JPH0243282A - Liquid crystal composition and liquid crystal element made by using it - Google Patents

Abstract

PURPOSE:To obtain a chiral smectic liquid crystal composition which has a high speed of response and such a wide drive temperature margin that good matrix drive of all picture elements can be realized even if there is some temperature variation on the display area of an element by mixing three kinds of specified liquid crystal compounds together. CONSTITUTION:A ferroelectric chiral smectic liquid crystal composition is prepared by mixing a compound (A) of formula I [wherein R1 is (substituted) 1-18C alkyl; R2 is (substituted) 1-14C alkyl; X1 and X2 are each a single bond, -O-, a group of formula II, etc.; m is 0 to 7; n is 0 or 1]; a compound (B) of formula III [wherein R3 and R4 are each (substituted) 1-18C alkyl; X3 and X4 are each a single bond, a group of formula IV, etc.; Z1 is a group of formula IV, -OCH2-, a single bond, etc.; groups of formula V and formula VI are each a group of, e.g., formula VII or VIII, and a group of formula IX is a group of formula VII or X, provided that at least one of the groups of formulas V, VI and IX is a group of formula X or VIII]; and a compound (C) of formula XI [wherein R5 and R6 are each (substituted) 1-18C alkyl, at least one of which is optically active; X5 is a single bond, -O-, a group of formula II, etc.; X6 is a single bond, -O-, a group of formula II, etc.].

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a liquid crystal composition used for liquid crystal elements used in liquid crystal display elements, liquid crystal light shutters, etc. The present invention relates to a novel liquid crystal composition and a liquid crystal element using the same.

[Prior Art] Liquid crystals have conventionally been applied as electro-optical elements in various fields. Most of the liquid crystal elements currently in practical use are, for example, M-Shut (M.

5chad t) and W Helfrich (W, 1l
elfrich) “Applied Physics Letters”
ters”) Vo, 18. No, 4 (
1971, 2, 15) P, 127-128 “V
oltage Dependent Optical
Activity of a Twisted Nem
It uses a TN (Twisted Nematic) type liquid crystal shown in ``Atic 1iquid (:rysta+'').

These are based on the dielectric alignment effect of liquid crystals, and utilize the effect that the average molecular axis direction is oriented in a specific direction due to the dielectric anisotropy of liquid crystal molecules due to an applied electric field. The optical response speed limit of these devices is said to be milliseconds, which is too slow for many applications. On the other hand, for application to large flat displays, driving by a simple matrix method is the most promising in terms of cost, productivity, etc. In the simple matrix method, an electrode configuration in which a scanning electrode group and a signal electrode group are arranged in a matrix is adopted, and in order to drive the electrode group, an address signal is selectively and periodically applied to the scanning electrode group, and the signal electrode group is A time division driving method is adopted in which a predetermined information signal is selectively applied in parallel in synchronization with an address signal.

However, when the above-mentioned TN type liquid crystal is adopted as an element of such a driving method, there is a region where the scanning electrode is selected and the signal electrode is not selected, or a region where the scanning electrode is not selected and the signal electrode is selected (so-called " A finite electric field is also applied to the half-selected point.

If the difference between the voltage applied to the selected point and the voltage applied to the half-selected point is sufficiently large, and the voltage threshold required to align the liquid crystal molecules perpendicular to the electric field is set to an intermediate voltage value,
Although the display element operates normally, the number of scanning lines (N
), the time during which an effective electric field is applied to one selected point (duty ratio) while scanning the entire screen (1 frame) decreases at a rate of 1/H.

For this reason, when repeated scanning is performed, the effective voltage difference between selected points and non-selected points becomes smaller as the number of scanning lines increases, resulting in a decrease in image contrast and crosstalk. This is a drawback that is difficult to avoid.

This phenomenon is caused by liquid crystals that do not have bistability (the stable state is when the liquid crystal molecules are aligned horizontally with respect to the electrode surface, and they are aligned vertically only while an electric field is effectively applied). )
This is essentially an unavoidable problem that arises when driving using the temporal accumulation effect (that is, repeatedly scanning).

In order to improve this point, voltage averaging method, dual-frequency driving method, multiple matrix method, etc. have already been proposed, but all of these methods are insufficient, and it is necessary to increase the screen size and density of display elements. Currently, the number of scanning lines has reached a plateau due to the inability to increase the number of scanning lines sufficiently.

The use of a bistable liquid crystal element is one way to improve these drawbacks of conventional liquid crystal elements.

Clark (C1ark) and Sigawell (Lager)
wall) (Japanese Patent Application Laid-open No. 107-1983)
No. 216, U.S. Patent No. 4,367,924, etc.)
.

As the bistable liquid crystal, a ferroelectric liquid crystal having a chiral smectic C phase (S■c'' phase) or H phase (S■H'' phase) is generally used.

This ferroelectric liquid crystal has a bistable state consisting of a first optically stable state and a second optically stable state in response to an electric field, and therefore is different from the optical modulation element used in the above-mentioned TN type liquid crystal. Differently, for example, the liquid crystal is oriented in a first optically stable state with respect to one electric field vector, and the liquid crystal is oriented in a second optically stable state with respect to the other electric field vector. Also,
This type of liquid crystal has a property (bistability) of taking one of the above two stable states in response to an applied electric field and maintaining that state when no electric field is applied.

In addition to the above-mentioned feature of bistability, ferroelectric liquid crystals have the excellent feature of high-speed response, which is due to the direct interaction between the spontaneous polarization of ferroelectric liquid crystals and the applied electric field. The response speed is 3 to 4 orders of magnitude faster than the response speed due to the 1M electric anisotropy and the action of the electric field.

In this way, ferroelectric liquid crystals potentially have extremely excellent properties, and by utilizing these properties, many of the problems of conventional TN-type devices mentioned above can be solved, which is quite essential. Improvement can be obtained. In particular, it is expected to be applied to high-speed optical shutters and high-density, large-screen displays. For this reason, extensive research has been conducted on liquid crystal materials with ferroelectric properties, but the ferroelectric liquid crystal materials developed to date have sufficient characteristics for use in liquid crystal devices, including low-temperature operation characteristics and high-speed response. It is difficult to say that it is equipped with the following.

There exists a relationship between the response time τ, the magnitude of spontaneous polarization Ps, and the viscosity η as expressed by the following formula % (where E is the applied voltage). Therefore, to increase response speed.

(a) Increase the magnitude of spontaneous polarization Ps (b) Viscosity η
There is a method of increasing the applied voltage E to reduce the . The applied electric field has an upper limit because it is driven by an IC or the like, and it is desirable that it be as low as possible.

Therefore, it is actually necessary to reduce the viscosity η or increase the value of the spontaneous polarization Ps.

In general, in ferroelectric chiral smectic liquid crystal compounds with large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is large, and there tends to be more restrictions on device configurations that can take a bistable state.

Moreover, even if the spontaneous polarization is increased unnecessarily, the viscosity tends to increase accordingly, and as a result, it is conceivable that the response speed will not become very fast.

In addition, when the actual operating temperature range for a display is set to, for example, 5 to 40°C, the response speed generally changes by about 20 times, which is currently beyond the limits of adjustment by drive voltage and frequency. It is.

In the case of a simple matrix display device as described above using an element in which this ferroelectric liquid crystal layer is sandwiched between a pair of substrates, for example, Japanese Patent Laid-Open Nos. 59-193426 and 60 Nos.
Driving methods disclosed in Japanese Patent Laid-open No. 156046-156046, Japanese Patent Application Laid-Open No. 60-156047, etc. can be applied.

