JPH0245590A - Liquid crystal composition and liquid crystal element using said composition - Google Patents

Abstract

PURPOSE:To obtain a liquid crystal composition suitable for liquid crystal element, light crystal-optical shutter, etc., having high response speed to electric field and low temperature dependence comprising three kinds of chiral smectic liquid crystal compositions having specific structures. CONSTITUTION:The aimed composition containing (A) a compound shown by formula I (R1 and R2 are 1-18C alkyl; X1 and X2 are single bond, -O- or -OCO-), (B) a compound shown by formula II (R3 and R4 are 1-18C alkyl: X3 and X4 are single hood, -O-, -OCO- or -CO2-; Z1 is -CO2-, -CH2O-, etc.; groups shown by formula III and formula IV are p-phenylene, cyclohexyl or group shown by formula V; group shown by formula VI is p-phenylene) and (C) a compound shown by formula VII (R5 and R6 are 1-18C alkyl; X5 and X6 are single bond, -O-, -CO2-, etc.; Z2 is-CN2O-; m and n are 1 or 2).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a liquid crystal assembly 1 & product used in a liquid crystal element used in a liquid crystal display element, a liquid crystal light shutter, etc. The present invention relates to a novel and improved 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 include M-Shut (M.

5etiadt) and Tabru Helfrich (W, l
“Applied Phys Letters”
cs Letters”) Vo, 18. No, 4 (
1971, 2, +5) P, 127-+28 “Vol.
stage Dependent Optical Ac
tivity of a Twisted N
It uses a TN (Twist, ed NemaLic) type liquid crystal shown in ``emat, ic 1iquid (:rysLal'').

These are based on the dielectric alignment effect of liquid crystals, and utilize the effect of the dielectric anisotropy of liquid crystal molecules causing them to be oriented in the average molecular axis direction or in a specific direction 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, considering cost, productivity, etc., driving using a simple matrix method is most likely. In the pure 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 it, an address signal is selectively and periodically applied to the scanning electrode group, and the signal electrode A time-division driving method is adopted for the group, 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 an area 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 large enough, and the voltage value is set to the voltage value required to align the liquid crystal molecules perpendicular to the electric field, or a voltage value in between,
Does the display element operate normally?The number of scanning lines (N
), the time (duty ratio) during which an effective electric field is applied to one selected point while scanning the entire screen (one frame) or the ratio of I/N decreases.

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 reduced 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 (liquid crystal molecules are in a stable state aligned horizontally with respect to the electrode surface, and are aligned vertically only when an electric field is effectively applied).
This is essentially an unavoidable problem that arises when driving (that is, repeatedly scanning) using the temporal planting effect.

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 because the number of scanning lines cannot be increased sufficiently.

To improve the drawbacks of conventional liquid crystal devices, the use of bistable liquid crystal devices or Clark (C1
ark) and Lage rwal I
) (Japanese Unexamined Patent Publication No. 56-107216, U.S. Pat. No. 4,367,924 #J Riko et al.).

As the bistable liquid crystal, a ferroelectric liquid crystal having a chiral metallic C phase (Sac" phase) or H phase (Salt" phase) is generally used.

This ferroelectric liquid crystal has a bistable state fg consisting of a first optically stable state and a second optically stable state with respect to an electric field,
Therefore, unlike the optical modulation element used in the above-mentioned TN type liquid crystal, the liquid crystal is oriented in a first optically stable state for one electric field vector, and a second optically stable state for the other electric field vector. The liquid crystal is aligned to an optically stable state. In addition, this type of liquid crystal responds to the applied electric field by
It has the property of being in one of two stable states and maintaining that state when no electric field is applied (bistability).

In addition to the above-mentioned characteristics of bistability, ferroelectric liquid crystals have the excellent feature of high-speed response. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied hot water directly interact to induce a transition in the orientation state, which is 3 to 4 orders of magnitude faster than the response speed due to the effects of dielectric anisotropy and electric field.

In this way, ferroelectric liquid crystals potentially have extremely excellent properties, and by utilizing these properties, many of the problems of the conventional TN type elements mentioned above can be solved by creating a wood-like liquid crystal. Improvements 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, ferroelectric liquid crystal materials have been extensively researched, and 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 hard to say that we are prepared.

There exists a relationship between the response time, the magnitude of spontaneous polarization Ps, and the viscosity η as expressed by the following formula % (where E is the applied voltage). Therefore, in order to increase the response speed, (a) increase the magnitude of spontaneous polarization PS (b) increase the viscosity η
There is a way to make the applied voltage E higher. However, since the applied electric field is driven by an IC, there is an upper limit, 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 metallic liquid crystal compounds that have a large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is also large, and there tends to be more restrictions on the device configuration 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 degrees Celsius, the response speed generally changes by about 20 times, which currently exceeds the limits of adjustment by drive voltage and frequency. be.

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.
It is possible to apply the driving method disclosed in Japanese Patent Laid-Open No. 156046-156046, Japanese Patent Application Laid-open No. 155047-1980, and the like.

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.

In FIG. 4(A), Ss is the selection scanning waveform applied to the selected scanning line, S8 is the unselected scanning waveform, and 1s is the selection information waveform (black) applied to the selected data line. ), and 1.1 represents a non-selection information signal (white) applied to an unselected data line. Also, in the figure (Is
Ss) and (1, -ss) are voltage waveforms applied to pixels on the selected scanning line; pixels to which voltage (+, -s,) is applied display black, and voltage (+N5S) The pixel to which the voltage is applied assumes a white display state.

FIG. 4(B) is a time series waveform when the drive waveform shown in FIG. 4(A) is displayed as shown in FIG. 6.

In the driving example shown in FIG. 4, the minimum application time ΔL of the unipolar voltage applied to the pixels on the selected scanning line corresponds to the writing phase L2 time, and the line clearing corresponds to the 1 phase time or 2Δt. It is set.

Now, each parameter vs, v of the drive waveform shown in FIG.
The values of I and ΔL 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 drive voltage (VS+VI) is changed while keeping the bias ratio, which will be described later, constant. Here,
Δt = 50gs, bias ratio V, / (V, +VS
) = 1/3 fixed tail. The positive side of Figure 7 is the 4th
The waveform shown in the figure (INS5) and the negative side (Is Ss) are applied.

