、低温作動特性、高速応答
性等を含めて液晶素子に用いる十分な特性を備えている
とは云い難い。As described above, ferroelectric liquid crystals have potentially excellent properties, and by utilizing such properties,
It is expected to be applied to high-speed optical shutters and high-density, large-screen displays. For this reason, liquid crystal materials with ferroelectricity have been widely studied, but the ferroelectric liquid crystal materials developed to date have sufficient characteristics to be used in liquid crystal devices, including low-temperature operation characteristics and high-speed response. It is hard to say that it has.
強誘電性液晶素子の応答速度を速くするには、 （ア）自発分極の大きさPsを大きくする （イ）粘度ηを小さくする （ウ）印加電圧Εを高くする 方法がある。しかし印加電圧は、IC等で駆動するため上
限があり、出来るだけ低い方が望ましい。よって、実際
には粘度ηを小さくするか、自発分極の大きさPsの値を
大きくする必要がある。In order to increase the response speed of the ferroelectric liquid crystal element, there are (a) increasing the magnitude Ps of spontaneous polarization, (a) decreasing the viscosity η, and (c) increasing the applied voltage Ε. However, the applied voltage has an upper limit because it is driven by an IC or the like, and it is desirable that the applied voltage be as low as possible. Therefore, it is actually necessary to reduce the viscosity η or increase the value of the magnitude Ps of the spontaneous polarization.
一般的に自発分極の大きい強誘電性カイラルスメクチ
ツク液晶化合物においては、自発分極のもたらすセルの
内部電界も大きく、双安定状態をとり得る素子構成への
制約が多くなる傾向にある。又、いたずらに自発電極を
大きくしても、それにつれて粘度も大きくなる傾向にあ
り、結果的には応答速度はあまり速くならないことが考
えられる。Generally, in a ferroelectric chiral smectic liquid crystal compound having a large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is large, and there is a tendency that restrictions on an element configuration which can take a bistable state are increased. Further, even if the spontaneous electrode is unnecessarily increased, the viscosity tends to increase with the spontaneous electrode, and as a result, the response speed may not be so high.
また、実際のデイスプレイとしての使用温度範囲が例
えば５〜40℃程度とした場合、応答速度の変化が一般に
20倍程もあり、駆動電圧及び周波数による調節の限界を
越えているのが現状である。In addition, when the operating temperature range of the actual display is, for example, about 5 to 40 ° C., the response speed generally varies.
At present, it is about 20 times, exceeding the limit of adjustment by drive voltage and frequency.
以上述べたように、強誘電性液晶素子を実用化するた
めには、粘度が低く高速応答性を有し、かつ応答速度の
温度依存性の小さな強誘電性カイラルスメクチツク液晶
組成物が要求される。As described above, in order to put a ferroelectric liquid crystal device into practical use, a ferroelectric chiral smectic liquid crystal composition having a low viscosity and a high-speed response and a small temperature dependence of a response speed is required. Is done.
代表的な強誘電液晶セルの構成は、ガラス基板上にIT
O等で電極パターンを形成し、その上にSiO2等で上下基
板のシヨート防止層を形成（約1000Å）その上にPI（東
レ社:SP510,710,…）膜を400Å位の膜厚で形成し、さら
にPI膜上をアセテート等の植毛布でラビング処理したも
のを上下対称な配向になるように向い合わせて構成し、
その基板間隔を１〜３μｍに保ったものである。A typical ferroelectric liquid crystal cell is composed of an IT
An electrode pattern is formed with O, etc., and a short prevention layer of the upper and lower substrates is formed thereon with SiO 2 or the like (approximately 1000 mm). A PI (Toray: SP510,710, ...) film is formed thereon with a thickness of about 400 mm. Formed and further rubbed with a flocking cloth such as acetate on the PI film, facing each other so as to be vertically symmetrical,
The distance between the substrates was kept at 1 to 3 μm.
一方、このような条件の下で配列したFLCは一般に基
板間をダイレクターがねじれた状態でつながり、スメ
クチツクＣ相で一軸性の配向を示さないことが知られて
いる（前述のS1,S2）。このような場合問題点のひとつ
に、液晶層の透過率が低いことである。On the other hand, it is known that FLCs arranged under such conditions are generally connected in a twisted state between the substrates and do not exhibit uniaxial orientation in the smectic C phase (S1, S2 described above). . One of the problems in such a case is that the transmittance of the liquid crystal layer is low.
安定な２状態S1,S2間の光学的選別は偏光子をクロス
ニコルに設定し、その間に上記セルを挿入して行われ、
S1,S2のいずれか、例えばS1の平均的分子軸に偏光子の
吸収軸と一致させると透過光を著しく低くなり、「黒」
を表現できる。次に、S2状態に分子位置をスイツチング
した場合、S1,S2間の角度を２θａとするとS2におい
て、分子位置は偏光軸より２θａだけずれることによ
り、透過光を生じ「白」を表現できる。The optical sorting between the stable two states S1 and S2 is performed by setting the polarizer to crossed Nicols and inserting the cell between them.
Any of S1 and S2, for example, when the average molecular axis of S1 is matched with the absorption axis of the polarizer, the transmitted light is significantly reduced, resulting in "black"
Can be expressed. Next, when the molecular position is switched to the S2 state, assuming that the angle between S1 and S2 is 2θa, in S2, the molecular position is shifted by 2θa from the polarization axis, thereby generating transmitted light and expressing “white”.
透過光量は分子配向の一軸性を仮定すると、クロスニ
コル下で入射光I0の強度に対してＩの強度を得る。When the amount of transmitted light is given the uniaxial molecular orientation, to obtain the intensity of I relative to the intensity of incident light I 0 under cross nicols.
ここで、ΔｎはFLCの屈折率異方性、ｄはセル厚、λは
入射光の波長である。 Here, Δn is the refractive index anisotropy of the FLC, d is the cell thickness, and λ is the wavelength of the incident light.
前述のようなセルを用いた場合に、ツイステイド配向
を取った場合はθａは５°〜８°で、材料にそれ程よら
ないことが実験的に知られている。It is experimentally known that when the above-described cell is used, when twisted orientation is taken, θa is 5 ° to 8 °, which is not so much depending on the material.
Δndπ／λの項のコントロールは、物性的に簡単には
行えないので、θａを大きくして、Ｉを大きくしたい
が、スタテイツクな配向技法によってはなかなか全てを
上手く達成出来ていない。Since the control of the term Δndπ / λ cannot be easily performed in terms of physical properties, it is desirable to increase θa and increase I, but it has not been possible to achieve all of the above well by a static orientation technique.
このような問題に対して、FLCのΔε項のトルクを用
いることによりθａを広げられることが知られている
（1983.SIDでAT＆Ｔにより発表、キヤノン特開昭61-245
142、61-246722、61-246723、61-246724、61-249024、6
1-249025）。スイツチング時以外に一定の実効値の電界
を印加しておくことにより、誘電分極の発生により、電
界中での分子の安定状態がS1,S2から変化することを利
用する（ACスタビライズ効果）状態のスイツチングに関
するFLC分子に働くトルクΓPs、ACスラビライズ効果に
関してFLC分子に働くトルクΓΔεとは各々次のような
物性に比例する。It is known that such problems can be widened by using the torque of the Δε term of the FLC (announced by AT & T in 1983. SID, Canon JP-A-61-245).
142, 61-246722, 61-246723, 61-246724, 61-249024, 6
1-249025). By applying an electric field with a constant effective value except during switching, the stable state of molecules in the electric field changes from S1 and S2 due to the occurrence of dielectric polarization (AC stabilization effect). torque gamma Ps acting on FLC molecules relating to switching-, each torque gamma [Delta] [epsilon] acting on FLC molecules for AC Surabiraizu effect proportional to physical properties as follows.
（３）式によっても明らかなようにFLCのΔεの符号及
び絶対値がきわめて重要な役割を示すことがわかる。 As is clear from equation (3), the sign and the absolute value of Δε of FLC play a very important role.
Δεに関する物性が異なる値を持つ４種のFLCのVrms
に対するθａの変化を第１図に示した。Vrms of four FLCs with different values of physical properties regarding Δε
FIG. 1 shows the change of θa with respect to.
測定はPsによる影響を除くために60KHzの矩形交流で
行った。The measurement was performed with a rectangular alternating current of 60 KHz to eliminate the influence of Ps.
（Ｉ）はΔε−5.5、（II）はΔε−3.0、 （III）はΔε−０、（IV）はΔε−1.0であり、定
性的にもΔεは（Ｉ）＜（II）＜（III）＜（IV）であ
った。(I) is Δε-5.5, (II) is Δε-3.0, (III) is Δε-0, and (IV) is Δε-1.0. Qualitatively, Δε is (I) <(II) <(III) ) <(IV).
グラグを見てもわかるようにΔεが負に大きい程低電
圧でθａが大きくなり、従って、Ｉに貢献することがわ
かる。As can be seen from the glug, it can be seen that as Δε becomes larger negatively, θa becomes larger at a low voltage, and thus contributes to I.
