JPH0312489A - Ferroelectric chiral smectic liquid crystal composition and liquid crystal element containing same - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing plural compounds expressed by specific structural formulas and a liquid crystal compound having a negative dielectric anisotropy, excellent in switching characteristics, having a large driving voltage margin and suitable as optical shutters, etc. CONSTITUTION:The objective composition, containing (A) at least one compound expressed by formula I (R1 is 1-18C alkyl which may have a substituent group; R2 is 1-14C alkyl which may have a substituent group; X1 and X2 are single bond, -O-, formula II, etc.; m is 0-7; n is 0 or 1), (B) at least one compound expressed by formula III (R3 and R4 are 1-18C alkyl which may have a substituent group; X3 and X4 are single bond, -O-, formula IV, etc; Y1 is -CH2O- or -OCH2-; p and q are 1 or 2) and (C) at least one liquid crystal compound having a negative dielectric anisotropy ( epsilon) (preferably epsilon<-2).

Description

[Detailed Description of the Invention] [Technical Field] 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 liquid crystal composition and a liquid crystal element containing the same.

[Background technology]

Conventionally, liquid crystals have been applied as electro-optical elements in various fields. Most of the liquid crystal elements currently in practical use are, for example, those described in "Applied Physics Letters" by M, 5chadt and W, He1frich.
Vo, 18, No. 4 (1971, 2, 15), P
, 127-128 Voltage-8pendent
0Ptical Activity of
aTwisted Nematic Liquid
TN (twisted) shown in Crysta
This uses a nematic type liquid crystal.

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 applications in large flat display systems, driving by a simple matrix method is the most promising in terms of cost, productivity, etc. In the simple matrix method, an electrode configuration is adopted in which a scanning electrode group and a signal electrode group are arranged in a matrix.
To drive this, a time-division drive method is adopted in which address signals are selectively and periodically applied to the scanning electrode group, and predetermined information signals are selectively applied in parallel to the signal electrode group in synchronization with the address signal. be done.

However, if the above-mentioned TN type liquid crystal is used as an element of such a driving method, there will be an area 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 (the so-called "half area"). A finite electric field is also applied to the 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 threshold required to align the liquid crystal molecules perpendicular to the electric field is set to an intermediate voltage value, the display The element operates normally, but when the number of scanning lines (N) is increased, the entire screen (
The time during which an effective electric field is applied to one selected point (duty ratio) decreases at a rate of 1/N while scanning one frame. For this reason, (the voltage difference as an effective value applied to the selected point and non-selected point when repeated scanning is performed is
As the number of scanning lines increases, the size becomes smaller, resulting in unavoidable drawbacks such as a reduction in image contrast and crosstalk.

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). ) 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.

In order to improve the drawbacks of conventional liquid crystal elements, the use of bistable liquid crystal elements has been proposed for C1ark and L
proposed by Agerwall (Japanese Unexamined Patent Application Publication No. 1983-1999)
107216, US Pat. No. 4,367,924, etc.). As the bistable liquid crystal, a ferroelectric liquid crystal having a chiral smectic C phase (SmC*) or H phase (SmH*) 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 similar to the optical modulation element used in the above-mentioned TN type liquid crystal. 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. Further, 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. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied electric field directly act to induce a transition in the orientation state, which is 3 to 4 orders of magnitude faster than the response speed due to the effect of the dielectric anisotropy and 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 overcome, 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.

In the case of a simple 7-trix 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 59-193 disclose
No. 427, No. 60-1!56046 and No. 60
The driving method disclosed in Japanese Patent No.-156047 and the like 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 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 disposed between the scanning line 52 and the data line 53 at the intersection.

In FIG. 4(A), S indicates the selection scanning waveform applied to the selected scanning line, SN indicates the non-selected scanning waveform, and ■ indicates the selection information waveform applied to the selected data line. (black) and IN represents a non-selection information signal (white) applied to an unselected data line. Also, in the figure (Is
Ss) and (IN Sg) are the voltage waveforms applied to the pixels on the selected scanning line, and the pixels to which the voltage (Is Ss) is applied assume a black display state, and the voltage (IN Sg)
The pixel to which S) is applied assumes 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 l line clear 1. The phase time is set to 2Δt.