Here, V and V are respectively called the actual drive dark value voltage and the crosstalk voltage. However, V2<Vl< V
3) Also, ΔV = ('h v+) is called a drive voltage margin, and is a voltage width that allows matrix drive. ■, is F
It can be said that this generally exists in terms of matrix driving of l and c. Specifically, it is the voltage value that causes switching due to v2 in the waveform of FIG. 4(A) (IN-3S). Of course, by increasing the bias ratio,
Is it possible to increase the value of v3? Increasing the bias ratio means increasing the amplitude of the information signal, which is undesirable in terms of image quality because it increases flickering and reduces 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 values of the upper and lower limits of the applied voltage and their widths (driving voltage margin ΔV) differ and are specific to each liquid crystal material. 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 response speed of a ferroelectric liquid crystal device by increasing its response speed, reducing its temperature dependence, or expanding the driving voltage margin so that a ferroelectric liquid crystal device can be put to practical use. To provide a chiral smectic liquid crystal 1iJ composition with a wide drive temperature margin capable of satisfactorily driving all pixels in a matrix even if there is some 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) (wherein R,, R2 are C1 to C11 linear or branched alkyl groups, and C7 as a substituent) ~CI2 may have an alkoxy group, provided that R,,R.

Neither of these groups is an n-alkyl group.

) and at least one compound represented by the following general formula (■
) R3X:l ■Reference YZ1-C)-X4R4(II)
1o linear or branched alkyl group, X3. X4
-C11□O-, -0CI+2-, single bond, now Tomoe No. 2, but Beeto.

At least one of the compounds represented by at least one of -G- and -〇D- and the following general formula (Ill). Among the compounds represented by the above-mentioned general formula (1), examples of preferable compounds include: (I-a) to (I-
p) Compounds represented by the formula are mentioned.

(In the formula, R5, l (a is C1 which may have a substituent)
- straight chain or branched alkyl group of CIll, X5.
X6Z2 is -CI+20- or 10 CII 2-
shows. m, n are l or 2) A ferroelectric chiral smectic liquid crystal set r! i
The present invention provides a liquid crystal device 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.

Further, as preferred examples of R,, R2 in the above-mentioned formulas (I-a to (1-p)), (I-i) to (ni V
) can be mentioned.

(Optical activity or racemate) ■ R2+CII 2h-CII -(CII 2 )-
T-OR.

(Optical activity or racemate) Compounds represented by formulas (II-a) to (II-q) can be mentioned.

(Optically active or racemic) R5 or -1-CII 2 C) I-119 (Optical active or racemic) CII 3 R2 is -(-CI+2)-=CII-R? (Optically active or racemic) R1+C112h-C11-119 (Optically active or racemic) C)13 R2+-C112i(:II-(CI+2)-=OR
Q (optically active or racemic) R7, Ra, and R'+ represent a linear or branched alkyl group. P and QIS are 0 to 7, and r is O or 1.

Further, in the compound represented by the above general formula (n),
Preferred examples of the compounds include the compounds shown below, and further preferred examples of the above-mentioned (H-a), -vm).

(II i) L is a single bond (II-0) X3 or a single bond (II rri) X, or -0 (II iV
) X:l or -0-<II v) L?
-0C- (II-i) in ~(n-q) ~ (II ×4 or single bond ×4? -〇- ×4 or single bond ×4? -〇- ×4 or single bond (II Vi) X:l is -0[knee
X, ka -O (II-vii) X-1 ka -c o
-x, or single bond (IT yi) Xi or -GO
-X4 car 0-Also, the above (II-a) ~
As a preferable example of R:I and R4 in formula (II-q), it is possible to mention that R3 and R4 are linear alkyl groups.

In addition, among the compounds represented by the above-mentioned general formula (III), preferred examples of compounds include the following (III-a) to (
[II-f) Compounds represented by the formula can be listed.

R1-X5+CI+20+X6-R.

R, -X s +OCIt 2bet X6-116115
-X=, +CI+203 X6-R2O, -X, +
OCIt□()℃sawax6-n6R5-X, 噸)(sawaC1
120+X 6- RaRs -X s W OCH2
+X 6- Rs(m-a) (m-b) (III-c) (III-d) (In-e) (I[If-f) (m-1ii) ×5 or single bond ×6 or C - (m -iv) (m-v) (III -vi) (III -vi) (m -vi) x5 or single bond X, or -0 X, or -〇- ×6 or -C〇- 1! Is x6 a single bond ×6? -〇- ×5 or X, or 〇- ×6 or -〇C- More preferable examples of R,, R6 are shown below (
It is possible to list m −ix ) to (m−xi).

In addition, ×5° (III-i ([-i (m-1t) Furthermore, as a more preferable example of x6 in the above formulas ([I-a) to (m-f), it is shown below) to ( III-vi
).

)×, or single bond x6 or single bond) XS or single bond x6 or −〇−R5 or n
-Alkyl group (m-x) R5 or n-alkyl group R6-(-CI12h-CIl-R,.

l16 is CII2CIICuI12u-r (III-x (Eng. ■) R5 or n Alkyl group C11゜ R6 force (-Cl12 h-C11-(C11□)9-OR,.

R1O+ R11゜ is a straight or branched alkyl basis, t, X.

Z is 0-7, U is 1-12, y is 0 (1,-3) indicates 1.

next, Above-Cost of clothes The ingredients of the compound shown in An example of a physical structural formula is shown below.

(1-1,8) υ U υ (1-+18) The compound represented by -Fukudai (I) is, for example, disclosed in JP-A-6
1. -93170, JP 61-24576, Special DH DH 61-129170, JP 1987-51-
2 (1 (1972 publication, JP 61-200973, JP 51-2+5:172, JP 1983-1982-1
-291574 Publication, East German Patent No. 95892 (+9
7:1 year). For example, it can be obtained using the synthetic route shown below.

A typical synthesis example of the compound represented by R2x2+CN (R, , R2, and X2 means those mentioned above)-Fukudai (I) is shown below.

Synthesis Example 1 (Synthesis of Compound No. 1-20) Pyridine 5n
1.05 g of 5-methoxyhexanol dissolved in j)
(8,0m5of), 183g p-toluenesulfonic acid chloride dissolved in pyridine 51 (9,6+*mo
j? ) was added dropwise at below 5°C in an ice water bath. After stirring for 6 hours at room temperature, the reaction mixture was poured into 100 μP with cold water.