この（Ｉ）と（III）を用いた場合の透過率の差を比
較してみると（Ｉ）では15％なのに対し、（III）では
６％であり明らかな差があった。Comparing the difference in transmittance between (I) and (III), the difference was clearly 15% in (I) and 6% in (III).
以上の例でも知られるように、ΔεとPs（η）の物性
をコントロールすることにより、SSFLCの表示特性を大
きく変えることができる。As is known from the above examples, by controlling the physical properties of Δε and Ps (η), the display characteristics of the SSFLC can be largely changed.
しかしながら、現状用いられている強誘電性液晶組成
物の多くはΔεがほとんど０に近いため、前述のACスタ
ビライズ効果による表示特性の向上はほとんど期待でき
ない。However, since most of the ferroelectric liquid crystal compositions currently used have Δε almost close to 0, improvement in display characteristics due to the above-described AC stabilization effect can hardly be expected.
本発明の目的は、前述の問題を解決し、新規な特性の
化合物を用い、応答特性が優れ、ACスタビライズ効果が
付与された液晶組成物を用いた高性能の液晶素子を提供
することにある。An object of the present invention is to solve the above-mentioned problems and provide a high-performance liquid crystal element using a liquid crystal composition having a novel characteristic, excellent response characteristics, and an AC stabilizing effect. .
下記一般式（Ｉ） ［上記一般式中、A1は単結合、 を示す。Ｘは水素、ハロゲンあるいはシアノ基を示し、
Ｙは酸素または硫黄を示す。R1及びR2は置換基を有して
もよい炭素数１〜18の直鎖状または分岐状のアルキル
基、アルコキシ基、アルキルカルボニルオキシ基、アル
キルオキシカルボニル基、またはアルキルオキシカルボ
ニルオキシ基を示し、この場合置換基は塩素、臭素、シ
アノ基、アルコキシ基、あるいはアルキルオキシカルボ
ニル基を示す。また、Ｂは を示す。］ で表される化合物を少なくとも１種含むACスタビライ
ズ効果を生じさせるために充分な負のΔεを有する液晶
組成物を、一対の基板間に配置してなり、ACスタビライ
ズ効果を生じさせるようなACを印加する手段を有する強
誘電性液晶素子を提供するものである。The following general formula (I) [In the above general formula, A 1 is a single bond, Is shown. X represents hydrogen, halogen or a cyano group,
Y represents oxygen or sulfur. R 1 and R 2 may have a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkoxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, or an alkyloxycarbonyloxy group. In this case, the substituent represents chlorine, bromine, a cyano group, an alkoxy group, or an alkyloxycarbonyl group. B is Is shown. A liquid crystal composition having a negative Δε sufficient to produce an AC stabilizing effect containing at least one compound represented by formula (I) is disposed between a pair of substrates, and an AC stabilizing effect is produced. To provide a ferroelectric liquid crystal element having a means for applying a voltage.
本発明者らは、環骨格中にヘテロ原子を導入し、特異
なπ電子構造をもたせて、分子短軸方向の誘電率を増大
させた一般式（Ｉ）で表わされる液晶性化合物を強誘電
性液晶化合物、強誘電性液晶組成物等に混合することに
より得られた強誘電性液晶組成物および該液晶組成物を
用いた強誘電性液晶素子は応答特性が優れていて、さら
にACスタビライズ効果が付与され、その結果良好な表示
特性が得られることを見いだしたものである。The present inventors have proposed a ferroelectric liquid crystal compound represented by the general formula (I) in which a hetero atom is introduced into the ring skeleton to give a unique π-electron structure and increase the dielectric constant in the minor axis direction of the molecule. The ferroelectric liquid crystal composition obtained by mixing with a ferroelectric liquid crystal compound, a ferroelectric liquid crystal composition, and the like, and a ferroelectric liquid crystal device using the liquid crystal composition have excellent response characteristics, and further have an AC stabilizing effect. Has been provided, and as a result, good display characteristics can be obtained.
本発明の一般式（Ｉ）で示される液晶性化合物のうち
Ｂが のものは次の経路で合成される。In the liquid crystalline compound represented by the general formula (I) of the present invention, B is Are synthesized by the following route.
但し、下記の方法でも合成できる。 However, it can also be synthesized by the following method.
Ｂが のものは以下の経路で合成される。 B is Are synthesized by the following route.
Ｂが-CH2Oのものは以下の経路で合成される。 When B is —CH 2 O, it is synthesized by the following route.
一般式（Ｉ）で表わされる液晶性化合物の具体例を示
す。 Specific examples of the liquid crystal compound represented by the general formula (I) are shown.
本発明の液晶組成物は前記一般式（Ｉ）で表わされる
液晶性化合物を少なくとも１種類配合成分として含有す
るものである。 The liquid crystal composition of the present invention contains at least one compound of the liquid crystal compound represented by the general formula (I).
本発明の液晶組成物は前記一般式（Ｉ）で表わされる
液晶性化合物の他に自発分極、らせんピツチ、相系列お
よびその温度範囲、応答特性、チルト角、誘電率異方性
等を調整するために、下記する各群に示される化合物か
ら選択される化合物を構成成分として含有するものであ
る。The liquid crystal composition of the present invention controls spontaneous polarization, helical pitch, phase series and its temperature range, response characteristics, tilt angle, dielectric anisotropy, and the like, in addition to the liquid crystal compound represented by the general formula (I). Therefore, a compound selected from the compounds shown in each of the following groups is contained as a component.
この場合、一般式（Ｉ）で示される液晶性化合物を、
得られる液晶組成物の0.5〜60重量％、好ましくは５〜4
0重量％で使用することが望ましい。In this case, the liquid crystal compound represented by the general formula (I) is
0.5 to 60% by weight, preferably 5 to 4% by weight of the obtained liquid crystal composition
It is desirable to use 0% by weight.
Ａ群：カイラルでないネマチツク相に添加することで
らせんを生ずる光学活性化合物 Ｂ群；カイラルでないスメクチツク相および（また
は）ネマチツク相を有する液晶化合物 そして前述の化合物例の中でも、本願発明の一般式
（Ｉ）で表わされる液晶性化合物と、Ｂ群の中でも特に
フエニルピリミジンを有する系の化合物とを有する強誘
電性液晶組成物は、良好な液晶組成物を形成することが
できる。Group A: Optically active compound that generates a helix when added to a non-chiral nematic phase Group B: liquid crystal compounds having non-chiral smectic phase and / or nematic phase Among the above-mentioned compound examples, a ferroelectric liquid crystal composition having a liquid crystal compound represented by the general formula (I) of the present invention and a compound having a phenylpyrimidine among groups B is particularly excellent. A liquid crystal composition can be formed.
以下実施例を用いて、本発明をさらに詳細に説明す
る。ただし本発明の具体例、実施例により本発明が限定
されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited by specific examples and embodiments of the present invention.
実施例１ ２−ｎ−デシル−５−［４−（トランス−４′−ｎ−
ペンチルシクロヘキシルカルボニルオキシ）−フエニ
ル］−1,3,4−オキサジアゾールの合成（例示化合物Ａ
−３） ２−ｎ−デシル−５−［４−ヒドロキシフエニル］−
1,3,4−オキサジアゾール1.5g（4.97×10-3モル）、ド
ライピリジン2.5ml、ドライトルエン2.5mlの混合溶液の
中に、トランス−４−ｎ−ペンチルシクロヘキサンカル
ボニルクロリド1.08g（4.97×10-3モル）のドライトル
エン2.5ml溶液を５℃以下にて、20分間で滴下した。滴
下後室温にて27時間撹拌した。反応終了後氷水50mlに反
応溶液を注入し、6N,HClでpH1にした。ベンゼンで抽
出、水洗い、脱水した後、溶媒（ベンゼン）を留去し、
粗生成物を得た。これをｎ−ヘキサン／酢酸エチル＝5/
1混合溶媒を用いたシリカゲルクロマトグラフイー精製
を行い、さらにエタノールで再結晶し、1.92gの２−ｎ
−デシル−５−［４−（トランス−４′−ｎ−ペンチル
シクロヘキシルカルボニルオキシ）−フエニル］−1,3,
4−オキサジアゾールを得た。（収率80.1％） 実施例2,3,4 実施例１で用いた２−ｎ−デシル−５−［４−ヒドロ
キシフエニル］−1,3,4−オキサジアゾールを用い、反
応相手を変えて、同様な方法で誘電体を合成した。Example 1 2-n-decyl-5- [4- (trans-4'-n-
Pentylcyclohexylcarbonyloxy) -phenyl] -1,3,4-oxadiazole (Exemplified Compound A
-3) 2-n-decyl-5- [4-hydroxyphenyl]-
In a mixed solution of 1.5 g (4.97 × 10 −3 mol) of 1,3,4-oxadiazole, 2.5 ml of dry pyridine and 2.5 ml of dry toluene, 1.08 g (4.97 g) of trans-4-n-pentylcyclohexanecarbonyl chloride was added. (× 10 −3 mol) in 2.5 ml of dry toluene was added dropwise at 5 ° C. or lower for 20 minutes. After the addition, the mixture was stirred at room temperature for 27 hours. After completion of the reaction, the reaction solution was poured into 50 ml of ice water, and the pH was adjusted to 1 with 6N HCl. After extracting with benzene, washing with water and dehydrating, the solvent (benzene) is distilled off,
A crude product was obtained. This is n-hexane / ethyl acetate = 5 /
(1) Purification by silica gel chromatography using a mixed solvent, and recrystallization with ethanol, 1.92 g of 2-n
-Decyl-5- [4- (trans-4'-n-pentylcyclohexylcarbonyloxy) -phenyl] -1,3,
4-Oxadiazole was obtained. (Yield 80.1%) Examples 2, 3, 4 A similar method was conducted using 2-n-decyl-5- [4-hydroxyphenyl] -1,3,4-oxadiazole used in Example 1 and changing the reaction partner. Synthesized the dielectric.