Now, each parameter Vg t of the drive waveform shown in FIG.
The value of vl +Δt is 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 drive voltage (Vs+V+) is changed while keeping the bias ratio constant, which will be described later. Here, △t=
so μs, bias ratio v, /(Vl +v3)=l/
It is fixed at 3. The positive side of Figure 7 is shown in Figure 4 (
IN SS), and the waveform shown as (Is ss) is applied to the negative side. Here, V I + vl are respectively referred to as an actual drive threshold voltage and a crosstalk voltage (=switching failure voltage). However, V2<V, <V3) and △v
” (v s - V 1 ) is called the voltage margin,
This is the voltage width that allows matrix drive. It can be said that vl exists in boat fishing due to the FLC matrix drive.

Specifically, this is the voltage value that causes switching due to vh in the waveform of FIG. 4(A) (IN SS). Of course, it is possible to increase the value of vl by increasing the bias ratio, but increasing the bias ratio means increasing the amplitude of the information signal, which reduces flickering in terms of image quality. This is undesirable because it increases the bias ratio and reduces the contrast.In 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 △V will depend on the switching characteristics of the liquid crystal material. 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 by changing the two directions of the information signal, and unselected pixels can write the "black" or "white" state into the selected pixel. The upper and lower limits of the applied voltage that can maintain the state and their width (drive voltage margin △V = V
, -V,) differs among liquid crystal materials and is 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 expanding the display area of such a matrix display device, the difference in the environment in which the liquid crystal exists in each pixel (specifically, the temperature and the cell gap difference between electrodes) naturally increases, and the driving With liquid crystals that have a small voltage margin, it is not possible to obtain a good image over the entire display area.

On the other hand, it is known that ferroelectric liquid crystals aligned under such conditions generally connect the upper and lower substrates in a twisted state and do not exhibit -axial alignment (spray alignment). One of the problems in such a case is that the transmittance of the liquid crystal layer is low.

Assuming that the molecular orientation is uniaxial, the amount of transmitted light has an intensity of I relative to the intensity of the incident light I0 under crossed Nicol conditions.

Here, Δn is the refractive index anisotropy, d is the cell thickness, λ is the wavelength of the incident light, and θa is the angle between bistable states (tilt angle).

When the above cell is used and spray orientation is adopted, θa is currently 5° to 8°. Control of Δndπ/λ cannot be easily performed in terms of physical properties, so it is desirable to increase θa to increase I, but this is difficult to achieve using static alignment techniques.

It is known that θa can be expanded by using the torque of the Δε term of the ferroelectric liquid crystal to solve such problems (published by ATT at SID in 1983, JP-A-61-245142.61- 246722.61-2
46723.61-246724.61-249024
．． 6l-249025).

When Δε of the liquid crystal is negative, the liquid crystal molecules tend to become parallel to the substrate due to the application of an electric field. Taking advantage of this property, i.e.
By applying a constant effective electric field even during switching, it is possible to eliminate this twisted arrangement, increase θa, and increase the transmittance (AC stabilization effect).

Acting on FLC molecules regarding state switching (torque r
Ps and AC stabilizing effect on FLC molecules (torque rΔ) are each proportional to the following physical properties.

r'Ps oOPs-E rΔ,oo Δε ・ε.・E!・・・・・・
(3) As is clear from equation (3), Δε of FLC
It can be seen that the sign and absolute value of play a very important role.

V of four types of FLC with different values of physical properties regarding Δε
FIG. 8 shows the change in θa with respect to r m s.

The measurements were performed using a 60 KHz rectangular alternating current to eliminate the influence of Ps.

(I) is Δe unit, 5, (II) is Δey-3, 0° (III) is Δε knee o, (rv) is Δε two i,
o, and qualitatively Δε is (I) < (n) < (m
)<(rV).

As can be seen from the graph, θa becomes large at extremely low voltages where Δε is large in the negative, and therefore it can be seen that it contributes to I.

Comparing the difference in transmittance when using (I) and (m), there was a clear difference between 15% for (I) and 6% for (III) (60KHz±8v (when applying a square wave).

As is known from the above examples, the display characteristics of SS FLC can be greatly changed by controlling the physical properties of Δε and Ps.

In order to make the Δε of the ferroelectric liquid crystal composition negative,
It is most effective to mix materials with a negative Δε and a large absolute value. For example, a compound with a large Δε can be obtained by introducing a halogen or cyano group in the short axis direction of the molecule, or by introducing a petero atom into the molecular groove skeleton.

The dielectric anisotropy of a compound where Δε<O varies depending on the structure. An example is shown below.

ε　く2 2≦ ε1 ≦ 5 N vinegar 5<181<10 N ε　　　　　　　　10 vinegar *R, R' represent an alkyl group.