The mixture was acidified with 6N hydrochloric acid and extracted with isopropyl ether. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 5-methoxyhexyl-p-toluenesulfonate.

10mj of dimethylformamide? 5-decyl-2-(
p-hydroxyphenyl)pyrimidine 2.0g (6,4
1 mmoi'), add 0.61 g of potassium hydroxide,
Stir at oooC for 40 minutes. To this was added the previously obtained 5-methoxyhexyl-p-toluenesulfonate, and 1
The mixture was heated and stirred at 00°C for 4 hours. After the reaction is complete, pour the reaction mixture into 10 mouths of cold water. ! 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. After purification by column chromatography (silica gel-ethyl acetate/benzene = 1/9), it was recrystallized from hexane to give 5-decyl-2-
(4-(5'-Methoxyhexyloxy)phenyl)pyrimidine (Compound No. 1-20) 1. :15g was obtained.

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

The reaction mixture was poured into ice water 150+si', adjusted to pH approximately 3 with 6N aqueous hydrochloric acid solution, and then extracted with ethyl acetate. This was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to (6-pentyloxyheptyl)-p-
2.98 g of toluenesulfonate was obtained.

3.12 g of 5-n-decyl-2-(4-hydroxyphenyl)pyrimidine and 0.53 g of potassium hydroxide were dissolved in dimethylformamide (14vj) and heated to 100°C for 3.
After heating and stirring, (6-pentyloxyheptyl)
Add 2.98g of p-toluenesulfonate, 1
The mixture was heated and stirred at 00°C for 5 hours.

The reaction mixture was poured into 200 mff of ice water, 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. This was purified by silica gel column chromatography (developing solution: n-hexane/ethyl acetate = 1O/2), and then recrystallized from hexane. 1.55 g of phenyl)pyrimidine were obtained.

IR (cm-') 2924.2852, 1610.158B, 1472° 1436.1254, 1168, 1096. 798
Phase transition temperature ('C) Synthetic route A Synthetic route B For compounds other than the synthetic side, the following synthetic routes A and B
It can be obtained by

(In the above formula.

R8゜ R2゜ ×1゜ r means the same as above) (q.

next, Said - Clothing charges (II) The ingredients of the compound shown in An example of a physical structural formula is shown below.

(2'-29) υ (2-36,) C, lI, No. OC () (Toc 112CIIC2115
134] (::lI+ 7+CII20 W OC1o II2
1C5fl+ l+ClI20 (C place (QCl 2
t(□5Cs II + + +CH20W OCI
4 H29<2-138) C611,3+clIa030f cl+□%-C61
1,4C, + I+, 8 (: 1120440m161
L30511□shac u2o ()(toc6HI ?C
8+11? No. CH20 () (To C1, H29C, 11,
Ic1120噸シE)-C, □82Sc4++9+c
H□0→γ◎zu, H,.

Cs1l++ No.ocu2% oc, 2++25 above-
Typical synthesis examples of the compound represented by ``rl'' are described below.

Synthesis Example 3 (Synthesis of compound No. 2-65) 5-dodecyl-2-(4'-hydroxyphenyl) and sewing machine 1.0
g (2,94gmoj') toluene 4mf! and pyridine 41IIβ. To this, 0.55 g of trans-4-n-propylcyclohexanecarboxylic acid chloride (manufactured by Kanto Kagaku ■) dissolved in toluene 4aR was gradually added dropwise at 5° C. or lower in an ice water bath. After the dropwise addition was completed, the mixture was stirred at room temperature for 12 hours, and the reaction mixture was poured into 100 mji 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 this was purified by column chromatography, ethanol/
Recrystallized from a mixed solvent of ethyl acetate to obtain the white title compound 0.
．． 94g was obtained. (Yield 64.8%) Phase transition temperature (°C) Synthesis example 4 (compound QNo., combination J& of 2-133) (1)
10 g of trans-4-n-propylcyclohexanecarboxylic acid chloride (S: 1.6 mmol) was dissolved in 30 mR of ethanol, 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 acidify the mixture, the mixture was extracted with isopropyl ether. The organic layer was washed repeatedly with water until the washing solution became neutral, and then dried with magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography to obtain 9.9 g of trans-4-lopropylcyclohexanecarboxylic acid ethyl ester.

(II) Lithium aluminum hydride 0.73g
(19,1mmoi') in dry ether for 30s! ! and heated under reflux for 1 hour. After cooling to about 10° C. in an ice water bath, 5 g (25,51 mo β) of trans-4-n-propylcyclohexanecarboxylic acid ethyl ester dissolved in 30 sj) of dry ether 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. After treating this with ethyl acetate and 6N hydrochloric acid aqueous solution, it was washed with 200ml of ice water! ! injected into.

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.

(IIlr) 3.4 g (22.4 mmoi) of trans-4-n-propylcyclohexylmethanol was dissolved in 20 mj of pyridine. To this was added 5.3 g of p-toluenesulfonic acid chloride dissolved in 20 mA' of pyridine in an ice water bath. It was added dropwise while cooling to below 5°C. After stirring at room temperature for 10 hours, it was poured into 200 sR of ice water. 6N
After making the mixture acidic with an aqueous hydrochloric acid solution, the mixture was 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-rl-propylcyclohexylmethyl-p-toluenesulfonate.

(TV) 5-decyl-2-(4'-hydroxyphenyl)pyrimidine in dimethylformamide 40126.
3g (2[+, 2mop) was dissolved. 85% to this
1.5 g of potassium hydroxide was added and stirred for 1 hour. 6.9 g of trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate was added and further stirred at 100°C for 4 hours. After the reaction was completed, this was poured into 200mj7 of ice water and extracted with benzene.The organic phase was washed with water and then dried with magnesium sulfate.After the solvent was distilled off, it was purified by silica gel column chromatography, and this was further purified with ethanol/ Recrystallized from ethyl acetate mixed solvent to obtain the exemplified compound No. 2-1.
I got 33.

If? (cm-') 2920.2840. 1608. +584. 1
428. 1258°11.64. 800 Phase transition temperature (°C) (S+2 is 5IIA, smectic phase other than Sac,
When Zl is a single bond (unidentified), a compound represented by the following formula can be synthesized by the following synthetic route.

(R3 and R4 have the same meanings as defined above) Next, examples of specific structural formulas of the compound represented by the above-mentioned formula (III) will be described below.