FIG. 4 is a waveform diagram of the driving method used in the embodiment of the present invention. Moreover, FIG. 5 is a plan view of a ferroelectric liquid crystal panel 5I in which matrix electrodes used in the present invention are arranged. Fifth
In the ferroelectric liquid crystal panel 51 shown in the figure, a scanning line 52 and a data line 53 are wired to cross each other, and a ferroelectric liquid crystal is arranged between the scanning line 52 and the data line 53 at the intersection. ing.

85 in FIG. 4(A) is the selection scanning waveform applied to the selected scanning line, SH is the unselected scanning waveform that is not selected, and 5 is the selection information waveform applied to the selected data line ( io represents a non-selection information signal (white) applied to an unselected data line. Also, in the figure (Is
Ss) and (IN-SS) are the voltage waveforms applied to the pixels on the selected scanning line, and the pixels to which the voltage (Is Ss) is applied display black, and the pixels to which the voltage (+--SS) is applied The pixel that has been displayed has a white display state.

FIG. 4(B) is a time series waveform when the display shown in FIG. 6 is performed using the drive waveform shown in FIG. 4(A).

In the driving example shown in FIG. 4, the minimum application time Δt of the unipolar voltage applied to the pixels on the selected scanning line corresponds to the time of the write phase t2, and the time of the line clear t1 phase is set to 2Δt. has been done.

Now, each parameter Vs of the drive waveform shown in FIG.
The values of V□ and Δt are determined by the switching characteristics of the liquid crystal material used.

FIG. 7 shows the change in transmittance T, that is, the VT characteristic, when the driving voltage (Vs+vl) is changed while keeping the bias ratio, which will be described later, constant. here,
Δt=50ps, bias ratio v+/ (v, +vs)
= fixed at 1/3. The waveform (IN-s) shown in FIG. 4 is applied to the positive side of FIG. 7, and the waveform shown (Is Ss) to the negative side.

Here, V□+V3 are called the actual drive threshold voltage and crosstalk voltage, respectively, provided that Vx<Vt< V3
) Also, Δv = (V3-Vl) is called a drive voltage margin, and is a voltage width that allows matrix drive. v3 is FCC
It can be said that it generally exists due to the matrix drive of
Specifically, this is the voltage value that causes switching due to vQ in the waveform of FIG. 4(A) (IN-3S). Of course, it is possible to increase the value of Vco by increasing the bias ratio, but increasing the bias ratio means increasing the amplitude of the information signal, which may lead to an increase in flickering in terms of image quality. , which is undesirable because it causes a decrease in contrast.

According to our study, a bias ratio of about 1/3 to 1/4 is practical. By the way, if the bias ratio is fixed, the voltage margin ΔV strongly depends on the switching characteristics of the liquid crystal material, and it goes without saying that a liquid crystal material with a large ΔV is very advantageous for 7-trix driving.

At a certain temperature like this, it is possible to write two states, "black" and "white", into the selected pixel depending on the two directions of the information signal, and unselected pixels can write the "black" or "white" state into the selected pixel. It is possible to maintain the state of The upper and lower limits of the applied voltage and their widths (driving voltage margin ΔV) differ among liquid crystal materials and are unique. Further, the drive margin also changes due to changes in the environmental temperature, so in the case of an actual display device, it is necessary to set the drive voltage to the optimum value for the liquid crystal material and the environmental temperature.

However, when the display area of such a matrix display device is expanded in practice, the difference in the environment in which the liquid crystal exists in each pixel (specifically, the difference in temperature and cell gap between electrodes) naturally increases. If a liquid crystal has a small drive voltage margin, it will not be possible to obtain a good image over the entire display area.

[Problems to be Solved by the Invention] An object of the present invention is to improve the speed of response of a ferroelectric liquid crystal device, reduce its temperature dependence, or expand the driving voltage margin, so that a ferroelectric liquid crystal device can be put to practical use. An object of the present invention is to provide a chiral smectic liquid crystal composition with a wide driving temperature margin capable of satisfactorily driving all pixels in a matrix even if there is a certain degree of temperature variation in a display area, and a liquid crystal element using the liquid crystal composition.

[Means for Solving the Problems] That is, the present invention provides the following general formula (I) (I) (wherein R3 is C1 to C+a which may have a substituent)
a linear or branched alkyl group, R2 is a C1 to C14 linear or branched alkyl group which may have a substituent, XI, X2 is a single bond *-0-e or l ) with at least one compound represented by

The following general formula (■) R3-X xa Z I+ X 4- R4 (II)
(In the formula, R3 and R4 are C1 which may have a substituent
~C16 linear or branched alkyl group, X3.
X4-C11□O-, -OCH,-, single bond, →Y,
At least one of the compounds represented by the following general formula (I
II) (In the formula, R5 and R6 are C8-C which may have a substituent)
C1a is a linear or branched alkyl group, and at least one of them is optically active.

A ferroelectric chiral smectic liquid crystal composition containing at least one of the compounds represented by
The present invention also provides a liquid crystal element in which the ferroelectric chiral smectic liquid crystal composition is disposed between a pair of electrode substrates.

The present invention will be explained in detail below.

X in the compound represented by the aforementioned general formula (I),
As preferable examples of X2, (I-1) to (I
-vi).

(I-i) L is a single bond x2 is 10-(I-
n) X+ is a single bond x2 is 10C- (I-0i) Xt is a single bond
L is -0-x2 is -0C-■ (I-vi)
is a straight-chain alkyl group with CI=C14.

Further, in the compound represented by the above general formula (n),
Preferred compound examples include (II-a) to (
Compounds represented by the formula II-q) can be mentioned.

R3-X3+Φ)-co heart X, -R.

crystal R1-X3W QC+ X5-Rs R3-X33 cu2o → needle X4-R4R3-X 3W
OCIf! + X 4- R4R3-X1+◎4X
4-R4 Rs-Xi9(,0+ X4-R4 n, -x3斗会0C(E)-X,-R.

R3-X31. +CLO+X--R4(n-g) (■-h) (II-1) (II-j) (■-k) (II-1) (■-proverb) (U　-n) Furthermore, the above (U-a) As a preferable example of X, , X, -vi).

(H-r) X3 is a single bond (II-i) X:+ is a single bond (II-m) X:+ is -0-(II-iv)
X3 is -〇- (■-V) ) ~ (■ x4 is a single bond x4 is -〇- x4 is a single bond x4 is -0- x4 is a single bond x4 is -〇- x4 is a single bond (II-vi) L is -CO-X4 is -〇-Also, R in the above formulas (■-a) to (H-q)
,, A preferred example of R4 is that R,, R, is a linear alkyl group.

Moreover, X5 in the compound represented by the above general formula (m)
．． A preferred example of X6 is:

Further, as more preferable examples of Rs and R6, the following (
It is possible to list m-i) to (m-v).

RS is an n-alkyl group R6 → publication 1 (2hrCH-Rt R% or +-cH2 sho "CH-R8 R6 is an n-alkyl group N%a1-t-i ■, force i L; N-H♂t
taρ)-fit12 Su7- U N -H? (m
-+v) R5 is -HH*h-CH-(CHthrOR*.

R6 is n-alkyl group R? ~ R1° is a linear or branched alkyl group, p.

q.

".

t is O~7, S.

U indicates 0 or l vinegar.

next, The above general formula Ingredients of the compound shown in An example of a heavy structural formula is shown below.

A typical synthesis example of the compound represented by the general formula (I) is shown below.