Broadly classified, compounds with 1ε1≦20Δε1 small);
Compounds with 2×1ε1≦10 (in lΔε1), 1Δεl
>10 (lΔε 1 large). 1
A small Δεl has almost no effect on increasing IΔε1. A material with 1Δε greater than 1 is a very effective material for increasing 1Δε. At present, dicyanohydroquinone derivatives are the only 1Δε1 material.

However, dicyanohydroquinone derivatives have 1Δ
Although the effect of increasing ε1 is large, since the viscosity is high, an increase in the content ratio tends to worsen the switching characteristics.

On the other hand, among those with moderate 1Δεi, the 1Δε increasing effect is smaller than the 1Δε [large component, but some have low viscosity to some extent.

From the above, it is clear that the switching characteristics are good and the A
In order to obtain a liquid crystal composition having a C stabilizing effect and a liquid crystal element containing the same, a compound having negative dielectric anisotropy,
Preferably] Δε1>2, the selection of compounds, mixing partners and mixing ratios should be (preferably).

(J2f"T #White) [Problems to be Solved by the Invention] The present invention aims at making a ferroelectric liquid crystal element practical, by providing a device with a large driving voltage margin and a certain degree of temperature variation in the display area of one liquid crystal element. The object of the present invention is to provide a chiral smectic liquid crystal composition with a wide driving temperature margin that allows all pixels to be satisfactorily driven in matrix, and to provide a liquid crystal element using the liquid crystal composition and the liquid crystal composition.

Another object of the present invention is to further mix a liquid crystal compound having negative dielectric anisotropy into the liquid crystal composition of the present invention.
It is an object of the present invention to provide a liquid crystal composition and a liquid crystal element that have a C stabilizing effect and greatly improve display characteristics.

[Means for solving the problem] The present invention is based on the following general formula (I) (wherein R1 is a linear or branched alkyl group which may have a C1 to CIII substituent, and R2 is a C1 to CIII substituent group). '
= straight-chain or branched alkyl group optionally having a substituent of CI4, Xl +
) (However, R3 and R4 are linear or branched alkyl groups that may have C1 to CII substituents, and Yl is -
It is characterized by containing at least one compound represented by CH20- or -OCH2-1p, where q is l or 2, and a small amount (at least one kind) of a liquid crystalline compound having negative dielectric anisotropy. The present invention provides a ferroelectric chiral smectic liquid crystal composition and a liquid crystal element formed by disposing the liquid crystal composition between a pair of electrode substrates.

(The following is a blank space) Further, in the present invention, the liquid crystalline compound having negative dielectric anisotropy preferably exhibits Δε<-2, more preferably Δε<-5,
More preferably, the present invention provides a ferroelectric chiral smectic liquid crystal composition which is further contained in the ferroelectric chiral smectic liquid crystal composition using a liquid crystal compound exhibiting Δε<-10, and a liquid crystal element having the same.

Further, the present invention provides the ferroelectric chiral smectic liquid crystal using a compound selected from the following general formulas (■-■) to (■-■) as the liquid crystalline compound having negative dielectric anisotropy. The present invention provides a ferroelectric chiral smectic liquid crystal composition, which further contains a ferroelectric chiral smectic liquid crystal composition, and a liquid crystal element having the same.

−Slaughter (■−■) General formula (■−■) (Re.

R1 is a linear or branched alkyl group which may have a substituent, or [R1゜Rh is a linear or branched alkyl group which may have a substituent, r is ÷.

building/ single bond, however As.

AI cannot be a single bond at the same time. ] General formula (■−■) Aa.

If both Abs are single bonds, Xb.

Xc is a single bond and X.

Xd is both a single bond or both is 10-, (AI is a single bond, -(U→Al is a single bond, +R+, and R1 is a straight chain or branched Ya that may have a substituent.

Yb is Cyano group.

halogen.

Hydrogen, an alkyl group, however, when AI is a single bond, a straight chain alkyl Ya
.

Yb cannot become hydrogen at the same time. ] is a kill group, and z is -0 or Sl - slaying However, A When is a single bond, XI is a single bond, [Rt.

Rm is a straight chain or public chain that may have a substituent. ÷ When xI is not a single bond branch alkyl group, When A is a single bond, XIc is a single bond. ]Ak.

AI cannot be a single bond at the same time.

(Margin below) X, -,,/ -CM2CH2- -C=C-) General formula (■−■) (Rn.

Ro is a linear or branched alkyl group which may have a substituent, -OCH2- -CH2CH2- Among the compounds represented by the above general formula (1), preferred examples of compounds include XI+ x2 as shown below ( 1-i)～(
I-iv).