I40 +1 UNa II-Ca Hl? +0 CIt□ Tsukasa) (To0- C7
II l 5n-C6II r z+oCH2WO O-
Ca li+ t -nn-(:4It91CII□4
0-C611n-C71115+CI+ 2 +0
Call+'y 530CI+, (To0-C, □1125n-C,,
II, ++CII□O+0-C+ oH□+C5It
+ + +CII203 C6If I 3- nC
7111,,+CII□OHC6HI:+-n7+C
1l□O publication) (ToC511+ +-nC611,3+0
CR2 is) (ToC6If l :1C!l Hl 7+
CII204)(to0(:6111 ff-nn-C
8If l 7+CII20 W OC, 1117-n
n-C6HI? + 1120 +O-C6It +
:+n-C7H+ s + H□0 +QC5If I
I -nn-Ca If l 7-0+OC112+
0- C6Hl :1CJ+s-0+0CIIz +O
-C, +119-nC, II, 5+OCII□噸(
ToC2II 2 .

The compound represented by the above-mentioned -Fukudai (III) is disclosed in, for example, JP-A-60-14954, JP-A-51-63633.
It can be obtained by the synthesis method described in the above publication. Typical synthesis examples are shown below.

Synthesis Example 5 (Synthesis of Compound No. 3-54) 1.0 g of the following alcohol derivative (4,81
Add m5oA), C,11,,o+CI+□011 While cooling, add thionyl chloride 31 and raise the temperature to room temperature while stirring.Additionally, attach a cooling tube and reduce the external temperature to 70°C~
The mixture was heated under reflux at 80°C for 4 hours. After the reaction, excess thionyl chloride was distilled off to obtain a chloride. Add this toluene 1
It was dissolved in 51.

Next, 200mf! 0.33 g of 60% oily sodium hydride was placed in a three-necked flask, and after washing several times with dry n-hexane, a TIIF solution of 1.52 g (4,81 off) of the following phenol derivative was added.
5 mj) was added dropwise at room temperature, and then 20 m of DMS and O were added dropwise at room temperature.
j! The mixture was added and stirred for 1 hour. To this, the toluene solution of the chloride mentioned above was slowly added dropwise, and after the dropwise addition was completed, stirring was continued for an additional 16 hours at room temperature.

After the reaction was completed, the organic layer was separated into approximately 200 mf of ice water, and the aqueous layer was extracted twice with 50 ml of benzene. After washing the previously separated organic layer twice with a 5% aqueous hydrochloric acid solution, the ions were extracted. Once with exchanged water and then 5% Na OII
The organic layer was washed once with an aqueous solution, and then the organic layer was washed with ion-exchanged water until the pH value of the aqueous layer became neutral.

The organic layer was removed and dried using magnesium sulfate.
The solvent was distilled off to obtain a crude product. This was purified by silica gel column chromatography using a developing solution of n-hexane/dichloromethane = 3/10.

The crystals obtained by distilling off the solvent were recrystallized using n-hexane to obtain the purified target product. Furthermore, vacuum drying was performed at room temperature to obtain 0.69 g of the final purified target product. Yield is 28
．． It was 5%.

Elemental analysis value (wt%) C Calculated value 78.33 Measured value 78.96 Phase transition temperature (°C) 8.57 8.69 0.00 0.02 Synthesis example 6 (synthesis of compound No. 3-68) 30+u? Put 1.25 g (49 mouths 1 x 0 β) of the following alcohol derivative into an eggplant flask, and add c811. , o or stool) Add 4 mJ of thionyl chloride to C112011 under cooling, raise the temperature to room temperature with stirring without stirring, and then attach a cooling tube and heat under reflux for 4 hours at an external temperature of 70°C to 80°C. I did it. After the reaction, excess thionyl chloride was distilled off to obtain a chloride. This toluene]Sm1)
dissolved in.

Next, 200mj! 60% oily sodium hydride in a three-necked flask with 0. : Il, g was added, washed several times with dry n-hexane, and then a THF solution 1 of 0.79 g (4,01 mmoj?) of the following phenol derivative was added.
5+ai) was added dropwise at room temperature, and then 20 m of DMSO was added.
j2 was added and stirred for 1 hour. To this, the toluene solution of the chloride mentioned above was slowly added dropwise, and after the dropwise addition was completed, stirring was continued for an additional 16 hours at room temperature.

Approximately 200m1 after the reaction is complete! The organic layer was separated, and the aqueous layer was extracted twice with benzene 50+i), washed with the previously separated organic layer twice with a 5% aqueous hydrochloric acid solution, and once with ion-exchanged water. Then, the organic layer was washed once with a 5% NaOH aqueous solution, and then the organic layer was washed with ion-exchanged water until the pH value of the aqueous layer became neutral.

The organic layer was removed and dried using magnesium sulfate.
The solvent was distilled off to obtain a crude product. This was purified by silica gel column chromatography using a developing solution of n-hexane/dichloromethane = 3/1.0.

The product obtained by distilling off the solvent was recrystallized using n-hexane to obtain the purified target product. Further, vacuum drying was performed at room temperature to obtain the final purified target product. I got g. Yield is 2
It was 6.0%.

CHN analysis value (wt%) CHN calculated value 7813 8.53 0.00 Theoretical value
78.62 8.86 0.02 Phase transition temperature (°C
) IR spectrum 2975° 1510° 1280° ] 020° S2. S:l unidentified 2925, 2850. 161.0°1470, 1
380. +295°1240, 1220. 11
30°1000, 810 cm-' The liquid crystal composition of the present invention comprises at least one compound represented by the general formula (I), at least one compound represented by the general formula (LT), and the compound represented by the general formula (LT). It can be obtained by mixing at least one of the compounds represented by (III) 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.

(1l) The liquid crystalline compound of the present invention represented by the general formula (I), the liquid crystalline compound represented by the general formula (II), and the liquid crystalline compound represented by the general formula (II)
The compounding ratio of each of the liquid crystal compounds shown in I) and one or more of the other liquid crystal compounds mentioned above, or the ferroelectric liquid crystal material 11t (hereinafter referred to as ferroelectric liquid crystal material) containing the same, is as follows: Per 100 parts by weight of the dielectric liquid crystal material, 1 to 300 parts by weight, more preferably 2 to 100 parts by weight of each of the liquid crystalline compounds represented by the general formula (1), general formula (■), and general formula (III) of the present invention. It is preferable to use parts by weight.