実施例２ 反応相手 トランス−４−ｎ−プロピルシクロヘキサン
カルボニルクロリド 生成物 ２−ｎ−デシル−５−［４−（トランス−４′
−ｎ−プロピルシクロヘキシルカルボニルオキシ）−フ
エニル］−1,3,4−オキサジアゾール（例示化合物Ａ−
２） 実施例３ 反応相手 ｐ−ｎ−デシル安息香酸クロリド 生成物 ２−ｎ−デシル−５−［（４−（４′−ｎ−デ
シルベンゾイルオキシ）−フエニル］−1,3,4−オキサ
ジアゾール（例示化合物A-12） 実施例４ 反応相手 ３−フルオロ−４−ｎ−オクチルオキシ安息
香酸クロリド 生成物 ２−ｎ−デシル−５−［４−（３−フルオロ−
４′−ｎ−オクチルオキシベンゾイルオキシ）−フエニ
ル］−1,3,4−オキサジアゾール（例示化合物A-15） 実施例５ ２−ｎ−オクチル−５−［４−ヒドロキシフエニル］
−1,3,4−オキサジアゾールとトランス−４−ｎ−プロ
ピルシクロヘキサンカルボニルクロリドを用い、実施例
１と同様な方法で反応させて、２−ｎ−オクチル−５−
［４−（トランス−４′−ｎ−プロピルシクロヘキシル
カルボニルオキシ）−フエニル］−1,3,4−オキサジア
ゾールを得た。（収率85％） 実施例６ ２−ｎ−デシル−５−［４−（トランス−４′−4n−
プロピルシクロヘキシルメチレンオキシ）−フエニル］
1,3,4−オキサジアゾールの合成（例示化合物A-22） ２−ｎ−デシル−５−［４−ヒドロキシフエニル］−
1,3,4−オキサジアゾール1.5g（4.97×10-3モル）を20m
lのジメチルホルムアミドに溶解した。これに85％水酸
化カリウム0.75gを加え100℃で１時間撹拌した。これに
トランス−４−ｎ−プロピルシクロヘキシルメチル−ｐ
−トルエンスルホネート1.54g（4.97×10-3モル）を加
え、さらに100℃で４時間撹拌した。反応終了後これを
氷水200mlに注入し、ベンゼンデ抽出、水洗、脱水した
後、溶媒を留去し、粗生成物を得た。これをシリカゲル
カラムクロマトグラフイー精製を行い、さらにエタノー
ルで再結晶し、0.94gの２−ｎ−デシル−５−［４−
（トランス−４′−ｎ−プロピルシクロヘキシルメチレ
ンオキシ）−フエニル］−1,3,4−オキサジアゾールを
得た。（収率43.2％） 実施例７ 前記強誘電性液晶化合物の具体例（Ａ群）のうち
（９）と前記本発明の一般式（Ｉ）で表わされる液晶性
化合物の具体例のうち、Ａ−２とを4:1の割合で混合し
て、液晶組成物Ａを得た。上記強誘電性液晶化合物
（９）と、液晶生成物Ａをそれぞれ電極を覆うポリイミ
ド被覆にラビング処理を施した一対の電極基板間（セル
厚２μｍ）に挟持し、液晶素子を作製した。これらの液
晶素子を用い、ピークトウピーク電圧20Vの電界印加に
より直交ニコル下での光学的な応答を検知して応答速度
を測定した。結果を下に示す。Example 2 Reaction partner trans-4-n-propylcyclohexanecarbonyl chloride product 2-n-decyl-5- [4- (trans-4 '
-N-propylcyclohexylcarbonyloxy) -phenyl] -1,3,4-oxadiazole (Exemplified compound A-
2) Example 3 Reaction partner pn-decylbenzoic acid chloride product 2-n-decyl-5-[(4- (4'-n-decylbenzoyloxy) -phenyl] -1,3,4-oxadiazole (Exemplified compound A-12) Example 4 Reaction partner 3-fluoro-4-n-octyloxybenzoic acid chloride product 2-n-decyl-5- [4- (3-fluoro-
4'-n-octyloxybenzoyloxy) -phenyl] -1,3,4-oxadiazole (exemplified compound A-15) Example 5 2-n-octyl-5- [4-hydroxyphenyl]
Using 1,3,4-oxadiazole and trans-4-n-propylcyclohexanecarbonyl chloride, the reaction was carried out in the same manner as in Example 1 to give 2-n-octyl-5-.
[4- (Trans-4'-n-propylcyclohexylcarbonyloxy) -phenyl] -1,3,4-oxadiazole was obtained. (85% yield) Example 6 2-n-decyl-5- [4- (trans-4'-4n-
Propylcyclohexylmethyleneoxy) -phenyl]
Synthesis of 1,3,4-oxadiazole (Exemplified Compound A-22) 2-n-decyl-5- [4-hydroxyphenyl]-
1.5 g (4.97 × 10 -3 mol) of 1,3,4-oxadiazole in 20 m
dissolved in 1 dimethylformamide. 0.75 g of 85% potassium hydroxide was added thereto and stirred at 100 ° C. for 1 hour. In addition, trans-4-n-propylcyclohexylmethyl-p
1.54 g (4.97 × 10 −3 mol) of toluenesulfonate was added, and the mixture was further stirred at 100 ° C. for 4 hours. After completion of the reaction, this was poured into 200 ml of ice water, extracted with benzene, washed with water and dehydrated, and the solvent was distilled off to obtain a crude product. This was purified by silica gel column chromatography and further recrystallized from ethanol to obtain 0.94 g of 2-n-decyl-5- [4-
(Trans-4'-n-propylcyclohexylmethyleneoxy) -phenyl] -1,3,4-oxadiazole was obtained. (Yield 43.2%) Example 7 Among the specific examples of the ferroelectric liquid crystal compound (group A), (9) and among the specific examples of the liquid crystal compound represented by the general formula (I) of the present invention, A-2 was replaced by 4: The mixture was mixed at a ratio of 1 to obtain a liquid crystal composition A. The ferroelectric liquid crystal compound (9) and the liquid crystal product A were sandwiched between a pair of electrode substrates (cell thickness 2 μm) each of which had been subjected to a rubbing treatment on a polyimide coating covering the electrodes, thereby producing a liquid crystal element. Using these liquid crystal elements, the response speed was measured by detecting the optical response under crossed Nicols by applying an electric field of peak-to-peak voltage of 20V. The results are shown below.
40℃ 25℃ 強誘電性液晶化合物（９） 400μｓ 610μｓ 液晶組成物Ａ 280μｓ 420μｓ 以上のことから、強誘電性液晶化合物［具体例
（９）］に本発明の液晶性化合物［具体例Ａ−２］を混
合することにより応答特性が向上することがわかった。40 ° C. 25 ° C. Ferroelectric liquid crystal compound (9) 400 μs 610 μs Liquid crystal composition A 280 μs 420 μs From the above, the liquid crystal compound of the present invention [specific example A-2] was added to the ferroelectric liquid crystal compound [specific example (9)]. ] Has been found to improve the response characteristics.
実施例８ 前記強誘電性液晶化合物の具体例（Ａ群）のうち
（１）と（38）を4:1の割合で混合し、液晶組成物Ｂを
得た。Example 8 Among the specific examples of the ferroelectric liquid crystal compound (Group A), (1) and (38) were mixed at a ratio of 4: 1 to obtain a liquid crystal composition B.
次に、上記液晶組成物Ｂと、前記本発明の一般式
（Ｉ）で表わされる液晶性化合物の具体例のうちA-23を
9:1の割合で混合し、液晶組成物Ｃを得た。Next, the liquid crystal composition B and A-23 of the specific examples of the liquid crystal compound represented by the general formula (I) of the present invention are shown below.