Synthesis Example 1 (Synthesis of Compound No. 1-20) Pyridine 5-
1! 1.06 g of 5-methoxyhexanol dissolved in
(8,0 mmoj)) dissolved in 5 ml of pyridine
-Toluenesulfonic acid chloride 1.83g (9,6
1 moR) was added dropwise at below 5°C in an ice water bath. 6 at room temperature
After stirring for an hour, the reaction mixture was poured into 100 mj' with cold water. After making the mixture acidic with 6N hydrochloric acid, the mixture was extracted with isopropyl ether. After washing the organic layer with water, it was dried over anhydrous magnesium sulfate, and then the solvent was distilled off to give 5-methoxyhexyl-
p-Toluenesulfonate was obtained.

Dimethylformamide 10-2 and 5-decifury 2-(
p-hydroxyphenyl)pyrimidine 2.0g (6,4
1s oR), add 0.61g of potassium hydroxide,
Stirred at 0°C for 40 minutes. To this, the previously obtained 5-methoxyhexyl-1)-toluenesulfonate was added, and 10
After the completion of the reaction, which was heated and stirred at 0° C. for 4 hours, the reaction mixture was poured into cold water (100 mj) and extracted with benzene.

After washing with water, it was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a pale yellow oil. Column chromatography (
After purification using silica gel - ethyl acetate/benzene = 1/9), recrystallization from hexane was performed to obtain 5-decyl-2-(4
1.35 g of -(5'-methoxyhexyloxy)phenyl)pyrimidine (compound No. 1-20) was obtained.

Phase transition temperature (°C) Synthesis Example 2 (Synthesis of Compound No. 1-25) 2.04 g of 6-pentyloxyheptanol was dissolved in pyridine 8- and cooled on ice, and then tosyl chloride 2 dissolved in pyridine 5 .26g was gradually dropped (below 5°C, 7 minutes),
Thereafter, the mixture was stirred at room temperature for 5 hours.

The reaction mixture was poured into ice water (150 mj), adjusted to pH approximately 3 with 6N aqueous hydrochloric acid solution, and then extracted with ethyl acetate.

After washing this with water and drying it with anhydrous magnesium sulfate,
The solvent was distilled off to obtain 2.98 g of (6-pentyloxyheptyl)-p-toluenesulfonate.

3.12 g of 5-n-decyl-2-(4-hydroxyphenyl) and 0.53 g of potassium hydroxide were dissolved in 14 P of dimethylformamide, heated and stirred at 100°C for 3 hours, and then (6-pentyloxy heptyl)
Add 2.98 g of p-toluenesulfonate, 10
The mixture was heated and stirred at 0°C for 5 hours.

The reaction mixture was poured into ice water (200+*j), adjusted to pH approximately 3 with a 6N aqueous hydrochloric acid solution, and then extracted with benzene.

This was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 4.71 g of a crude product. After this was purified by silica gel column chromatography (developing solution: n-hexane/ethyl acetate = IO/2), it was recrystallized from hexane and converted to 5-n-decyl-2-(4-(6-pentyloxy). 1.56 g of butyloxy)phenyl)pyrimidine was obtained.

(cm-') Synthetic route B 2924.2852, 1610, 1586, 1472°14:16.1254.1168, 1096. 798
Phase transition temperature ("C) For compounds other than the synthesis side, the following synthetic routes A and H
It can be obtained by

Synthetic route A x.

(In the above formula, R1° means the same thing.) Next, examples of specific structural formulas of the compound represented by the general formula (TI) are shown below.

R2゜n is the same as above υ (2-as) υ c, +-+, +CHaOM OC+oHz+\(2-1
31) Cs H+ r+C1120zu) (Sawa OC+J2sCs
No. 801 CH2OW 0C14H29CbH+++CH
2OM Sawa O→C1l□→-C611,.

C5H,'') c++, o3 Ca1ll yCaII
r t+CHz03 C14H29C3H? +c H2
O()(sawaC6Hl3Cyama+C11□0()(sawaoc,
. H2□C3Ht+CIItOW Cal (l 7C
sHt+C)! 20 W CtJtsC,H,-()C
) 120th edition (Sawa(:al(ttCs80 issue 0C11□
) (SawaOCr*H25) A typical synthesis example of the compound represented by the above general formula (II) is described below.

Synthesis Example 1 (Synthesis of Compound No. 2-65) 5-dodecyl-2-(4'-hydroxyphenyl)pyrimidine 1. O
g (2.94 mmoff) was dissolved in 4 mj) of toluene and 4 ml of pyridine. To this, 0.55 g of trans-4-n-propylcyclohexanecarboxylic acid chloride (manufactured by Kanto Kagaku ■) dissolved in 4 arl of toluene was gradually added dropwise at 5° C. or lower in an ice water bath. After dropping, leave at room temperature for 12 hours.
After stirring for an hour, the reaction mixture was poured into 10 hf of ice water.

The mixture was made acidic with 6N hydrochloric acid, extracted with benzene, and washed successively with water, a 5% aqueous sodium bicarbonate solution, and water. After drying with magnesium sulfate, the solvent was distilled off to obtain a cream-colored crude product. After purifying this by column chromatography, it was further recrystallized from a mixed solvent of ethanol/ethyl acetate, yielding 0.94 g of the white title compound.
I got it. (Yield 64.8%) Phase transition temperature (°C) Synthesis Example 2 (Synthesis of Compound No. 2-133) (I) 10 g of trans-4-n-propylcyclohexanecarboxylic acid chloride (5:1.6 layer Layer 0Il) was dissolved in ethanol]Omi', a small amount of triethylamine was added thereto, and the mixture was stirred at room temperature for 10 hours.
After adding 6N hydrochloric acid aqueous solution to make the mixture acidic, the mixture was extracted with isopropyl ether. The organic layer was washed with water repeatedly until the washing solution became neutral, and then dried with magnesium sulfate. After distilling off the solvent, it was purified by silica gel column chromatography to obtain trans-4-n-propylcyclohexanecarboxylic acid ethyl ester9.9
I got g.

(■) Lithium aluminum hydride 0.73g (19
, 1 smol was added to dry ether: 10 ml),
The mixture was heated under reflux for 1 hour. After cooling to about 10°C in an ice water bath, trans-4 dissolved in 30 cm of dry ether was added.
-n-propylcyclohexanecarboxylic acid ethyl ester (5 g (25,5 mmoj)) was gradually added dropwise.
After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and further heated under reflux for 1 hour. This was treated with ethyl acetate and a 6N aqueous hydrochloric acid solution, and then poured into 200 si' of ice water.

After extraction with isopropyl ether, the organic phase was extracted with water,
It was washed successively with an aqueous sodium hydroxide solution and water, and dried over magnesium sulfate. After distilling off the solvent, it was purified by silica gel column chromatography to obtain trans-4-n-
3.5 g of propylcyclohexylmethanol was obtained.

(■) 3.4 g of trans-4-n-propylcyclohexylmethanol (22,4s oj') was dissolved in 20mj of pyridine. 20 yen of pyridine for this! 5.3 g of p-to-J reninsulfonic acid chloride dissolved in the solution was added dropwise while cooling to below 5° C. in an ice water bath. 10 at room temperature
After stirring for an hour, the mixture was poured into 200 ml of ice water. The mixture was made acidic with a 6N aqueous hydrochloric acid solution, and then extracted with isopropyl ether. The organic phase was washed with water repeatedly until the washing liquid became neutral, and then dried with magnesium sulfate. The solvent was distilled off to obtain trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate.