Furthermore, when using two or more of the liquid crystalline compounds represented by general formula (1), general formula (n), and general formula (I [I) of the present invention, it is also possible to combine them with ferroelectric liquid crystal materials. The compounding ratios are general formula (I), general formula (II), and general formula (II) of the present invention per 100 parts by weight of the ferroelectric liquid crystal material described above.
It is desirable that the amount of any one or a mixture of two or more of the liquid crystal compounds represented by I) be 1 to 500 parts by weight, more preferably 2 to 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, 8 is a polarizing plate, 9 indicates a light source.

The two glass substrates 2 each have fnzoi+SnO.
□Or I'rO (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 arranged in the rubbing direction of the liquid crystal. Further, as an insulating material, for example, silicon nitride, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen,
Cerium oxide, aluminum oxide, zirconium oxide.

An inorganic insulating layer such as titanium oxide or magnesium fluoride is formed, and then polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyvaraxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, The insulating orientation control layer 4 may be formed of two layers using an organic insulating material such as polyamide, polystyrene, cellulose resin, melamine resin, Yulia resin, acrylic resin, or photoresist resin as the orientation control layer, or an insulating orientation control layer 4 made of an inorganic material. It may be an insulating orientation control layer or a single layer of an organic material insulating orientation control layer. If this insulating alignment control layer is inorganic, it can be formed by a vapor deposition method, or if it is organic, it can be formed by a solution containing an organic insulating material or its precursor solution (0.1 to 20%
% by weight, preferably 0.2 to 10% by weight) by a spinner coating method, dip coating method, screen printing method, spray coating method, roll coating method, etc., and under predetermined curing conditions (for example, under heating). ) can be cured and formed.

The thickness of the insulating orientation control layer 4 is usually 30 to 1 JL-1, preferably 30 to 3,000, and more preferably 50 to 1,000.

These two glass substrates 2 are kept at an arbitrary distance by a spacer 5. For example, there is a method in which silica beads or alumina beads having a predetermined diameter are sandwiched between two glass substrates as spacers, and the periphery is sealed using a sealing material, such as an epoxy 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 the ferroelectric liquid crystal is encapsulated is generally 0.5 to 20 l, preferably 1 to 5 l.

Further, it is desirable that this ferroelectric liquid crystal has an S■C3 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 desired that the temperature dependence of the response speed be small and that the drive voltage margin be wide.

In addition, in order to obtain a monodomain state exhibiting good uniform alignment, especially when used as an element, the ferroelectric liquid crystal should be changed from the tomoyoshi phase to the ch phase (cholesteric phase) - S layer phase (smectic phase) - 8IlG'' phase (chiral smectic C phase) is desirable.

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, so it 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. 2], a and 21b are In2O:+, SnO2 or ITO, respectively.
It is a substrate (glass plate) coated with a transparent electrode consisting of 13 films such as (Indium-Tin Oxide), between which a liquid crystal molecular layer 22 of 5raC2 phase or S11'' phase is oriented perpendicular to the glass surface. A liquid crystal is sealed.The thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 23 has a dipole moment (Pl) 24 in a direction perpendicular to the molecule.Substrates 21a and 21
When a voltage above a certain threshold is applied between the electrodes on b.

The helical structure of the liquid crystal molecules 23 is unraveled, and the liquid crystal molecules 23 can change their alignment direction so that 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 its major and minor 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 changes.

The thickness of the liquid crystal cell preferably used in the optical modulation element of the present invention can be made sufficiently thin (eg, 10 mm or less). As the liquid crystal layer becomes thinner in this way, 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 (34a) or downward (34b).
). When an electric field Ea or Eb of different polarity above a certain dark value is applied to such a cell by voltage applying means 31a and 31b, as shown in FIG.
The dipole moment changes its direction upward 34a or downward 34b in response to the electric field vector of the electric field Ea or Eb, and the liquid crystal molecules accordingly move into the first stable state 7933a or the second stable state 33b. Orient in one direction.

There are two advantages of using such a ferroelectric liquid crystal element as an optical modulation element as mentioned above.

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 voltage is applied, the liquid crystal molecules are oriented in the first stable state 7!133a, or this state is stable even when the electric field is turned off. or,
When an electric field Eb in the opposite direction is applied, the liquid crystal molecules are oriented in a second stable state 7gi:13b and the orientation of the molecules is changed, but they remain in this state even after the electric field is turned off. or,
As long as the applied electric field Ea or Eb does not exceed a certain darkness 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 Laid-Open Nos. 59-193426 and 59
Driving methods disclosed in Japanese Patent Application Laid-open No. 193427, Japanese Patent Application Laid-Open No. 156046-1982, and Japanese Patent Application Laid-open No. 156047-1987 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 for unexploded use 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 1 is placed between the scanning line 52 and the data MA 53 at the intersection. There is.

In FIG. 4(A), Ss is the selection scanning waveform applied to the selected scanning line, So is the unselected scanning waveform, and l is the selection information waveform applied to the selected data line ( 8 represents a non-selection information signal (white) applied to an unselected data line. Also, in the figure (+S-
SS) and (Is Ss) 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 (iHss) is applied are Takes a white display state.

FIG. 4(B) is a time series waveform when the drive waveform shown in FIG. 4(A) is displayed as shown in FIG. 6.

In the driving example shown in FIG. 4, the minimum application time ΔL 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 line clearing and one phase becomes 2ΔL. It is set.

Now, each parameter of the drive waveform shown in FIG.
The values of l and ΔL 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 (VS+V+) is changed while keeping the bias ratio, which will be described later, constant. here,
Δt = 50 ps, bias ratio V+/ (v, + v
s) = l/3. The positive side of Figure 7 is shown in Figure 4 (IN Ss), and the negative side is (Is
A waveform indicated by Ss) is applied.

Here, V, V3 are called actual drive I value voltage and crosstalk voltage, respectively. However, v2<V,<V
) Also, Δv '' (V:l v+) is called the drive voltage margin, and is the voltage width that allows matrix drive.■3
It can be said that this generally exists in FLC matrix driving. Specifically, Fig. 4 (A) (+, -3,)
This is the voltage value that causes switching due to v2 in the waveform of . 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 cause flickering in image quality. This is undesirable because it causes an increase in color and 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", to a selected pixel depending on the two directions of the information signal, and unselected pixels can write their "black" or "white" states. It is usable if the state of the item is maintained. The upper and lower limits of the applied voltage and their widths (driving voltage margin ΔV) differ between liquid crystal materials and are unique. Furthermore, 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, in practice, when increasing the display surface area of such a matrix display device, 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 driving voltage margin, it will not be possible to obtain a good image over the entire display area.