(1-i) Xl is a single bond, x2 is -〇-
(I-ii) X (is a single bond, x2 is -0C-
(1-iii) XH is a single bond, x2 is -CO
-(1-iv)Xl is 10-1X2 is 10-Also, R1+
A more preferable example of R2 is a linear alkyl group having 1 to 14 carbon atoms.

Among the compounds represented by the above-mentioned general formula (II), preferred compound examples include the following (II-a) to (II-
f) Compounds represented by the formula can be mentioned.

R3-x3-◎-CH20-◎-X4-R4 (1-a)
R3-X3-◎-0CH2-◎-X4-R4(I-b)
R, -X3-◎-CH20←◎-◎-x4-R4(I-
c) R, -X3-◎-OCH20+◎-X4-R4(1
-d) R3-X3-◎-◎-CH2o-◎-X4R4(
I-e) R3-X3-◎-◎-〇CH2-◎-X4-R
4(I-f) Also, the above-mentioned (II-a) to (II
Preferred examples of X 3 * X 4 in formula -f) include (II-i) to (II-viii).

x3 is a single bond, X4 force single bond (I 1) x3
is a single bond, X4 is a single bond, X4 is -Co-(I-iii)X3
is a single bond, x4 is -QC-(1-4v)X3
is -〇-1x4 is a single bond (I-
v) x3 is 10-1x4 is 10-(I-vi) X3 is 10-1x4 is -Co-(1-vii) X3 is 10-1x
4 is 100-(I-viii), and furthermore, the above-mentioned (I-viii)
R3 in formulas I-a) to (II-f). Preferred examples of R4 include (II-iX) to (II-xii
i).

(II-xi) (II-xii) * (p is O~7, R6 is a linear or branched alkyl group) Un(p, q is O~7, R,, R6 is a straight chain or branched alkyl group) chain or branched alkyl group) R3 is an n-alkyl group.

R4 is -CH2-CH-CrH2r+1-n* (r is 1 to 12) R3 is an n-alkyl group.

An example of a specific structural formula of a liquid crystalline compound represented by (S is O to 7, t is O or 1.R, is a linear or branched alkyl group) is shown below. show.

H3 l-36 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) 1.06 5-methoxyhexanol dissolved in 5 ml of pyridine
g (8,0 m m+)1 ) and 1.83 g of p-toluenesulfonic acid chloride dissolved in 5 ml of pyridine (
9.6 mmol) was added dropwise at 5° C. or lower in ice water. After stirring for 6 hours at room temperature, the reaction mixture was poured into 100 ml of 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-) Luenesulfonate was obtained.

Dimethylformamide 1 Ornj! 5-decyl-2-
(p-hydroxyphenyl)pyrimidine 2.0g (6,
41 mm, add 0.61 g of potassium hydroxide,
Stirred at 0°C for 40 minutes. To this was added the previously obtained 5-methoxyhexyl-p-toluenesulfonate, and 100
The mixture was heated and stirred at ℃ for 4 hours. After the reaction was completed, the reaction mixture was poured into 100 ml 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-
1.35 g of (5'-methoxyhexyloxy)phenyl)pyrimidine (exemplified compound No. 21) was obtained.

Phase transition temperature ('C) Synthesis Example 2 (Synthesis of compound No. 1-25) 2.04 g of 6-bentyloxyhebutanol was added to 8 mj of pyridine.
! After cooling on ice, 2.26 g of tosyl chloride dissolved in 5 ml of pyridine was gradually added dropwise (below 5°C,
7 minutes). Thereafter, the mixture was stirred at room temperature for 5 hours.

The reaction mixture was poured into 150 ml of ice water, adjusted to pH approximately 3 with 6N aqueous hydrochloric acid, and extracted with ethyl acetate. This was washed with water, dried over anhydrous magnesium sulfate, and then 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)pyrimidine and 0.53 g of potassium hydroxide were dissolved in 14 ml of dimethylformamide, heated and stirred at 100°C for 3 hours, and then (6-pentyloxyheptyl) p
-) luenesulfone) was added, and 10
The mixture was heated and stirred at 0°C for 5 hours.

The reaction mixture was poured into 200 mA 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 the solvent was distilled off to obtain 4.71 g of a crude product. This was purified by silica gel column chromatography (n-hexane/ethyl acetate = 10/2)
After that, it was further recrystallized from hexane to give 5-n-decyl-2-[4-(6-pentyloxyhebutyloxy)
1.56 g of phenyl]pyrimidine was obtained.