(TV) dimethylformamide-2-(4'-hydroxyphenyl)pyrimidine 6,
3 g (20.2 mmoJ) was dissolved. To this was added 1.5 g of 85% potassium hydroxide, and the mixture was stirred at ion°C't' for 1 hour. To this was added 6.9 g of trans-4-n-propylcyclohexylmethyl-11-)-luenesulfonate.
was added and further stirred at 100°C for 4 hours. After the reaction was completed, the mixture was poured into 200 ml of ice water and extracted with benzene. After washing the organic phase with water, it was dried with magnesium sulfate. After distilling off the solvent, it was purified by silica gel column chromatography, and further recrystallized from a mixed solvent of ethanol/ethyl acetate to obtain the above-mentioned Exemplified Compound No. 2-1
I got 33.

IR (cm-') 2920, 284G, 1608, 1584, 1
428. 125B.

1164, 800 Phase transition temperature (°C) (Sm2 is a smectic phase other than SmA and Sac, unidentified) In addition, when zl is a single bond, the compound represented by the formula, for example, can be synthesized by the following synthetic route. Can be done.

~■ H0 (R3゜ R4 means the same as above) next, The general formula (m) Compounds shown in An example of a heavy structural formula is shown below.

vinegar υ The general formula (m) The compound represented by for example It can be obtained by synthetic routes.

(R5 and R6 mean the same thing as above) The liquid crystal composition of the present invention includes at least one compound represented by the general formula (CI), at least one compound represented by the general formula (II), and at least one compound represented by the general formula (m) above in an appropriate ratio.

Further, the liquid crystal composition according to the present invention and other liquid crystal compounds 1
The liquid crystal composition of the present invention may be prepared by further mixing at least one species in an appropriate ratio.

Further, the liquid crystal composition according to the present invention is preferably a ferroelectric liquid crystal composition, particularly a ferroelectric chiral smectic liquid crystal composition.

Specific examples of other liquid crystal compounds used in the present invention are listed below.

Liquid crystal compound represented by general formula (I), liquid crystal compound represented by general formula (II), and general formula (m) of the present invention
The blending ratio of each of the liquid crystal compounds shown in
Per 100 parts by weight of the ferroelectric liquid crystal material, the general formula (I
), general formula (■)°, and general formula (III) in an amount of 1 to 300 parts by weight, more preferably 2 to 100 parts by weight.

Furthermore, when using two or more of any or all of the liquid crystal compounds represented by the general formula (1), general formula (n), and general formula (m) of the present invention, the blending ratio with the ferroelectric liquid crystal material is at least two or more of the liquid crystalline compounds represented by the general formula (I), -general formula (Il), and general formula (m) of the present invention, per 100 parts by weight of the above-mentioned ferroelectric liquid crystal material. 1 to 500 parts by weight, more preferably 2 to 500 parts by weight of a mixture of
The amount is preferably 100 parts by weight.

FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal element having a ferroelectric liquid crystal layer of the present invention, for explaining the structure of the ferroelectric liquid crystal element.

In Fig. 1, the symbol l is a ferroelectric liquid crystal layer, 2 is a glass substrate, 3 is a transparent electrode, 4 is an insulating alignment control layer, 5 is a spacer, 6 is a lead wire, 7 is a power source, and 8 is a polarizing plate. , 9 indicates a light source.

The two glass substrates 2 each have In1103+5n
Ot or ITO (indium tin oxide;
A transparent electrode 3 made of a thin film such as Indium Tin Oxide is coated thereon. Thereon, a thin film of a polymer such as polyimide is rubbed with gauze or acetate flocked cloth to form an insulating alignment control layer 4 in which the liquid crystals are aligned in the rubbing direction. Insulating materials such as silicon nitride, hydrogen-containing silicon carbide, silicon oxide, boron nitride, hydrogen-containing boron nitride,
An inorganic insulating layer made of cerium oxide, aluminum oxide, zirconium oxide, titanium oxide or magnesium fluoride is formed, and then polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyparaxylene, polyester, Insulating orientation control with two layers using organic insulating materials such as polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, Yulia resin, acrylic resin, and photoresist resin as the orientation control layer. Layer 4 may be formed, or it may be a single layer of an insulating orientation control layer of an inorganic material or an insulating orientation control layer of an organic material.If this insulating orientation control layer is inorganic, it may be formed by a vapor deposition method or the like. If it is an organic type, a solution containing an organic insulating material or its precursor solution (0.1
~20% by weight, preferably 0.2~IO% by weight), and coated using a spinner coatability 1 dip coating method, screen printing method, spray coating method, roll coating method, etc., and under predetermined curing conditions (e.g. It can be cured and formed by heating (under heating).

The layer thickness of the insulating orientation control layer 4 is usually 30 to 100 mm, ff.
1, preferably 30 to 3000 people, more preferably 50 to 1000 people.

These two glass substrates 2 are kept at an arbitrary distance by a spacer 5. For example, silica beads or alumina beads having a predetermined diameter are sandwiched between the two glass substrates as spacers, and the periphery is covered with a sealing material, such as epoxy. There is a method of sealing using adhesive. In addition, a polymer film or glass fiber may be used as a spacer.

A ferroelectric liquid crystal is sealed between these two glass substrates.

The ferroelectric liquid crystal layer l in which ferroelectric liquid crystal is sealed generally has a thickness of 0.5 to 207A11. Preferably it is 1 to 5 p■.

In addition, it is desirable that this ferroelectric liquid crystal has a Sac" phase (chiral smectic phase) in a wide temperature range including room temperature (particularly on the low temperature side) and has high-speed response. Furthermore, it is desirable that the temperature dependence of the response speed is It is desirable that the capacitor be small and have a wide drive voltage margin.

In addition, in order to obtain a monodomain state exhibiting good uniform alignment, especially when used as an element, the ferroelectric liquid crystal is changed from an isotropic phase to a ch phase (cholesteric phase) - SmA phase (smectic phase) - 3sC phase. ” phase (chiral smectic C phase)
It is desirable to have the following phase transition series.

The transparent electrode 3 is connected to an external power source 7 by a lead wire.

Further, a polarizing plate 8 is bonded to the outside of the glass substrate 2.

The device shown in FIG. 1 is of a transmission type and is equipped with a light source 9.

FIG. 2 schematically depicts an example of a cell for explaining the operation of a ferroelectric liquid crystal element. 21a and 21b are
lnJ:+, Snow or ITO (I
A substrate (glass plate) coated with a transparent electrode made of a thin film such as ndium-tin oxide), between which a liquid crystal molecular layer 22 is oriented perpendicularly to the glass surface.
IIC'' phase or SmH'' phase liquid crystal is sealed. A thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 23 has a dipole moment (PA) 24 in a direction perpendicular to the molecule. When a voltage higher than a certain threshold is applied between the electrodes on the substrates 21a and 21b.

The orientation direction of the liquid crystal molecules 23 can be changed so that the helical structure of the liquid crystal molecules 23 is unraveled and all of the dipole moments (P, ) 24 are oriented in the direction of the electric field. liquid crystal molecule 23
has an elongated shape and exhibits refractive index anisotropy in the long and short axis directions. Therefore, for example, if crossed Nicol polarizers are placed above and below the glass surface, the optical properties can be changed depending on the polarity of voltage application. It is easily understood that the liquid crystal optical modulation element will change.