[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 %formula% Structural formula Weight part Exemplary compound no.

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

n-(:,l+,,-0+OC1!2+ O-C,I+
9-n-A Next, device characteristics and the like were observed using a cell prepared using this liquid crystal M1 composition 1-B according to the following procedure.

Two glass plates with a thickness of 1.1 mm were prepared, an ITO film was formed on each glass plate, a voltage application electrode was created, and 5in2 was further deposited on this to form an insulating layer.

On this substrate, a polyimide resin precursor [manufactured by Toshi ■, SP-
710) A 1.0% dimethylacetamide solution was applied for 15 seconds using a spinner with a rotation speed of 2500 r, p, m. After the film was formed, it was subjected to a condensation firing process at 300°C for 60 minutes. The thickness of the coating film at this time was approximately 20 (one person).

After firing, the film was rubbed with acetate flocked cloth, then washed with isopropyl alcohol solution, and silica beads with an average particle size of 1.5 mm were sprinkled on one glass plate. The processing axes were made parallel to each other, glass plates were glued together using an adhesive sealant (manufactured by Chisso ■, Rixonbond), and heated and dried at +00°C for 60 minutes to create a cell. When the cell thickness of this cell was measured using a Berek phase plate, it was found that
It was about 1.5 liters long.

A ferroelectric liquid crystal element was prepared by injecting the liquid crystal composition 1-B described above in an isotropic liquid state into this cell and slowly cooling it from the isokyoshi phase to 25°C at a rate of 20°C/h.

Using this ferroelectric liquid crystal element, the driving voltage margin Δv is obtained using the driving waveform (1/3 bias) shown in FIG.
(V: l v+) was measured.

In addition, the pulse width Δt set at the time of measurement is the drive dark value voltage V + "2
It was set to 0V. At this time, ΔV, = 20
V) is the drive-to-drive value voltage pulse width, which indicates the response speed.

10°C 25°C 40°C Drive voltage Mar';> A V l: 1.8V 14.5V
12.8V (setting at the time of measurement (470 (17
0 (70 pulse width Δt) psec) gse
c) gsec) Furthermore, when the voltage is set to the median value of the drive voltage margin at 25°C and the measured temperature is changed, the temperature difference between the drive IT (hereinafter referred to as drive temperature margin) is ±4. It was 4°C.

Further, the contrast during driving at 25°C was 12.

Comparative Example 1 Instead of liquid crystal composition 1-B used in Example 1, Exemplified Compound No. 1-20.1-89 was not mixed, and Exemplified Compound No. 2-57 was used for 1-8. .2-1.65.3
12, Liquid crystal set J&, compound 1-C1 and exemplified compound No. 2, in which only 1-27 was mixed in the same parts by weight as in Example 1
Exemplary compound ¥ for 1-A without mixing -67, 2-165! 1INo, 1-20.1-89.3-12.3
Liquid crystal composition 1-D in which only -27 was mixed with Example 1 in parts by weight, and further, exemplified compound No. 1-12.3-27
Exemplary compound No. 1-2 for l-A without mixing
0.1-89.2-67°2-1.65 only in Example 1
A liquid crystal composition 1-E was prepared by mixing the same parts by weight.

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 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 I-A 9. OV 9.0V (890 interval 5ec) (248 supply 5ea) 40 ℃ 7.8v (92g5ec) 1-CIl, SV 11.8V
9.8V (710ILsec) (240#
Lsec) (85ILsec)-D 10, SV 11. Mouth V
9. OV(525gsec) (185gsec
c) (60g5ec) 12.7V
13. DV I 1.5V (520 end 5e
c) (175 tao 5 ec) (55 琲 5 ec)
Driving temperature margin 1-A ± 1.6°C 1-C ± 2.6°C 1-D ± 2.4°C 1-E ± 3. As is clear from Example 1 and Comparative Example 1, the driving margin of the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention is wider, and it can withstand changes in environmental temperature and variations in cell gap. , he has the ability to keep images in good condition.

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.

Example 2 Liquid crystal composition 2-B was obtained by mixing the following exemplified compounds in the following parts by weight with respect to the liquid crystal composition J & 1-A used in Example 1.

Exemplary compound no.

Structural formula A ferroelectric liquid crystal element was created in the same manner as in Example 1 except that this liquid crystal assembly J& was used, and the driving voltage margin was measured in the same manner as in Example 1 and the switching state etc. was observed. did. 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 (Δ constant pulse width ΔL) 10°C 25°C 40°C Drive voltage? −
Shin ΔV 13.5V 14. IV 12. O
V (Measurement setting (420 (145 (55 pulse width Δ) pscc) gsec) p
sec) Also, the driving temperature margin at 25°C is ±3
．． It was 90C.

Further, the contrast during this driving at 25° C. was 13.

Comparative Example 2 In place of liquid crystal composition 2-B used in Example 2, Exemplified Compound No. 2-10.2-69 was not mixed, and Exemplified Compound No. 1-54 was used for 1-A. .1-84.112
A liquid crystal composition 2-C was prepared by mixing only 0,3-51 with Example 2 in parts by weight.

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 (pulse width Δt set during measurement) lOoC25℃ 1-A 9. OV 9.0V (890
Color 5ec) (248μ5ec) 40℃ 7.8V (92end 5ec) -C ]0.7V 11.5V (475gse
c) (160 psec) 8.5 V (55 end 5 ee) Driving temperature margin 1-A ± 1.66C 2-C ± 2.5°C As is clear from Example 2 and Comparative Example 2, the liquid crystal composition according to the present invention The liquid crystal element having the characteristics '1' has a wider driving margin and is superior in its ability to maintain a good image against changes in environmental temperature and variations in cell gap.

Furthermore, focusing on the pulse width Δt set at the time of measurement, it can be seen that the liquid crystal Mll according to the present invention has a high strength? The temperature dependence of response speed is also reduced in the J5 conductive liquid crystal element.