The mixture was mixed at a ratio of 9: 1 to obtain a liquid crystal composition C.
上記液晶組成物Ｂと、液晶組成物Ｃを用い、実施例６
の場合と同様にそれぞれ液晶素子を作製した。これらの
液晶素子を用い、印加電圧を30Vにした他は、実施例６
と全く同様な方法で応答速度を測定した。下に結果を示
す。Example 6 using the liquid crystal composition B and the liquid crystal composition C,
Liquid crystal elements were produced in the same manner as in the above case. Example 6 except that these liquid crystal elements were used and the applied voltage was 30 V
The response speed was measured in the same manner as described above. The results are shown below.
35℃ 25℃ 液晶組成物Ｂ 685μｓ 1275μｓ 液晶組成物Ｃ 450μｓ 680μｓ 以上のことから、液晶組成物Ｂに、本発明の液晶性化
合物A-23を混合することにより、応答特性が向上するこ
とがわかった。35 ° C. 25 ° C. Liquid crystal composition B 685 μs 1275 μs Liquid crystal composition C 450 μs 680 μs From the above results, it can be seen that the response characteristics are improved by mixing the liquid crystal composition B with the liquid crystal compound A-23 of the present invention. Was.
実施例９ 実施例７で用いた液晶組成物Ｂと前記カイラルでない
スメクチツク液晶化合物の具体例（Ｂ群）のうちと、
本発明の一般式（Ｉ）で表わされる液晶性化合物のうち
Ａ−３とA-12とを下記比率で混合して液晶組成物Ｄを得
た。Example 9 Among the liquid crystal composition B used in Example 7 and the specific examples (Group B) of the non-chiral smectic liquid crystal compound,
Liquid crystal composition D was obtained by mixing A-3 and A-12 at the following ratio among the liquid crystal compounds represented by the general formula (I) of the present invention.
液晶組成物Ｄ 液晶組成物B::A−3:A-12＝14:4:1:1 上記液晶組成物Ｄを用い実施例７と全く同じ条件で液
晶素子を作製し、全く同じ条件で応答速度を測定した。Liquid crystal composition D Liquid crystal composition B :: A-3: A-12 = 14: 4: 1: 1 Using the above liquid crystal composition D, a liquid crystal element was produced under exactly the same conditions as in Example 7, and under exactly the same conditions. The response speed was measured.
下に結果を示す。The results are shown below.
35℃ 25℃ 液晶組成物Ｂ（実施例７） 685μｓ 1275μｓ 液晶組成物Ｄ 470μｓ 620μｓ 以上のことから、液晶組成物Ｂに、本発明の液晶性化
合物Ａ−３とA-12と、他のカイラルでないスメクチツク
液晶化合物とを組み合わせて混合することにより応答
特性が向上することがわかった。35 ° C. 25 ° C. Liquid crystal composition B (Example 7) 685 μs 1275 μs Liquid crystal composition D 470 μs 620 μs From the above, the liquid crystal composition B was added to the liquid crystal compounds A-3 and A-12 of the present invention and another chiral compound. It was found that the response characteristics were improved by mixing and mixing with a smectic liquid crystal compound.
実施例10 Δεがほとんど０であるチツソ社製液晶CS1014［Δε
−0.4（sin波、100KHz）］と本発明の一般式（Ｉ）で
表わされる液晶性化合物の具体例のうちA-22を92:8の割
合で混合し液晶組成物Εを得た。上記CS1014と、液晶組
成物Εを用い、液晶層厚を1.5μｍとした他は、実施例
６と全く同様な方法でそれぞれ液晶素子を作製した。Example 10 A liquid crystal CS1014 [Δε manufactured by Chitso Corporation in which Δε is almost 0
−0.4 (sin wave, 100 KHz)] and A-22 in a specific example of the liquid crystal compound represented by the general formula (I) of the present invention were mixed at a ratio of 92: 8 to obtain a liquid crystal composition Ε. Liquid crystal devices were each manufactured in exactly the same manner as in Example 6, except that the above CS1014 and the liquid crystal composition Ε were used and the liquid crystal layer thickness was 1.5 μm.
上記液晶素子を用い、25℃において直交ニコル下でチ
ルト角を測定したところ、CS1014は７°、液晶組成物Ε
は7.2°であった。次に60KHzの周波数で±8Vのの矩形波
を印加しながら、顕微鏡観察を行いチルト角を測定した
ところ、CS1014は8.8°、液晶組成物Εは11.4°になっ
た。この時透過率を測定したところCS1014は7.8％、液
晶組成物は11％であった。またさらにコントラスト比を
測定したところCS1014は8:1、液晶組成物Εは30:1であ
った。The tilt angle was measured at 25 ° C. under crossed Nicols using the above liquid crystal element.
Was 7.2 °. Next, while applying a rectangular wave of ± 8 V at a frequency of 60 KHz, the microscope was observed and the tilt angle was measured. As a result, CS1014 was 8.8 ° and liquid crystal composition Ε was 11.4 °. At this time, the transmittance was measured, whereby CS1014 was 7.8% and the liquid crystal composition was 11%. Further, when the contrast ratio was further measured, CS1014 was 8: 1 and liquid crystal composition Ε was 30: 1.
以上のことからΔεがほとんど０であるCS1014に本発
明の一般式（Ｉ）で表わされる液晶性化合物A-22を混合
することにより得られた液晶素子はACスタビライズ効果
による表示特性が改善できることがわかった。From the above, it can be seen that the liquid crystal device obtained by mixing the liquid crystal compound A-22 represented by the general formula (I) of the present invention with CS1014 having Δε of almost 0 can improve the display characteristics by the AC stabilization effect. all right.
実施例11 ２−ｎ−デシル−５−［４−（トランス−４′−ｎ−
プロピルシクロヘキシルカルボニルオキシ）−フエニ
ル］−1,3,4−チアジアゾールの合成（例示化合物B-2
0） ２−ｎ−デシル−５−［４−ヒドロキシフエニル］−
1,3,4−チアジアゾール1.2g（3.77×10-3モル）、ドラ
イピリジン2.5ml、ドライトルエン2.5mlの混合溶液の中
に、トランス−４−ｎ−プロピルシクロヘキサンカルボ
ニルクロリド0.71g（3.77×10-3モル）のドライトルエ
ン2.5ml溶液を５℃以下にて、15分間で滴下した。滴下
後室温にて19時間撹拌した。反応終了後氷水50mlに反応
溶液を注入し、6N,HClでpH1にした。ベンゼンで抽出、
水洗、脱水した後、溶媒（ベンゼン）を留去し、粗生成
物を得た。これをｎ−ヘキサン／酢酸エチル＝3/1混合
溶媒を用いたシリカゲルクロマトグラフイー精製を行
い、さらにエタノールで再結晶し、1.15gの２−ｎ−デ
シル−５−［４−（トランス−４′−ｎ−プロピルシク
ロヘキシルカルボニルオキシ）−フエニル］−1,3,4−
チアジアゾールを得た。（収率64.9％） IR（cm-1） 2925,2850,1740,1600,1510,1470,1450,1205,1165,1130,
980,862 実施例12 ２−ｎ−デシル−５−［４−（トランス−４−ｎ−ペ
ンチルシクロヘキシルカルボニルオキシ）−フエニル］
−1,3,4−チアジアゾールの合成（例示化合物B-34） 実施例11において、トランス−４−ｎ−プロピルシク
ロヘキサンカルボニルクロリドの代りに、トランス−４
−ｎ−ペンチルシクロヘキサンカルボニルクロリドを用
いることにより、２−ｎ−デシル−５−［４−（トラン
ス−４−ｎ−ペンチルシクロヘキシルカルボニルオキ
シ）フエニル］−1,3,4−チアジアゾールを得た。Example 11 2-n-decyl-5- [4- (trans-4'-n-
Propylcyclohexylcarbonyloxy) -phenyl] -1,3,4-thiadiazole (Exemplified compound B-2
0) 2-n-decyl-5- [4-hydroxyphenyl]-
In a mixed solution of 1.2 g (3.77 × 10 −3 mol) of 1,3,4-thiadiazole, 2.5 ml of dry pyridine and 2.5 ml of dry toluene, 0.71 g of trans-4-n-propylcyclohexanecarbonyl chloride (3.77 × 10 3 mol) -3 mol) in 2.5 ml of dry toluene was added dropwise at 5 ° C. or lower over 15 minutes. After the addition, the mixture was stirred at room temperature for 19 hours. After completion of the reaction, the reaction solution was poured into 50 ml of ice water, and the pH was adjusted to 1 with 6N HCl. Extract with benzene,
After washing and dehydration, the solvent (benzene) was distilled off to obtain a crude product. This was purified by silica gel chromatography using a mixed solvent of n-hexane / ethyl acetate = 3/1 and further recrystallized from ethanol to obtain 1.15 g of 2-n-decyl-5- [4- (trans-4). '-N-Propylcyclohexylcarbonyloxy) -phenyl] -1,3,4-
Thiadiazole was obtained. (Yield 64.9%) IR (cm -1 ) 2925,2850,1740,1600,1510,1470,1450,1205,1165,1130,
980,862 Example 12 2-n-decyl-5- [4- (trans-4-n-pentylcyclohexylcarbonyloxy) -phenyl]
Synthesis of -1,3,4-thiadiazole (Exemplary Compound B-34) In Example 11, trans-4-n-propylcyclohexanecarbonyl chloride was replaced with trans-4
By using -n-pentylcyclohexanecarbonyl chloride, 2-n-decyl-5- [4- (trans-4-n-pentylcyclohexylcarbonyloxy) phenyl] -1,3,4-thiadiazole was obtained.