The liquid crystal cell preferably used in the optical modulation element of the present invention has a sufficiently thin thickness (for example, 1 OuL or less).
can do. As the liquid crystal layer becomes thinner, the helical structure of the liquid crystal molecules unravels even when no electric field is applied, as shown in Figure 3, and the dipole moment Pa or pb is directed upward (: 14a) or downward (:14a). 3
Either state 4b) is taken. In such a cell, an electric field Ea of different polarity above a certain threshold value is applied as shown in FIG.
Alternatively, when Eb is applied by the voltage applying means 31a and 31b, the dipole moment changes its direction to upward direction 34a or downward direction 34b corresponding to the electric field vector of electric field Ea or Eb, and accordingly, the liquid crystal molecules become first stable. Status $:l:
la or the second stable state 13b.

As mentioned earlier, there are two advantages to using such a ferroelectric liquid crystal element as an optical modulation element.

The first is that the response speed is extremely fast, and the second is that the alignment of liquid crystal molecules has bistability. To further explain the second point, for example with reference to FIG. 3, the electric field Ea
When the electric field is applied, the liquid crystal molecules are aligned in the first stable state $33a, and this state remains stable even when the electric field is turned off. Moreover, when an electric field εb in the opposite direction is applied, the liquid crystal molecules enter the second stable state $
33b and changes the orientation of the molecule, but it remains in this state even after the electric field is turned off. Further, as long as the applied electric field Ea or Eb does not exceed a certain threshold value, the previous orientation state is maintained.

When a ferroelectric liquid crystal material having such characteristics is used as a simple matrix display device using an element sandwiched between a pair of substrates, for example, Japanese Patent Application Laid-Open No. 59-193426, #Open No. 59
Driving methods disclosed in JP-A-193427, JP-A-60-156046, JP-A-60-156047, etc. can be applied.

FIG. 4 is a waveform diagram of the driving method used in the embodiment of the present invention. Further, FIG. 5 is a plan view of a ferroelectric liquid crystal panel 51 on which matrix electrodes used in the present invention are arranged. Fifth
In the ferroelectric liquid crystal panel 51 shown in the figure, a scanning line 52 and a data line 53 are wired to cross each other, and a ferroelectric liquid crystal is arranged between the scanning line 52 and the data line 53 at the intersection. ing.

85 in FIG. 4(A) is the selected scanning waveform applied to the selected scanning line, SN is the non-selected scanning waveform that is not selected, 1. represents a selection information waveform (black) applied to a selected data line, and I,1 represents a non-selection information signal (white) applied to an unselected data line. Also, in the figure (r,
-ss) and (Is-3s) are the voltage waveforms applied to the pixels on the selected scanning line. The pixels to which the voltage (IS-ss) is applied display black, and the pixels to which the voltage (In Ss) is applied The displayed pixels assume a white display state.

FIG. 4(B) is a time series waveform when the display shown in FIG. 6 is performed using the drive waveform shown in FIG. 4(A).

In the driving example shown in FIG. 4, the minimum application time Δ1 of the unipolar voltage applied to the pixels on one selected scanning line corresponds to the time of the writing phase t2, and the time of the third phase of line clearing is 2Δt. is set to .

Now, each parameter v8 of the drive waveform shown in FIG.
The values of vl and Δt are determined by the switching characteristics of the liquid crystal material used.

FIG. 7 shows the change in transmittance T, that is, the V-T characteristic, when the driving voltage (v, +vl) is changed while keeping the bias ratio, which will be described later, constant. here,
Δt =501Ls, bias ratio Vl/(v++v
s) = 1/3. The positive side of Figure 7 is shown in Figure 4 (■o-S,), and the negative side is (15-ss).
The waveform shown is applied.

Here, V, and Vl are called actual drive threshold voltage and crosstalk voltage, respectively, provided that V*<Vl< V
l) Also, ΔV = (Vl-V,) is called a driving voltage margin, and it can be said that a Vl, which is the voltage width that allows matrix driving, exists in -boat fishing in FLC matrix driving. Specifically, Fig. 4 (A) (1, -3,
) is the voltage value that causes switching due to v2 in the waveform. Of course, it is possible to increase the value of ■3 by increasing the bias ratio, but increasing the bias ratio means increasing the amplitude of the information signal, which may lead to an increase in flickering in terms of image quality. , which is undesirable because it causes a decrease in contrast.

According to our study, a bias ratio of about 1/3 to 1/4 is practical. By the way, if the bias ratio is fixed, the voltage margin ΔV strongly depends on the switching characteristics of the liquid crystal material, and it goes without saying that a liquid crystal material with a large ΔV is very advantageous for matrix driving.

At a certain temperature like this, it is possible to write two states, "black" and "white", into the selected pixel depending on the two directions of the information signal, and unselected pixels can write the "black" or "white" state into the selected pixel. It is possible to maintain the state of The upper and lower limits of the applied voltage and its @ (driving voltage margin ΔV) differ between liquid crystal materials and are unique. Further, the drive margin also changes due to changes in the environmental temperature, so in the case of an actual display device, it is necessary to set the drive voltage to the optimum value for the liquid crystal material and the environmental temperature.

However, when the display area of such a matrix display device is expanded in practice, the difference in the environment in which the liquid crystal exists in each pixel (specifically, the difference in temperature and cell gap between electrodes) naturally increases. With a liquid crystal display having a small driving voltage margin, it becomes impossible to obtain a good image in all five display areas.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal composition 1.
-A was created.

Exemplary compound No.

Structural formula Structural formula Weight part Exemplary compound No.

Structural Formula Further, the following exemplified compounds were mixed with the liquid crystal composition vsl-A in the weight parts shown below to prepare a liquid crystal composition 1-B.

Exemplary compound no.

Structural Formula Next, device characteristics etc. were observed using a cell prepared using this liquid crystal composition 1-B according to the following procedure.

Two glass plates with a thickness of 1.1 ms were prepared, ITO15I was formed on each glass plate to create a voltage application electrode, and then Sin was vapor-deposited thereon to form an insulating layer.

On this substrate, a polyimide resin precursor (manufactured by Bunshishi ■, 5P-
710) Apply a 1.0% dimethylacetamide solution for 15 seconds using a spinner with a rotation speed of 2500 r, p,
A heating condensation firing process was performed at 300° C. for 30 minutes. The thickness of the coating film at this time is approximately 200
It was a person.

After firing, the film was rubbed with acetate flocked cloth, then washed with isopropyl alcohol, and silica beads with an average particle size of 1.5 g were sprinkled on one glass plate, followed by each rubbing treatment. The glass plates were glued together using an adhesive sealant (manufactured by Chisso ■, Rixon Bond) so that their axes were parallel to each other, and dried by heating at 100° C. for 60 minutes to create a cell. When the cell thickness of this cell was measured using a Berek phase plate, it was approximately 1.5 mm thick.

The above-mentioned liquid crystal composition 1-B was injected into this cell in an isotropic liquid state and slowly cooled from the isokyoshi phase to 25°C at a rate of 20°C/h, thereby producing a ferroelectric liquid crystal element 1.

Using this ferroelectric liquid crystal element, the driving voltage margin Δv is calculated using the driving waveform (l/3 bias) shown in FIG.
(V3-Vl) was measured.

In addition, the pulse width Δt set at the time of measurement is the drive threshold voltage vs=z
ov. At this time, Δt(V+=20
V) is the driving gjJ threshold voltage pulse width, which indicates the response speed.

10℃ 25℃ 40℃ Drive voltage margin A V 13.5V 14.5V 12.5
VFurthermore, if the voltage is set to the median value of the driving voltage margin at 25°C and the measurement temperature is changed, the driveable temperature difference (hereinafter referred to as driving temperature margin) is ±4.0°C.
Met.