Example 3 Liquid crystal composition 1-A used in Example 1 was mixed with the exemplified compounds shown below in the mixing section shown below to obtain liquid crystal composition 3-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. etc. were 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 Δt set during measurement)! 0'C25°C40°C Drive voltage? - Shin ΔV]: 1.2V 14. O
V 11.9V (, i!11 fixed time setting (6
25 (220 (85 pulse width ΔL) ILsec
) psec) psec) Also, the driving temperature margin at 25°C was ±4.00C.

Also, the contrast during this drive at 25°C is 1
There were 4.

Comparative Example 3 Instead of liquid crystal set I & 3-H used in Example 3, 1-A was used without mixing exemplified compound No. 2-5.2-176.
For example compound No. 1-17.1-49. :
A liquid crystal composition 3-C was prepared by mixing only l-:17 and 3-44 in the same weight parts as in Example 3.

Ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, except that liquid crystal compositions 3-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 Δ■ (Pulse width ΔL set during measurement) 10℃ 25℃ 40℃ 1-A 9. OV 9.
OV 7.8V (890psec)
(248gsec) (92g5ec)3-CIo
, 9V 11.7V 9.
0V (690ILsec) (230ILsec)
(80 psec) Driving temperature margin 1-A ± 1.6″c 3-C ± 2.6°C As can be seen 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 Δ 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 set I & product 4-A.

Exemplary compound no.

Structural formula Exemplary compound no.

Structural Formula Structural Formula Parts by Weight -20 Further, the following exemplary compounds were mixed with the liquid crystal composition I & 4-A in the weight parts shown below to prepare a liquid crystal composition 4-B.

-A A ferroelectric liquid crystal element was produced 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 (Pulse width ΔL set during measurement) IOoC25'C40°C Drive voltage margin ΔV 12. OV 14. :I
V13. OV (setting during measurement (345(1)
20 (45 pulse width Δt) gsec) g
sec) #Lsec) Further, the driving temperature margin at 25°C was 13.9°C.

Also, the contrast during this drive at 25°C is 1
There were two.

Comparative Example 4 In place of liquid crystal composition 4-H used in Example 4, exemplified compounds No. 2-67, 2 were added to 4-A without mixing exemplified compound No. 120.1-89. -165.312
, 3-27 in the same weight parts as in Example 4 and exemplified compound No. 4-C9 and exemplified compound No. 2-67, 2-
For 4-A without mixing 165, exemplified compound No.
1-20. Liquid crystal composition 4-D in which only l-89, 3-12, and 3-27 were mixed in the same weight parts as in Example 4, and 4 without further mixing exemplified compound No. 1-12.3-27.
-A, exemplified compound No. 1-20.1-89.
Liquid crystal composition 4-E was prepared by mixing only 2-67 and 2-165 in the same weight parts as in Example 4.

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 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 256C 4-A 7. OV lo, 0V (567 end 5ec) (160 end 5ec) 40℃ 9.0v 59 interval 5ec) 11, OV 11.5V (455t 5e
e) (150 end 5ee) io, sv (55 end 5ea) -D 9, OV 11. O.V.
9.5V (390psec) (130psec
) (45g5ec)-E 11.5V 12.8V
11. OV (380gsec) (125gsec
c) (454sec) Driving temperature margin 4-A-! : 1.7°C 2°6°C above 4-C 4-D ± 2.3°C 4-E ± 3.0°C As is clear from Example 4 and Comparative Example 4, the liquid crystal composition according to the present invention A ferroelectric liquid crystal element having a material has a wider driving margin and is superior in its ability to maintain a good image 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 Liquid crystal composition 5-B was obtained by mixing the following exemplified compounds in the following parts by weight with liquid crystal composition 4-A used in Example N4.

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 (pulse width Δt set during measurement) 10°C 25°C 40°C Drive voltage margin ΔV 12.8V 14. OV 121
V (setting during measurement (300 (105 (40 pulse width Δ) ILsec) psec)
Furthermore, the driving temperature margin at 25°C was 3° to 9°C.

Also, the contrast during this drive at 25°C is ↑
It was 3.

Comparative Example 5 In place of the liquid crystal set R & Product 5-B used in Example 5, exemplified compounds No. 1-77, 1-85. :1-29.3-
Example compound No. 2-11 was added to 4-A without mixing 38 with 2-A.
．． Liquid crystal composition 5-C was prepared by mixing only 2-148 in the same weight parts as in Example 5.

Except for using these liquid crystal compositions 5-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 (pulse width Δt set during measurement) 10°C25°C 40°C 4-A 7. OV ]O, OV
9.0V (568ILsec) (160psec)
(59ILsec)5-C10,OV
Il,, 4V ], ], 0V (510 pse
c) (1654sec) (60psec)
Driving temperature margin 4-A ± 1.7°C 3-C ± 2.5°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 has a higher driving temperature. The margins are wide, and the camera has 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.

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, and the switching state was determined. etc. were observed. The uniform alignment within this liquid crystal element is excellent;
A monodomain state was obtained. The measurement results are shown below.

Drive voltage margin ΔV (pulse width set during measurement Δ0 10'c 25'C40°C drive voltage -
Shin ΔV 13.3V 14.5V l:1.
5V (setting during measurement (410(145(+35)
Pulse width Δt) psec) gsec)
#Lsec) Furthermore, the driving temperature margin at 25°C was ±4.1°C.

Also, the contrast during this drive at 25°C is 1
It was 2.

Comparative Example 6 In place of the liquid crystal composition 6-H used in Example 6, exemplified compound No. 2-12.2-36.2-102 was mixed.
Exemplary compound No. 1-28.1- for 4-A without A
A liquid crystal composition 6-C was prepared by mixing only 95.3-36 in the same weight parts as in Example 6.

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 (pulse width Δt set during measurement) 10°C 25°C 40°C 4-A 7. OV 10. O.V.
9. OV (567gsec) (160μ5ec)
(59 psec) 6-C9, OV 10.
5V 9.5V (480ILsec)
(155ILsec) (554sec) Driving temperature margin 4-A ± 1.7°C 6-C ± 2.2°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 Elements have a wider drive margin and are better able 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 7 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal Ml composition 7-A.

Exemplary compound no.

Structural formula % Formula % Structural formula parts by weight Further, the following exemplified compounds were mixed with the liquid crystal composition % J7-A in the weight parts shown below to prepare liquid crystal composition 7-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.

Drive voltage margin ΔV (pulse width Δt set during measurement) 106C25℃ 40℃ Drive voltage margin A V 12.5V 14. O
V13. (LV(Measurement setting (320(
115 (45 pulse intensity ΔL) psec)
psec) 4sec) Furthermore, the driving temperature margin at 25°C was ±4,200.