収率:60.2％ IR（cm-1） 2860,2825,1750,1600,1508,1470,1450,1205,1162,1135,
980,860 実施例13 ２−ｎ−デシル−５−［４−（トランス−４−ｎ−プ
ロピルシクロヘキシルメチレンオキシ）フエニル］−1,
3,4−チアジアゾールの合成（例示化合物Ｂ−３） ２−ｎ−デシル−５−［４−ヒドロキシフエニル］−
1,3,4−オキサジアゾール1.0g（3.28×10-3モル）を20m
lのジメチルホルムアミドに溶解した。これに、85％水
酸化カリウム0.5gを加え、100℃で１時間撹拌した。こ
れに、トランス−４−ｎ−プロピルシクロヘキシルメチ
ル−ｐ−トルエンスルホネート1.02g（3.28×10-3モ
ル）を加え、さらに100℃で４時間撹拌した。反応終了
後、これを氷水200mlに注入し、ベンゼンで抽出、水
洗、脱水した後、溶媒を留去し粗生成物を得た。これを
シリカゲルクロマトグラフイー精製を行い、さらにエタ
ノールで再結晶し、0.8gの２−ｎ−デシル−５−［４−
（トランス−４′−ｎ−プロピルシクロヘキシルメチレ
ンオキシ）−フエニル］−1,3,4−チアジアゾールを得
た。（収率53.3％） IR（cm-1） 2945,2860,1608,1580,1520,1480,1460,1320,1260,1180,
1125,1040,985,858 実施例14 ２−（１−メチルプロピル）−５−〔４−（トランス
−４−ｎ−ペンチルシクロヘキシルカルボニルオキシ）
−フエニル〕−1,3,4−チアジアゾールの合成（例示化
合物B-51） １−メチルプロピル−５−〔４−ヒドロキシフエニ
ル〕−1,3,4−チアジアゾール0.3g（1.28×10-3モ
ル）、トランス−４−ｎ−ペンチルシクロヘキシルカル
ボン酸0.26g（1.31×10-3モル）ジシクロヘキシルカル
ボジイミド0.27g（1.31×10-3モル）、４−（１−ピロ
リジニル）ピリジン0.03gに塩化メチレン15mlを加え、
室温にて20時間撹拌した。反応終了後、反応溶液をろ過
し、さらに塩化メチレンで洗浄した。ろ液と洗液を脱水
した後、溶媒を留去し粗生成物を得た。これをエタノー
ルで２回再結晶し、0.24gの２−（１−メチルプロピ
ル）−５−〔４−（トランス−４−ｎ−ペンチルシクロ
ヘキシルカルボニルオキシ）−フエニル〕−1,3,4−チ
アジアゾールを得た。（収率45.2％） 実施例15 具体例（Ａ群）のうち（９）と前記本発明の一般式
（Ｉ）で表わされる液晶性化合物の具体例のうち、Ｂ−
７とを4:1の割合で混合して、液晶組成物Ｆを得た。上
記強誘電性液晶化合物（９）と、液晶組成物Ｆをそれぞ
れ電極を覆うポリイミド被覆にラビング処理を施した一
対の電極基板間に挟持し、実施例７と同様にして液晶素
子を作製した。これらの液晶素子を用い、ピークトウピ
ーク電圧20Vの電界印加により直交ニコル下での光学的
な応答を検知して応答速度を測定した。結果を下に示
す。Yield: 60.2% IR (cm -1 ) 2860,2825,1750,1600,1508,1470,1450,1205,1162,1135,
980,860 Example 13 2-n-decyl-5- [4- (trans-4-n-propylcyclohexylmethyleneoxy) phenyl] -1,
Synthesis of 3,4-thiadiazole (Exemplified Compound B-3) 2-n-decyl-5- [4-hydroxyphenyl]-
1,3,4-oxadiazole 1.0 g (3.28 × 10 -3 mol) 20m
dissolved in 1 dimethylformamide. To this, 0.5 g of 85% potassium hydroxide was added and stirred at 100 ° C. for 1 hour. To this, 1.02 g (3.28 × 10 −3 mol) of trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate was added, and the mixture was further stirred at 100 ° C. for 4 hours. After completion of the reaction, this was poured into 200 ml of ice water, extracted with benzene, washed with water and dehydrated, and then the solvent was distilled off to obtain a crude product. This was purified by silica gel chromatography and further recrystallized from ethanol to give 0.8 g of 2-n-decyl-5- [4-
(Trans-4'-n-propylcyclohexylmethyleneoxy) -phenyl] -1,3,4-thiadiazole was obtained. (53.3% yield) IR (cm -1 ) 2945,2860,1608,1580,1520,1480,1460,1320,1260,1180,
1125,1040,985,858 Example 14 2- (1-methylpropyl) -5- [4- (trans-4-n-pentylcyclohexylcarbonyloxy)
-Phenyl] -1,3,4-thiadiazole (Exemplary Compound B-51) 0.3 g (1.28 × 10 −3 ) of 1-methylpropyl-5- [4-hydroxyphenyl] -1,3,4-thiadiazole mol), trans -4-n-pentyl cyclohexyl carboxylic acid 0.26 g (1.31 × 10 -3 mol) dicyclohexylcarbodiimide 0.27 g (1.31 × 10 -3 mol), 4- (1-pyrrolidinyl) pyridine 0.03g in methylene chloride 15ml And add
The mixture was stirred at room temperature for 20 hours. After completion of the reaction, the reaction solution was filtered and further washed with methylene chloride. After the filtrate and washings were dehydrated, the solvent was distilled off to obtain a crude product. This was recrystallized twice with ethanol to obtain 0.24 g of 2- (1-methylpropyl) -5- [4- (trans-4-n-pentylcyclohexylcarbonyloxy) -phenyl] -1,3,4-thiadiazole. I got (Yield 45.2%) Example 15 Among the specific examples of the liquid crystalline compound represented by the general formula (I) of the present invention (9) in the specific examples (group A), B-
And 7 were mixed at a ratio of 4: 1 to obtain a liquid crystal composition F. The ferroelectric liquid crystal compound (9) and the liquid crystal composition F were sandwiched between a pair of electrode substrates obtained by subjecting a rubbing treatment to a polyimide coating covering electrodes to prepare a liquid crystal element in the same manner as in Example 7. Using these liquid crystal elements, the response speed was measured by detecting the optical response under crossed Nicols by applying an electric field of peak-to-peak voltage of 20V. The results are shown below.
40℃ 25℃ 強誘電性液晶化合物（９） 400μｓ 610μｓ 液晶組成物Ｆ 320μｓ 435μｓ 以上のことから、強誘電性液晶化合物［具体例
（９）］に本発明の液晶性化合物［具体例Ｂ−７］を混
合することにより応答特性が向上することがわかった。40 ° C. 25 ° C. Ferroelectric liquid crystal compound (9) 400 μs 610 μs Liquid crystal composition F 320 μs 435 μs From the above, the liquid crystal compound of the present invention [specific example B-7] was added to the ferroelectric liquid crystal compound [specific example (9)]. ] Has been found to improve the response characteristics.
実施例16 前記具体例（Ａ群）のうち（１）と（38）を4:1の割
合で混合し、液晶組成物Ｂを得た。Example 16 A liquid crystal composition B was obtained by mixing (1) and (38) in the specific example (Group A) at a ratio of 4: 1.
次に、上記液晶組成物Ｂと、前記本発明の一般式
（Ｉ）で表わされる液晶性化合物の具体例のうちＢ−２
を9:1の割合で混合し、液晶組成物Ｇを得た。Next, among the above liquid crystal composition B and specific examples of the liquid crystal compound represented by the general formula (I) of the present invention, B-2
Were mixed at a ratio of 9: 1 to obtain a liquid crystal composition G.
上記液晶組成物Ｂと、液晶組成物Ｇを用い、実施例15
の場合と同様にそれぞれ液晶素子を作製した。これらの
液晶素子を用い、印加電圧を30Vにした他は、実施例15
と全く同様な方法で応答速度を測定した。下に結果を示
す。Example 15 was prepared using the liquid crystal composition B and the liquid crystal composition G.