Further, the contrast during driving at 25° C. was 12.0.

Comparative Example 1 Instead of liquid crystal composition 1-H used in Example 1, Exemplified Compound No. 2-11.2-100 was used for l-A without mixing Exemplified Compound No. 1-23. .2-145゜3
Liquid crystal composition 1-C1 and exemplified compound No. 2-11.2-10 in which only -40 was mixed in the same weight parts as in Example 1
Liquid crystal composition 1-D in which exemplified compound No. 0, 2-145 was not mixed with 1-A and exemplified compound No. 1-23. , Exemplified Compound No. 1-23.2-11.2-100.2- for 1-A without mixing Exemplified Compound No. 3-40
Liquid crystal composition 1-E was prepared by mixing only 145 in the same weight parts as in Example 1.

These liquid crystal compositions 1-C, 1-D, 1-E and 1-A
A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that a ferroelectric liquid crystal element was used, and a driving voltage margin ΔV and a driving temperature margin at 25° C. were measured in the same manner as in Example 1. The results are shown below.

Drive voltage margin ΔV (pulse width Δt set during measurement) 10°C 25°C 1-A Io, OV 10.5V (115
0gsec) (:120g5ec) 40°C 8.0v (114 end 5ee) 1-CI2. OV 12. O.V.
10.5v (950 end 5ec) (:10
0 bowls 5ee) (115 ends 5ec) -D 11, OV 11. O.V.
9.0V (1000μ5ec) (:]110g5
ec (llogsec)-E 12.5V 13.5V 1
1.0V (885) isec) (2904sec)
) (1154sec) Drive temperature margin 1-A ± 1. [1℃ 1-C±2.8℃ 1-D Upper 2゜1"C 1-E Soil 3.3'C As is clear from Example 1 and Comparative Example 1, the liquid crystal composition according to the present invention is contained. Ferroelectric liquid crystal elements have a wider drive margin and are better able to maintain good images despite changes in environmental temperature and variations in cell gap.

Furthermore, when focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 2 Liquid crystal composition 1-A used in Example 1 was mixed with the following exemplified compounds in the weight parts shown below to obtain liquid crystal composition 2-B.

Exemplary compound No.

Structural Formula A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that this liquid crystal composition was used, and the driving voltage margin was measured in the same manner as in Example 1, and the switching state, etc., was observed. . The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

Driving voltage margin ΔV (Pulse width Δt set during measurement) l'C25°C40°C Driving voltage margin ΔV 14. OV 14.5V
12. OV (Measurement setting (880 (29)
0 (110 pulse cap Δt) μ5ec) μ5
ec) psec) Furthermore, the driving temperature margin at 25°C was 3° to 7°C.

Also, the contrast during this drive at 25°C is 1
It was 3.0.

Comparative Example 2 In place of liquid crystal composition 2-B used in Example 2, exemplified compound No. 2-34.2-83.2-114 was mixed.
A, 1 example compound No. 1-18.1 for 1-A
Liquid crystal composition 2-C was prepared by mixing only -26.3-49 in the same parts by weight as in Example 2.

Ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, except that liquid crystal compositions 2-C and 1-A were used, and the driving voltage margin ΔV and The driving temperature margin at 25°C was measured. The results are shown below.

Drive voltage margin ΔV (a regular setting pulse width Δt) 10°C 25°C 40°C 1-A lO, OV 10.
5V 8. OV(1150gsec)
(320 Hec) (1144 sec) 2-C11
,OV 11.5V 9.0V
(950psec) (300μ5ec) (
105 psec) Driving temperature margin 1-A ± 1.6°C 2-C upper 2°2°C As is clear from Example 2 and Comparative Example 2, the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention has a higher The drive margin is wide, and the ability to maintain good images despite changes in environmental temperature and variations in cell gap is excellent.

Furthermore, when focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 3 Liquid crystal composition 1-A used in Example 1 was mixed with the following exemplified compounds in the weight parts shown below to obtain liquid crystal composition 3-B.

Exemplary compound No.

Structural Formula A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that this liquid crystal composition was used, and the driving voltage margin was measured in the same manner as in Example 1, and the switching state, etc., was observed. . The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

Drive voltage margin ΔV ([periodic setting pulse width Δt) 10°C 25°C 400C Drive voltage margin 'i A V 14. OV 14.2V 1
2.5V (Jig fixed time setting (810 (280
(110 pulse width Δt) End 5ee) End 5e
c) μ5ec) Furthermore, the driving temperature margin at 25°C was 4°C to 1°C.

Also, at 25°C. The contrast during this drive is 1
It was 3.5.

Comparative Example 3 In place of the liquid crystal composition 3-H used in Example 3, exemplified compound No. 2-12.2-26.2-155 was mixed.
Liquid crystal composition 3-C was prepared by mixing only exemplified compound eJNo. 1-19°3-12.3-44 in the same weight parts as in Example 3 with respect to l-A without A.

Except for using these liquid crystal compositions 3-C and 1-A, ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, and the driving voltage margin ΔV and The driving temperature margin at 25°C was measured. The results are shown below.

Driving voltage margin ΔV (Pulse width Δt set during measurement) l'C25°C4Q °C 1- A lO, OV lO, 5V
8. OV (1150g, 5ec) (320ps
ec) (114gsec) -C 11.5V 11.5V (960l 5ee) (: 1 mouth 5μ5ec)9.
5V (105 psec) Driving temperature margin 1-A ± 1.6°C 3-C ± 2.2°C As is clear from Example 3 and Comparative Example 3, the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention The drive margin is wider, and the ability to maintain good images despite changes in environmental temperature and variations in cell gap is excellent.

Furthermore, when focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 4 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal composition 4.
-A was created.

Exemplary compound No.

Structural formula % Formula % Structural formula parts by weight Further, the following exemplary compounds were mixed with the liquid crystal composition 4-A in the weight parts shown below to prepare a liquid crystal composition 4-B.

Exemplary compound no.

Structural formula % Formula % A ferroelectric liquid crystal element was prepared in the same manner as in Example 1 except that this liquid crystal composition was used, and the driving voltage margin was measured in the same manner as in Example 1. observed. The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

Drive voltage margin ΔV (Pulse width Δt set during measurement) 10°C 25°C 40°C Drive voltage margin ΔV 12. OV 14. OV 12.5
V (Measurement setting (435 (14G (5)
5 pulse duration Δt) psec) usec)
esec) Furthermore, the driving temperature margin at 25°C was 3° to 9°C.

Also, at 25°C. The contrast during this drive is 1
It was 3.0.

Comparative Example 4 In place of the liquid crystal composition 4-H used in Example 4, Exemplified Compound No. 2-11.2-100 was added to 4-A without mixing Exemplified Compound No. 1-23. .2-145゜3
Liquid crystal composition 4-C1 and exemplified compound No. 2-11.2-10 in which only -40 was mixed in the same weight part as in Example 4
Exemplary compound No. 1-23. Liquid crystal composition 4-D in which only 3-40 was mixed in the same weight part as in Example 4, and further exemplified compound N
Exemplary compound No. 1-2:l, 2-11.2-100.2-14 for 4-A without mixing o, 3-40
Liquid crystal composition 4 in which only 5 was mixed in the same weight part as in Example 4.
-E was created.

These liquid crystal compositions 4-C, 4-D, 4-E and 4-A
A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that a ferroelectric liquid crystal device was used, and the driving voltage margin ΔV and the driving temperature margin at 25°C were measured in the same manner as in Example 1. . The results are shown below.