Also, the contrast during this drive at 25°C is 1
It was 3.

Comparative Example 7 Instead of liquid crystal composition 7-H used in Example 7, exemplified compound No. 2-11 was added to 7-A without mixing exemplified compound No. 1-77, 1-85. .2-148.3-
Liquid crystal composition 7-C was prepared by mixing only 29.3-38 in the same weight parts as in Example 7.

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°C 25°C 7-A 7. OV 9.5V (504 end 5ec) (142 end 5ee) 40 °C 8.5v (54 end 5ec) -C 11, OV 12.0V (370 hiro 5ee) (+30 end 5ec) 11.5
V (50 times 5 ec) Driving temperature margin 7-A fl, 8°C As is clear from Example 7 and Comparative Example 7, the ferroelectric liquid crystal element having the liquid crystal composition according to the present invention has a wider driving margin. It has an excellent ability 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.

7-C±3.2℃ 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 (Pulse width ΔL set during measurement) 10°C 25°C 40°C Drive voltage margin ΔV 13. OV 14.5V 1:1.
2V (Measurement setting <340 (125(
50 pulse width Δt) ILsec) 4se
c) psec) Furthermore, the driving temperature margin at 25°C was 4° above 40°C.

Further, the contrast during this driving at 25° C. was 13.

Comparative Example 8 In place of the liquid crystal composition 8-H used in Example 8, exemplified compounds No. 1-12.1-57.2-76, 2-93.
Exemplary compound No. 3-24. was added to 7-A without mixing 2-143. :A liquid crystal composition 8-C was prepared by mixing only 1-40 in the same weight parts as in Example 8.

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

Drive voltage margin ΔV (set pulse width Δ during measurement) 10℃ 25℃40℃ 7-A 7. OV9.5V
8.5V (5044sec) (142gsec)
(54ILsec)8-C8,5V Io
, 3V 10.0V (450ILsec)
(150 psec) (55 psec) Driving temperature margin 7-A ± 1.8°C 2°4°C on B-C As is clear from Example 8 and Comparative Example 8, the ferroelectric liquid crystal having the liquid crystal composition according to the present invention The driving margin of the element is wide, and the Ie ability to maintain a good image 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.

Examples 9 to 16 In place of the exemplified compounds and liquid crystalline mJ&m used in Example 1, the exemplified compounds and liquid crystalline compositions shown in Table 1 were used in respective parts by weight to obtain the liquid crystalline properties of 9-B to 16-B. A composition was obtained. A ferroelectric liquid crystal element was prepared in the same manner as in Example 1 except for using these, and the driving voltage margin was measured in the same manner as in Example 1, and the switching state etc. were observed.

Uniform alignment within each liquid crystal element created was good;
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, focusing on the pulse width ΔL 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 excellent, and a monodomain state was obtained. The measurement results are shown below.

Drive voltage margin Δ■ (Pulse width Δt set during measurement) 10°C25°C 1-B 14.4V 14.8V (455
psec) (170gsec) -A ■ -E 9.5V 9.8V (870 interval 5ec) (240psec) 12,
OV 12.2V (700)zsec)
(2:15μ5ec) 10.8V
11.0V (505ILsec) (180gs
ec) 12.8V 1:1. :IV(5
1,0 psec) (17511,5 ec) Driving temperature margin 1-B Upper 4゜7℃ 1-A ± 1.8℃ 1-C Upper 2゜9”C I-D Upper 2゜5℃ 1-E ± 3 .6℃ 40℃ +3.OV (754sec) 8.3v (90 end 5ea) 10, OV (85 colors 5ec) 9, Ov (60psec) 11.9V (70ILsec) As is clear from Example I7, the element configuration Even when the ferroelectric liquid crystal composition according to the present invention is changed, the driving margin of the device having the ferroelectric liquid crystal composition according to the present invention is widened as in Example 1 compared to the device having other liquid crystal compositions, and even when It is excellent in how to maintain a good image despite variations in the image quality.

Furthermore, when focusing on the pulse width Δ 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 driving voltage margin, and a certain degree of temperature variation over the display area of the element. It is also possible to obtain a liquid crystal element with a wide driving temperature margin that allows all pixels to be satisfactorily driven in matrix, 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 3... Transparent electrode 5... Spacer 7... Power source 9... Light source ■... Transmitted light 21a... Substrate 21b... Substrate 22...
-Liquid crystal molecule layer 23...Liquid crystal molecule 24...Dipole moment (P): 11a, :Ilb...Voltage application means 2...Glass substrate 4...Insulating alignment control layer 6...・Lead wire 8...Polarizing plate ■. ...Incoming light 33a...First stable state 33b...Second stable state 34a...Upward dipole moment 34b...Downward dipole moment Ea...Upward electric field Eb... downward electric field

Claims (2)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are linear or branched alkyl groups of C_1 to C_1_8, and C_1 as a substituent
It may have an alkoxy group of ~C_1_2. However, both R_1 and R_2 are not n-alkyl groups. X_1 and X_2 are single bonds, -O-, ▲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,
At least one compound represented by the following general formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_3 and R_4 represent substituents. C that may have
_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 the compounds represented by ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼ and at least one of 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.
_1 to C_1_8 linear or branched alkyl group,
X_5 and X_6 are single bonds, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z_2 is -CH_
Indicates 2O- or -OCH_2-. 1. A ferroelectric chiral smectic liquid crystal composition, characterized in that it contains at least one compound represented by the formula (m and n are 1 or 2). (2) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are linear or branched alkyl groups of C_1 to C_1_8, and C_1 as a substituent
It may have an alkoxy group of ~C_1_2. However, both R_1 and R_2 are not n-alkyl groups. X_1 and X_2 are single bonds, -O-, ▲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,
At least one of the compounds represented by the following general formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_3 and R_4 represent substituents. C that may have
_1 to C_1_8 linear or branched alkyl group,
X_3, 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 the compounds represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼), and at least one of the following general formulas (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.
_1 to C_1_8 linear or branched alkyl group,
X_5 and X_6 are single bonds, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z_2 is -CH_
Indicates 2O- or -OCH_2-. m, n are 1 or 2) A ferroelectric chiral smectic liquid crystal composition containing at least one compound represented by the following formula is disposed between a pair of electrode substrates.