Liquid crystal elements were produced in the same manner as in the above case. Example 15 except that these liquid crystal elements were used and the applied voltage was 30 V
The response speed was measured in the same manner as described above. The results are shown below.
35℃ 25℃ 液晶組成物Ｂ 685μｓ 1275μｓ 液晶組成物Ｇ 510μｓ 820μｓ 以上のことから、液晶組成物Ｂに、本発明の液晶性化
合物Ｂ−２を混合することにより、応答特性が向上する
ことがわかった。35 ° C. 25 ° C. Liquid crystal composition B 685 μs 1275 μs Liquid crystal composition G 510 μs 820 μs From the above results, it can be seen that the response characteristics are improved by mixing liquid crystal composition B with liquid crystal compound B-2 of the present invention. Was.
実施例17 実施例16で用いた液晶組成物Ｂと前記具体例（Ｂ群）
のうちと、本発明の一般式（Ｉ）で表わされる液晶性
化合物のうちＢ−３とB-34とを下記比率で混合して液晶
組成物Ｈを得た。Example 17 The liquid crystal composition B used in Example 16 and the specific examples (Group B)
Among them, B-3 and B-34 of the liquid crystal compound represented by the general formula (I) of the present invention were mixed at the following ratio to obtain a liquid crystal composition H.
液晶組成物Ｈ 液晶組成物B::B−3:B-34＝14:4:1:1 上記液晶組成物Ｈを用い実施例15と全く同じ条件で液
晶素子を作製し、全く同じ条件で応答速度を測定した。
下に結果を示す。Liquid crystal composition H Liquid crystal composition B :: B-3: B-34 = 14: 4: 1: 1 Using the above liquid crystal composition H, a liquid crystal element was produced under exactly the same conditions as in Example 15, and under exactly the same conditions. The response speed was measured.
The results are shown below.
35℃ 25℃ 液晶組成物Ｂ（実施例16） 685μｓ 1275μｓ 液晶組成物Ｈ 520μｓ 670μｓ 以上のことから、液晶組成物Ｂに、本発明の液晶性化
合物Ｂ−３とB-34と、他の液晶化合物とを組み合わせ
て混合することにより応答特性が向上することがわかっ
た。35 ° C. 25 ° C. Liquid crystal composition B (Example 16) 685 μs 1275 μs Liquid crystal composition H 520 μs 670 μs From the above, the liquid crystal composition B was added to the liquid crystal compounds B-3 and B-34 of the present invention and another liquid crystal. It was found that the response characteristics were improved by combining and mixing with the compound.
実施例18 Δεがほとんど０であるチツソ社製液晶CS1014［Δε
−0.4（sin波、100KHz）］と本発明の一般式（Ｉ）で
表わされる液晶性化合物の具体例のうちB-20を9:1の割
合で混合し液晶組成物Ｉを得た。上記CS1014と液晶組成
物Ｉを用い、液晶層厚を1.5μｍとした他は、実施例15
と全く同様な方法でそれぞれ液晶素子を作製した。Example 18 Liquid Crystal CS1014 [Δε manufactured by Chitso Corporation having Δε of almost 0
−0.4 (sine wave, 100 KHz)] and B-20 in a specific example of the liquid crystal compound represented by the general formula (I) of the present invention were mixed at a ratio of 9: 1 to obtain a liquid crystal composition I. Example 15 was repeated except that the liquid crystal layer thickness was 1.5 μm using CS1014 and the liquid crystal composition I.
Liquid crystal elements were produced in exactly the same manner as in the above.
上記液晶素子を用い、25℃において直交ニコル下でチ
ルト角を測定したところ、CS1014は７°、液晶組成物Ｉ
は8.2°であった。次に60KHzの周波数で±8Vの矩形波を
印加しながら、顕微鏡観察を行いチルト角を測定したと
ころ、CS1014は8.8°、液晶組成物Ｉは14.2°になっ
た。この時透過率を測定したところCS1014は7.8％、液
晶組成物は13％であった。またさらにコントラスト比を
測定したところCS1014は8:1、液晶組成物Ｉは40:1であ
った。Using the above liquid crystal device, the tilt angle was measured at 25 ° C. under crossed Nicols.
Was 8.2 °. Then, while applying a rectangular wave of ± 8 V at a frequency of 60 KHz, microscopic observation was performed and the tilt angle was measured. As a result, CS1014 was 8.8 ° and liquid crystal composition I was 14.2 °. At this time, when the transmittance was measured, it was 7.8% for CS1014 and 13% for the liquid crystal composition. Further, when the contrast ratio was further measured, CS1014 was 8: 1 and liquid crystal composition I was 40: 1.
以上のことからΔεがほとんど０であるCS1014に本発
明の一般式（Ｉ）で表わされる液晶性化合物B-20を混合
することにより得られた液晶素子はACスタビライズ効果
による表示特性が改善できることがわかった。From the above, it can be seen that the liquid crystal element obtained by mixing the liquid crystal compound B-20 represented by the general formula (I) of the present invention with CS1014 in which Δε is almost 0 can improve the display characteristics by the AC stabilization effect. all right.
実施例19 前記カイラルでないネマチツク相に添加することでら
せんを生ずる光学活性化合物の具体例（Ａ群）のうち、
（８），（13），（17），（18），（20），（33），
（34），（36），（38）を、またカイラルでないスメク
チツク相および（または）マネチツク相を有する液晶化
合物（Ｂ群）のうち、，，，，を下記比率で
混合して液晶組成物Ｊを得た。Example 19 Among the specific examples (Group A) of the optically active compound which generates a helix when added to the non-chiral nematic phase,
(8), (13), (17), (18), (20), (33),
(34), (36), and (38) are mixed with a liquid crystal compound (Group B) having a non-chiral smectic phase and / or a monetic phase in the following ratio to form a liquid crystal composition J I got
液晶組成物Ｊ （８）：（13）：（17）：（18）：（20）：（33）：
（34）：（36）：（38）：：：：：＝10:9:1
0:10:5:6:3:5:5:5:6:6:12:8 次に上記組成物Ｊと、前記本発明の一般式（Ｉ）で表
わされる液晶化合物の具体例のうち、Ａ−2,A−6,A-17,
A-23,A-26,B−3,B-21,B-33とを下記比率で混合して液晶
組成物Ｋを得た。Liquid crystal composition J (8): (13): (17): (18): (20): (33):
(34) :( 36) :( 38) ::::: = 10: 9: 1
0: 10: 5: 6: 3: 5: 5: 5: 6: 6: 12: 8 Next, among the specific examples of the composition J and the liquid crystal compound represented by the general formula (I) of the present invention, , A-2, A-6, A-17,
A-23, A-26, B-3, B-21, and B-33 were mixed at the following ratio to obtain a liquid crystal composition K.
液晶組成物Ｋ 液晶組成物J:A−2:A−6:A-17:A-23:A-26:B−3:B-21:B-3
3＝80:3:2:3:3:2:2:2:3 上記液晶組成物Ｊと液晶組成物Ｋを用い実施例７と全
く同様に液晶素子を作成した。この液晶素子を用いて、
印加電圧をピーク・トウ・ピーク35Vとした他は、全く
同様の条件で応答速度を測定した。結果を下に示す。Liquid crystal composition K Liquid crystal composition J: A-2: A-6: A-17: A-23: A-26: B-3: B-21: B-3
3 = 80: 3: 2: 3: 3: 2: 2: 2: 3 Using the above liquid crystal composition J and liquid crystal composition K, a liquid crystal element was produced in exactly the same manner as in Example 7. Using this liquid crystal element,
The response speed was measured under exactly the same conditions except that the applied voltage was 35 V peak-to-peak. The results are shown below.
10℃ 25℃ 40℃ 液晶組成物Ｊ 980μsec 358μsec 135μsec 液晶組成物Ｋ 900μsec 362μsec 137μsec 次に、これらの液晶素子を用い、実施例７と全く同じ
条件でチルト角を測定したところ（60KHz,±8V矩形波）
液晶組成物Ｊは8.3°、液晶組成物Ｋは13.8°になっ
た。10 ° C. 25 ° C. 40 ° C. Liquid crystal composition J 980 μsec 358 μsec 135 μsec Liquid crystal composition K 900 μsec 362 μsec 137 μsec Next, using these liquid crystal elements, the tilt angle was measured under exactly the same conditions as in Example 7 (60 KHz, ± 8 V rectangular). wave)
The liquid crystal composition J was 8.3 ° and the liquid crystal composition K was 13.8 °.
以上のことから液晶組成物Ｊに本発明の液晶化合物を
混合することにより、反応速度の温度依存性が改善さ
れ、さらにACスタビライズ効果による表示方法に用いる
場合、表示特性が改善されることがわかった。From the above, it can be seen that by mixing the liquid crystal compound of the present invention with the liquid crystal composition J, the temperature dependence of the reaction rate is improved, and further, the display characteristics are improved when the liquid crystal composition J is used for a display method using the AC stabilization effect. Was.