Drive voltage margin ΔV (pulse width Δt set during measurement) 10°C 25°C 4-A 7. OV lO,5V(5,67
4sec) (160 psec) 40°C 9, Ov (59 end 5 ec) -C 10,5V 12.5 V (4901 sec) (150 end 5ee) 11, O
V (60 end 5ec) -D 9, OV 11.5V 9
．． 5V (500 end 5ec) (150μ5ec)
(551ec)-E 11, OV 12.5V 1
1.5V (4754sec) (145μ5ec)
(60 psec) Driving temperature margin 4-A ± 1.7°C 4-C top 2°9°C 4-D top 2°2°C 4-E top 3°06°C As is clear from Example 4 and Comparative Example 4, A ferroelectric liquid crystal element having a liquid crystal composition according to the present invention has a wider driving margin and is superior in its ability to maintain good images against changes in environmental temperature and variations in cell gap.

Furthermore, when focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 5 The following exemplified compounds were mixed with the liquid crystal composition 4-A used in Example 4 in the parts by weight shown below to obtain a liquid crystal composition 5-B.

Exemplary compound no.

A ferroelectric liquid crystal element was created in the same manner as in Example 1, except that a liquid crystal composition having the structural formula was used, and the driving voltage margin was measured in the same manner as in Example 1, and the switching state, etc., was observed. . The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

Driving voltage margin ΔV (Pulse width Δt set during measurement) 10°C 25°C 40°C Drive voltage? -Shin AV 11.8V 13.5V 12.5V
(Measurement setting (450 (140 (55 pulse width Δt) psec) 4sec) ps
ec) Also, the driving temperature margin at 25°C is ±3.
The temperature was 7°C.

Also, the contrast during this drive at 25°C is 1
It's 3.5.

Comparative Example 5 In place of liquid crystal composition 5-H used in Example 5, exemplified compound No. 1-16.3-23.3-18 was not mixed with 4-A. , 2-7.2-66
Liquid crystal composition 5- in which the same weight parts as in Example 5 were mixed with
Created C.

Ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, except that liquid crystal compositions 5-C and 4-A were used, and the driving voltage margin ΔV and The driving temperature margin at 25°C was measured. The results are shown below.

Drive voltage margin ΔV (pulse width Δt set during measurement) 10°C 25°C 40°C 4-A 7. OV 10. O.V.
9.0V (5674sec) (160g, 5ec)
(59g5ec)5-C8,5V 11
．． OV 9.7V (510psec)
(150 psec) (60 psec) Driving temperature margin 4-A fl, 76C 5-C±2.4°C As is clear from Example 5 and Comparative Example 5, the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention On the other hand, the drive margin is wide, and the ability to maintain good images despite changes in environmental temperature and variations in cell gap is excellent.

Furthermore, when focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 6 Liquid crystal composition 4-A used in Example 4 was mixed with the following exemplified compounds in the weight parts shown below to obtain liquid crystal composition 6-B.

Exemplary compound no.

Ferroelectric liquid crystal elements were prepared in the same manner as in Example 1 except that a liquid crystal composition having the structural formula % was used, and the driving voltage margin was measured in the same manner as in Example 1 to determine the switching state. etc. were observed. The uniform alignment within this liquid crystal element is good;
A monodomain state was obtained. The measurement results are shown below.

Driving voltage margin ΔV (I regular setting pulse width Δt) 10°C 25°C40°C Driving voltage v-shin ΔV 11.5V 14.5V
12. OV (Measurement setting (425 (13)
5 (55 pulse width Δt) to 5ec) end 5e
e) μ5ec) Also, the driving temperature margin at 25°C was 3° to 9°C.

Also, the contrast during this drive at 25°C is 1
It was 3.0.

Comparative Example 6 In place of liquid crystal composition 6-H used in Example 6, exemplified compound No. 2-10.2-169.3-41 was not mixed with 4-A, and exemplified compound No. 2-10.2-169.3-41 was mixed. 1-21.1-1
Liquid crystal composition 6 in which only 1 was mixed in the same weight part as in Example 6
-C was created.

Except for using these liquid crystal compositions 6-C and 4-A, ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, and the driving voltage margin ΔV and The driving temperature margin at 25°C was measured. The results are shown below.

Drive voltage margin ΔV (all fixed time setting pulse intensity Δt) 10°C 25°C 40°C 4-A 7. OV 10. O.V.
9.0V (567 end 5eC) (160 pots 5ec)
(59μ5ec)6-C9,OV 12.
OV 10.5V (480ILsec)
(145 Hec) (50 psec) Driving temperature margin 4-A fl, 7°C 2°1”C on 6-C As is clear from Example 6 and Comparative Example 6, the ferroelectric liquid crystal having the liquid crystal composition according to the present invention The element has a wider drive margin and is superior in its ability to maintain one image well against changes in environmental temperature and variations in cell gap.

Furthermore, when focusing on the pulse intensity Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 7 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal composition 7.
-A was created.

Exemplary Compound Structural Formula Parts by Weight Two exemplary compounds shown in the structural formula were mixed in the following parts by weight to prepare Liquid Crystal Composition 7-B.

Exemplary Compound Structural Formula %Formula % For this liquid crystal composition 7-A, the following -A was prepared in the same manner as in Example 1 except that this liquid crystal composition was used. The driving voltage margin was measured in the same manner as in Example 1, and the switching state etc. were observed. The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

Drive voltage margin ΔV (pulse width Δt set during measurement) 10°C 25°C 40°C Drive voltage v
-S:/AV 11.5V 13.2V
12-3V (setting during measurement (41G (1
25 (55 pulse width Δt) usec) 6
sec) 4 sec) Furthermore, the driving temperature margin at 25°C was ±3.6°C.

Also, the contrast during this drive at 25°C is 1
It was 3.5.

Comparative Example 7 Instead of liquid crystal composition 7-H used in Example 7, Exemplified Compound No. 2-7.2-66 was added to 7-A without mixing Exemplified Compound No. 1-16. , 3-18.3-23
Liquid crystal composition 7- in which the same weight parts as in Example 7 were mixed with
Created C.

Except for using these liquid crystal compositions 7-C and 7-A, ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, and the driving voltage margin ΔV and The driving temperature margin at 25°C was measured. The results are shown below.

Drive voltage margin ΔV (Pulse width Δt set during measurement) 10℃ 25℃ 40℃ Two A 7. OV9.5V
8.5V (504 psec) (142 gsec)
(54 psec) 7-C9, 2V 12
．． OV 11.0V (460#Lsec)
(135sec) (55μ5ec) Driving temperature margin 7-A ± 1.8°C 7-C ± 2.7°C As is clear from Example 7 and Comparative Example 7, the ferroelectric liquid crystal having the liquid crystal composition according to the present invention The element has a wider drive margin and is better able to maintain good images despite changes in environmental temperature and variations in cell gap.

Furthermore, when focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention has a higher
The temperature dependence of response speed is also reduced.

Example 8 Liquid crystal composition 7-A used in Example 7 was mixed with the following exemplified compounds in the weight parts shown below to obtain liquid crystal composition 8-B.

Exemplary compound no.

Structural Formula A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that this liquid crystal composition was used, and the driving voltage margin was measured in the same manner as in Example 1, and the switching state, etc., was observed. . The uniform alignment within this liquid crystal element was excellent, and a monodomain state was obtained. The measurement results are shown below.

Drive voltage margin ΔV (Pulse width ΔL set during measurement) 10°C 25°C 40°C Drive voltage margin ΔV 11. OV 14. OV 13.2
V (Measurement setting (430 (130 (55 pulse width Δt) #Lsec) ILsec)
xsec) Furthermore, the driving temperature margin at 25°C was ±3.7°C.

Also, the contrast during this drive at 25°C is 1
It was 3.0.

Comparative Example 8 In place of liquid crystal composition 8-B used in Example 8, exemplified compound No. 31.2-74.2-144.2-151 was used.
Exemplary compound No. 7-A without mixing.

Liquid crystal composition 8-C was prepared by mixing only No. 3-57 in the same weight parts as in Example 8.

Except for using these liquid crystal compositions 8-C and 7-A, ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, and the driving voltage margin ΔV and The driving temperature margin at 25°C was measured. The results are shown below.

Drive voltage margin ΔV (pulse width Δt set during measurement) 10°C 25°C 40°C 7-A 7. OV9.5V
8.5V (504 psec) (142 gsec)
(54 psec) 8- C8, OV 9
．． 5V 9.0V (490psec)
(140gsec) (55g5ec) Driving temperature margin? -A ± 1.86C 8-C ± 1.9°C As is clear from Example 8 and Comparative Example 8, the driving margin of the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention is wider; It has an excellent ability to maintain good images despite changes in environmental temperature and variations in cell gap.

Furthermore, focusing on the pulse width Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention shows that
The temperature dependence of response speed is also reduced.

Examples 9 to 16 In place of the exemplified compounds and liquid crystal compositions used in Example 1, the exemplified compounds and liquid crystal compositions shown in Table 1 were used in respective parts by weight to produce liquid crystals of 9-B to 16-B. A sexual composition was obtained. A ferroelectric liquid crystal element was created in the same manner as in Example 1, and the driving voltage margin was measured in the same manner as in Example 1, and the switching state, etc., was observed. The uniform alignment within the liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown in Table 1.

As is clear from Examples 9 to 16, the driving margin of the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention is wider, and the image performance is improved against changes in environmental temperature and variations in cell gap. Excellent ability to keep it in good condition.

Furthermore, when focusing on the pulse intensity Δt set at the time of measurement, the ferroelectric liquid crystal element containing the liquid crystal composition according to the present invention also has reduced temperature dependence of response speed.

Example 17 The liquid crystal composition used in Example 1 and Comparative Example 1 was
A ferroelectric liquid crystal element was created in the same manner as in Example 1, except that the alignment control layer was created only with polyimide resin without using The switching status etc. were observed. The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

Drive voltage margin ΔV (pulse intensity Δt set during measurement) 10°C 25°C 1-B 14.5V 15. IV (795
gsec) (275psec) 1-A Io
, 5V 11.0V (1100μ5ec) (
:110g5ec) 40℃ 12.7V (110μ5ec) 8.5v (115gsec) -C 12.8V 12.5V (930 pot 5ee) (290μ5ec) 10.5
V (115gsec) 1-D 11.4V 11.5
V (960 μ5 ec) (:105 end 5 ec) 1-
E 13.0V (870μ5ec) 1], 8V (285 end 5ee) 9.5V (110psec) 11.7V (115psec) Driving temperature margin 1-B Upper 4°3℃ 1-A f: 1.9”c 1 -C top 3゜0℃ 1-D top 2゜4”C I-E ± 3.5℃ Example! As is clear from 7, even when the element configuration is changed, the driving margin of the element having the ferroelectric liquid crystal composition according to the present invention is wider than that of the element having other liquid crystal compositions, as in Example 1. It has an excellent ability to maintain one image well despite changes in environmental temperature and variations in cell gap.

Furthermore, when focusing on the pulse width Δt set during measurement, the temperature dependence of the response speed is also reduced in the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention.

[Effects of the Invention] The ferroelectric liquid crystal composition according to the present invention and the liquid crystal element containing the same have good switching characteristics, a large drive voltage margin, and a certain degree of temperature variation over the display area of the element. It is also possible to create a liquid crystal element with a wide driving temperature margin in which all pixels can be satisfactorily matrix driven, and a liquid crystal element with reduced temperature dependence of response speed.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal device using the ferroelectric liquid crystal layer of the present invention, and FIGS. 2 and 3 show an example of an element cell for explaining the operation of the ferroelectric liquid crystal device. 4(A) and 4(B) are waveform diagrams of the driving method used in the examples. FIG. 5 is a plan view of a ferroelectric liquid crystal panel with matrix electrodes arranged. The figure is Figure 4 (B)
FIG. 7 is a schematic diagram of a display pattern when actual driving is performed using the time-series drive waveform shown in FIG. l... Ferroelectric liquid crystal layer 2... Glass substrate 3...
Transparent electrode 4... Insulating alignment control layer 5... Spacer 6... Riet wire 7... Power supply
8...Polarizing plate 9...Light source ■.・・・
・Incoming light■...Transmitted light 21a...Substrate 21b...Substrate 22...
-Liquid crystal molecule layer 23...Liquid crystal molecules 24-...Dipole moment (P) 31a, 31b...Voltage application means 33a...First stable state 33b...Second stable state 34a- =Upward dipole moment 14b...Downward dipole moment Ea...Upward electric field Eb...Downward electric field

Claims (2)

[Claims] (1) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R_1 is C_1 to C which may have a substituent
_1_8 linear or branched alkyl group, R_2 is C_1 to C_1_4 linear or branched alkyl group which may have a substituent, X_1, X_2 are single bonds,
-O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. (m is 0 to 7, n is 0 or 1) and the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_3 and R_4 are C which may have a substituent
_1 to C_1_8 linear or branched alkyl group,
X_3 and X_4 are single bonds, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
Z_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
Chemical formulas, tables, etc. are available▼, -CH_2O-, -OCH
＿２−、Single bond、▲Mathematical formula, chemical formula, table, etc.▼、
▲There are mathematical formulas, chemical formulas, tables, etc.▼ is ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. There are , tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
At least one of ▼ has tables, etc. is ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ has mathematical formulas, chemical formulas, tables, etc. ▼) and at least one of the compounds represented by the following general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_5 and R_6 are C which may have a substituent.
It is a linear or branched alkyl group of _1 to C_1_8, and at least one of them is optically active. X_5 is a single bond, -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, X_6 is a single bond, -O-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
A ferroelectric chiral smectic liquid crystal composition characterized by containing at least one of the compounds shown in the table below (indicated by ▼). (2) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (I) (In the formula, R_1 is C_1 to C which may have a substituent
_1_8 linear or branched alkyl group, R_2 is C_1 to C_1_4 linear or branched alkyl group which may have a substituent, X_1, X_2 are single bonds,
-O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. (m is 0 to 7, n is 0 or 1) and the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_3 and R_4 are C which may have a substituent
_1 to C_1_8 linear or branched alkyl group,
X_3 and X_4 are single bonds, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
Z_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, CH_2O-, -OCH_
2-, single bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, but ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
At least one of ▼ has tables, etc. is ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ has mathematical formulas, chemical formulas, tables, etc. ▼) and at least one of the compounds represented by the following general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_5 and R_6 are C which may have a substituent.
It is a linear or branched alkyl group of _1 to C_1_8, and at least one of them is optically active. X_5 is a single bond, -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, X_6 is a single bond, -O-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
1. A liquid crystal element characterized in that a ferroelectric chiral smectic liquid crystal composition containing at least one of the compounds shown in Table 1 (indicated by ▼) is disposed between a pair of electrode substrates.