実施例20 実施例19で使用した液晶組成物Ｊに対して、前記本発
明の一般式（Ｉ）で表わされる液晶化合物の具体例のう
ち、A-10,A-20,A-25,A-31,A-32,B−2,B-17,B-34,B-41,B
-43を下記比率で混合して液晶組成物Ｌを得た。Example 20 With respect to the liquid crystal composition J used in Example 19, among the specific examples of the liquid crystal compound represented by the general formula (I) of the present invention, A-10, A-20, A-25, A -31, A-32, B-2, B-17, B-34, B-41, B
-43 were mixed in the following ratio to obtain a liquid crystal composition L.
液晶組成物Ｌ 液晶組成物J:A-10:A-20:A-25:A-31:A-32:B−2:B-17:B-3
4:B-41:B-43＝80:2:2:2:1:1:3:2:5:1:1 上記液晶組成物Ｌを用い実施例19と全く同様に液晶素
子を作成し、全く同様の条件で応答速度、チルト角を測
定した。結果を下に示す。Liquid crystal composition L Liquid crystal composition J: A-10: A-20: A-25: A-31: A-32: B-2: B-17: B-3
4: B-41: B-43 = 80: 2: 2: 2: 1: 1: 3: 2: 5: 1: 1 Using the above liquid crystal composition L, a liquid crystal element was prepared in exactly the same manner as in Example 19. The response speed and the tilt angle were measured under exactly the same conditions. The results are shown below.
応答速度 10℃ 25℃ 40℃ 945μsec 370μsec 139μsec チルト角 14.3° 以上のことから、液晶組成物Ｊに本発明の液晶化合物
を混合することにより、応答速度の温度依存性が改善さ
れ、さらにACスタビライズ効果による表示方法に用いる
場合、表示特性が改善されることがわかった。Response speed 10 ° C 25 ° C 40 ° C 945μsec 370μsec 139μsec Since the tilt angle is 14.3 ° or more, by mixing the liquid crystal compound of the present invention with the liquid crystal composition J, the temperature dependence of the response speed is improved, and the AC stabilizing effect is further improved. It was found that the display characteristics were improved when the method was used for the display method according to (1).
実施例21 前記具体例（Ａ群）のうち、（14），（21），（3
9），（107），（110）と、（Ｂ群）のうち，，
，，，を下記比率で混合して液晶組成物Ｍを得
た。Example 21 Among the specific examples (Group A), (14), (21), (3)
9), (107), (110) and (Group B)
,... Were mixed in the following ratio to obtain a liquid crystal composition M.
液晶組成物Ｍ （14）：（21）：（39）：（107）：（110）：：：
：：：＝8:2:9:5:3:15:10:10:15:3:20 次に、上記液晶組成物Ｍと前記一般式（Ｉ）で表わさ
れる液晶性化合物の具体例のうちＢ−６とを下記比率で
混合して液晶組成物Ｎを得た。Liquid crystal composition M (14): (21): (39): (107): (110) :::
::: == 8: 2: 9: 5: 3: 15: 10: 10: 15: 3: 20 Next, specific examples of the liquid crystal composition M and the liquid crystal compound represented by the general formula (I) will be described. Among them, B-6 was mixed at the following ratio to obtain a liquid crystal composition N.
液晶組成物Ｎ 液晶組成物M:B−６＝93:7 上記液晶組成物Ｍと液晶組成物Ｎを用いて実施例７と
同様にそれぞれ液晶素子を作製した。上記液晶素子を用
い、実施例７と全く同じ条件でチルト角を測定したとこ
ろ（60KHz,±8V矩形波）、液晶組成物Ｍは8.6°、液晶
組成物Ｎは12.8°になった。Liquid crystal composition N Liquid crystal composition M: B-6 = 93: 7 Using the above liquid crystal composition M and liquid crystal composition N, liquid crystal elements were produced in the same manner as in Example 7. When the tilt angle was measured using the above liquid crystal element under the same conditions as in Example 7 (60 KHz, ± 8 V rectangular wave), the liquid crystal composition M was 8.6 ° and the liquid crystal composition N was 12.8 °.
以上のことから。液晶組成物Ｍに、本発明の一般式
（Ｉ）で表わされる液晶性化合物Ｂ−６を混合すること
により得られた液晶組成物Ｎを用いた液晶素子は、ACス
タビライズ効果による表示特性が改善されることがわか
った。From the above. A liquid crystal device using the liquid crystal composition N obtained by mixing the liquid crystal composition M with the liquid crystal compound B-6 represented by the general formula (I) of the present invention has improved display characteristics due to the AC stabilization effect. It turned out to be.
実施例22 実施例21の液晶組成物Ｍと前記一般式（Ｉ）で表わさ
れる液晶性化合物の具体例のうちB-19とを9:1の比率で
混合して液晶組成物Ｏを得た。Example 22 A liquid crystal composition O was obtained by mixing the liquid crystal composition M of Example 21 and B-19 among the specific examples of the liquid crystal compound represented by the general formula (I) at a ratio of 9: 1. .
上記液晶組成物Ｏを用いて実施例７と同様の方法で液
晶素子を作製し、実施例７と全く同じ条件でチルト角を
測定した（60KHz,±8V矩形波）ところ14.2°になった。Using the above liquid crystal composition O, a liquid crystal device was produced in the same manner as in Example 7, and the tilt angle was measured under the same conditions as in Example 7 (60 KHz, ± 8 V rectangular wave). The result was 14.2 °.
実施例23 実施例21の液晶組成物Ｍと前記一般式（Ｉ）で表わさ
れる液晶性化合物の具体例のうちB-22,B-37,B-40とを下
記比率で混合して液晶組成物Ｐを得た。Example 23 A liquid crystal composition was prepared by mixing the liquid crystal composition M of Example 21 with B-22, B-37, and B-40 of the specific examples of the liquid crystal compound represented by the general formula (I) at the following ratio. The product P was obtained.
液晶組成物Ｐ 液晶組成物M:B-22:B-37:B-40＝90:6:2:2 上記液晶組成物Ｐを用いて実施例７と同様の方法で液
晶素子を作製し、実施例７と全く同じ条件（60KHz,±8V
矩形波）でチルト角を測定したところ、13.7°になっ
た。Liquid crystal composition P Liquid crystal composition M: B-22: B-37: B-40 = 90: 6: 2: 2 Using the above liquid crystal composition P, a liquid crystal device was produced in the same manner as in Example 7, Exactly the same conditions as in Example 7 (60 KHz, ± 8 V
When the tilt angle was measured with a square wave), it was 13.7 °.
実施例24 前記具体例（Ａ群）のうち、（30），（40），（10
6）と、前記液晶化合物（Ｂ群）のうち，，，
，，，，を下記比率で混合して液晶組成物Ｑ
を得た。Example 24 Among the specific examples (Group A), (30), (40), (10)
6) and, among the liquid crystal compounds (Group B),
,,, Are mixed in the following ratio to obtain a liquid crystal composition Q
I got
液晶組成物Ｑ （30）：（40）：（106）：：：：：：：
：＝3:4:3:7:12:9:15:12:18:8:9 次に、上記液晶組成物Ｑと前記本発明の一般式（Ｉ）
で表わされる液晶性化合物の具体例のうちＢ−3,B-15,B
-21,B-23,B-33とを下記比率で混合して液晶組成物Ｒを
得た。Liquid crystal composition Q (30) :( 40) :( 106) ::::::::
: = 3: 4: 3: 7: 12: 9: 15: 12: 18: 8: 9 Next, the liquid crystal composition Q and the general formula (I) of the present invention are described.
Among the specific examples of the liquid crystal compound represented by B-3, B-15, B
-21, B-23 and B-33 were mixed at the following ratio to obtain a liquid crystal composition R.
液晶組成物Ｒ 液晶組成物Q:B−3:B-15:B-21:B-23:B-33＝90:2:2:2:3:1 上記液晶組成物Ｑと液晶組成物Ｒを用い実施例７の場
合と同様にそれぞれ液晶素子を作製した。これらの液晶
素子を用い、実施例７と全く同じ条件で応答速度を測定
した。下に結果を示す。Liquid crystal composition R Liquid crystal composition Q: B-3: B-15: B-21: B-23: B-33 = 90: 2: 2: 2: 3: 1 The above liquid crystal composition Q and liquid crystal composition R And liquid crystal elements were produced in the same manner as in Example 7. Using these liquid crystal elements, the response speed was measured under exactly the same conditions as in Example 7. The results are shown below.
35℃ 25℃ 15℃ 液晶組成物Ｑ 93μｓ 160μｓ 290μｓ 液晶組成物Ｒ 110μｓ 170μｓ 305μｓ 次に、これらの液晶素子を用い、実施例７と全く同じ
条件でチルト角を測定したところ（60KHz,±8V矩形
波）、液晶組成物Ｑは8.2°、液晶組成物Ｒは13.4°に
なった。35 ° C. 25 ° C. 15 ° C. Liquid crystal composition Q 93 μs 160 μs 290 μs Liquid crystal composition R 110 μs 170 μs 305 μs Next, using these liquid crystal elements, the tilt angle was measured under exactly the same conditions as in Example 7 (60 KHz, ± 8 V rectangular). Wave), the liquid crystal composition Q was 8.2 °, and the liquid crystal composition R was 13.4 °.
以上のことから、液晶組成物Ｑに本発明の液晶化合物
を混合した液晶組成物Ｒは応答特性の温度依存性が改善
され、さらに、ACスタビライズ効果による表示方法に用
いる場合、表示特性が大幅に改善されることがわかっ
た。From the above, the liquid crystal composition R in which the liquid crystal compound Q is mixed with the liquid crystal compound of the present invention has improved temperature dependence of the response characteristics, and further, when used for a display method by the AC stabilization effect, the display characteristics are significantly reduced. It was found to be improved.
実施例25 前記光学活性化合物の具体例（Ａ群）のうち、
（６），（８），（26），（31），（33），（34），
（39），（50），（92），（116）と、液晶化合物（Ｂ
群）のうち、，，，，を下記比率で混合して
液晶組成物Ｓを得た。Example 25 Among the specific examples (Group A) of the optically active compound,
(6), (8), (26), (31), (33), (34),
(39), (50), (92), (116) and the liquid crystal compound (B
) Was mixed at the following ratio to obtain a liquid crystal composition S.
液晶組成物Ｓ （６）：（８）：（26）：（31）：（33）：（34）：
（39）：（50）：（92）：（116）：：：：：
＝5:6:4:8:3:7:20:10:2:5:3:4:3:14:6 次に、上記液晶組成物Ｓと前記本発明の一般式（Ｉ）
で表わされる液晶性化合物の具体例のうちＢ−5,B-17,B
-31,B-36とを下記比率で混合して液晶組成物Ｔを得た。Liquid crystal composition S (6): (8): (26): (31): (33): (34):
(39) :( 50) :( 92) :( 116) :::::
= 5: 6: 4: 8: 3: 7: 20: 10: 2: 5: 3: 4: 3: 14: 6 Next, the liquid crystal composition S and the general formula (I) of the present invention
Among the specific examples of the liquid crystal compound represented by B-5, B-17, B
-31 and B-36 were mixed at the following ratio to obtain a liquid crystal composition T.
液晶組成物Ｔ 液晶組成物S:5:17:31:36＝85:3:2:4:6 上記液晶組成物Ｓと液晶組成物Ｔを用い、セル厚を1.
3μｍとした他は実施例７と同様に液晶素子を作製し
た。これらの液晶素子を用い、印加電圧をピークトウピ
ーク40Vとした他は、同様の条件で応答速度を測定し
た。下に結果を示す。Liquid crystal composition T Liquid crystal composition S: 5: 17: 31: 36 = 85: 3: 2: 4: 6 Using the above liquid crystal composition S and liquid crystal composition T, the cell thickness was 1.
A liquid crystal element was produced in the same manner as in Example 7, except that the thickness was 3 μm. Using these liquid crystal devices, the response speed was measured under the same conditions except that the applied voltage was set to a peak-to-peak of 40 V. The results are shown below.
35℃ 25℃ 15℃ 液晶組成物Ｓ 75μｓ 175μｓ 330μｓ 液晶組成物Ｔ 70μｓ 150μｓ 285μｓ 次に、これらの液晶素子を用い、実施例７と全く同じ
条件でチルト角を測定したところ（60KHz,±8V矩形
波）、液晶組成物Ｓは14.6°、液晶組成物Ｔは15.9°に
なった。35 ° C. 25 ° C. 15 ° C. Liquid crystal composition S 75 μs 175 μs 330 μs Liquid crystal composition T 70 μs 150 μs 285 μs Next, using these liquid crystal elements, the tilt angle was measured under exactly the same conditions as in Example 7 (60 KHz, ± 8 V rectangular). Wave), the liquid crystal composition S was 14.6 °, and the liquid crystal composition T was 15.9 °.
以上のことから、液晶組成物Ｓに本発明の液晶化合物
を混合することにより、応答速度およびその温度依存性
が改善され、さらに、ACスタビライズ効果による表示方
法に用いる場合、表示特性が改善されることがわかっ
た。From the above, by mixing the liquid crystal compound of the present invention into the liquid crystal composition S, the response speed and its temperature dependency are improved, and further, when used in a display method by the AC stabilization effect, the display characteristics are improved. I understand.
以上の実施例からわかるように、本発明の一般式
（Ｉ）で表わされるACスタビライズ効果を生じさせるた
めに充分なΔεを有する液晶組成物を与えるような液晶
性化合物を用いる液晶組成物および液晶素子は、応答特
性が良く、またACスタビライズ効果による表示方法に用
いる場合、表示特性が大幅に改善されることがわかっ
た。As can be seen from the above examples, a liquid crystal composition and a liquid crystal using a liquid crystal compound that provides a liquid crystal composition having a sufficient Δε to produce the AC stabilizing effect represented by the general formula (I) of the present invention. It has been found that the element has good response characteristics, and the display characteristics are significantly improved when used in a display method using the AC stabilization effect.
第１図はΔεの値の異なるFLCのVrmsに対するθａの変
化を示す。FIG. 1 shows the change of θa with respect to Vrms of FLCs having different values of Δε.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 滝口 隆雄 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (72)発明者 北山 宏之 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (72)発明者 片桐 一春 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (56)参考文献 特開 昭64−−61472（ＪＰ，Ａ) 特開 平２−500191（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing on the front page (72) Takao Takiguchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Hiroyuki Kitayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Kazuaki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-64-61472 (JP, A) JP-A-2-500191 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) REGISTRY (STN) CA (STN)
Claims (1)
Ｙは酸素または硫黄を示す。R1及びR2は置換基を有して
もよい炭素数１〜18の直鎖状または分岐状のアルキル
基、アルコキシ基、アルキルカルボニルオキシ基、アル
キルオキシカルボニル基、またはアルキルオキシカルボ
ニルオキシ基を示し、この場合置換基は塩素、臭素、シ
アノ基、アルコキシ基、あるいはアルキルオキシカルボ
ニル基を示す。また、Ｂは を示す。］ で表される化合物を少なくとも１種含むACスタビライズ
効果を生じさせるために充分な負のΔεを有する液晶組
成物を、一対の基板間に配置してなり、ACスタビライズ
効果を生じさせるようなACを印加する手段を有する強誘
電性液晶素子。1. A compound represented by the following general formula (I) [In the above general formula, A 1 is a single bond, Is shown. X represents hydrogen, halogen or a cyano group,
Y represents oxygen or sulfur. R 1 and R 2 may have a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkoxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, or an alkyloxycarbonyloxy group. In this case, the substituent represents chlorine, bromine, a cyano group, an alkoxy group, or an alkyloxycarbonyl group. B is Is shown. A liquid crystal composition having a negative Δε sufficient to produce an AC stabilizing effect containing at least one compound represented by formula (1) is disposed between a pair of substrates, and the AC stabilizing effect is produced. A ferroelectric liquid crystal device having a means for applying a voltage.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/329,316 US5034151A (en) | 1988-03-28 | 1989-03-27 | Mesomorphic compound, ferroelectric liquid crystal composition containing same and ferroelectric liquid crystal device |
| DE68925987T DE68925987T3 (en) | 1988-03-28 | 1989-03-28 | Mesomorphic compound, ferroelectric liquid crystal composition containing it, and ferroelectric liquid crystal device |
| EP89105489A EP0335348B2 (en) | 1988-03-28 | 1989-03-28 | Mesomorphic compound, ferroelectric liquid crystal composition containing same and ferroelectric liquid crystal device |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-75078 | 1988-03-28 | ||
| JP7507888 | 1988-03-28 | ||
| JP15767588 | 1988-06-24 | ||
| JP63-157675 | 1988-06-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02275868A JPH02275868A (en) | 1990-11-09 |
| JP2872260B2 true JP2872260B2 (en) | 1999-03-17 |
Family
ID=26416224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1064775A Expired - Fee Related JP2872260B2 (en) | 1988-03-28 | 1989-03-15 | Ferroelectric liquid crystal device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2872260B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730859A1 (en) * | 1987-04-16 | 1989-03-30 | Merck Patent Gmbh | THIAZOL AND THIADIAZOL DERIVATIVES WITH SMEKTIC LIQUID CRYSTALLINE PHASE |
| DE3819972C2 (en) * | 1987-07-01 | 1997-04-10 | Samsung Electronic Devices | 2,5-disubstituted 1,3,4-thiadiazoles with extended smectic C phases and use in liquid crystalline mixtures |
-
1989
- 1989-03-15 JP JP1064775A patent/JP2872260B2/en not_active Expired - Fee Related
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