IR (cm-') 2924.2852, 1610, 1586, 1472° 1436.1254, 1168, 1096. 798 Phase transition temperature ('C) 22.7 33.3 J
So. For compounds other than 6 Synthesis Examples, use the following synthetic route A.
.

It can be obtained by B.

Synthetic Route A An example of a specific structural formula of the compound represented by the above-mentioned -sakuhatsu (I[) is shown below.

Synthetic route B (R1, R2, X 1 , m, and n are as described above) The compound represented by -Sakuhatsu (I[) is described, for example, in JP-A No. 60-149547 (1985), JP-A No. 60-149547 (1985); Showa 6l-6
3633 (1986).

Typical synthesis examples are shown below.

Synthesis Example 1 (Synthesis of Compound No. 2-54) The following alcohol derivative C6H,30-@)- was placed in a 30 ml eggplant flask.
Add 1.0 g (4.81 mmol) of CH20H, add 3 ml of thionyl chloride under cooling, raise the temperature to room temperature while stirring, then attach a cooling tube and heat under reflux at an external temperature of 70°C to 80°C for 4 hours. Ta. After the reaction, excess thionyl chloride was distilled off to obtain a chloride. This is 15mj of toluene? dissolved in.

Next is 200mj? Put 0.33 g of 60% oily sodium hydride into a three-neck flask, wash it several times with dry n-hexane, and add 1.52 g of the following phenol derivative (4,81
mmol) THF solution 15mj! Soak at room temperature and add 20 mj? of DMSO. 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 16 hours at room temperature.

After the reaction is complete, pour into approximately 200ml of ice water, separate the organic layer, and add 50ml of benzene to the aqueous layer. Extracted twice at
The previously separated organic layer was washed twice with a 5% aqueous hydrochloric acid solution, then once with ion-exchanged water, and then once with a 5% aqueous NaOH solution, and then washed with ion-exchanged water until the pH value of the aqueous layer became neutral. The organic layer was washed with water.

The organic layer was taken out, dried using magnesium sulfate, and the solvent was distilled off to obtain a crude product. Add this to the developing solution n-hexane/
Purification was performed by silica gel column chromatography using dichloromethane, 3/10.

The crystals obtained by distilling off the solvent were recrystallized using n-hexane to obtain the purified target product. Further, the product was dried under reduced pressure at room temperature to obtain 0.69 g of the final purified target product. The yield was 28.5%.

Elemental analysis value (wt%) CHN Calculated value 78.33 8.57 0.00 Measured value 78.96 8.69 0.02 Phase rearrangement synthesis example 2 (synthesis of compound No. 2-68) 30mj? Put 1.25 g (4.01 mmol) of the following alcohol derivative c8H,,o ((Sawa◎zuH20H) into an eggplant flask, add 4 ml of thionyl chloride under cooling, raise the temperature to room temperature while stirring, and then attach a cooling tube. , 4 at an external temperature of 70°C to 80°C
Heat reflux was performed for a period of time. After the reaction, excess thionyl chloride was distilled off to obtain a chloride. This was dissolved in 15mf of toluene.

Next, 0.31 g of 60% oily sodium hydride was placed in a 200 ml three-necked flask, washed several times with dry n-hexane, and then 0.79 g of the following phenol derivative (4,0
1 mmol) of THFHF solution was added to the mixture at room temperature, and 20 ml of DMSO was added thereto and stirred for 1 hour. to this,
Slowly drop the toluene solution of chloride mentioned above,
After the dropwise addition was completed, stirring was continued for 16 hours at room temperature.

After the reaction was completed, it was poured into about 200 ml of ice water, the organic layer was separated, and the aqueous layer was extracted twice with 50 mf of benzene. After washing with the previously separated organic layer twice with 5% aqueous hydrochloric acid, the ions were extracted. After washing once with exchanged water and once with 5% NaOH aqueous solution, the organic layer was washed with ion-exchanged water until the pH value of the aqueous layer became neutral.

The organic layer was taken out, dried using magnesium sulfate, and the solvent was distilled off to obtain a crude product. Add this to the developing solution n-hexane/
Purification was performed by silica gel column chromatography using dichloromethane, 3/10.

The crystals obtained by distilling off the solvent were recrystallized using n-hexane to obtain the purified target product. Further, drying was carried out under reduced pressure at room temperature to obtain 0.5-1 g of the final purified target product.

was 26.0%.

CHN analysis value (wt%) CHN calculated value 78.33 8,63 0.00 Theoretical value 78.62 8,86 0.02 Phase dislocation yield Examples of specific structural formulas of liquid crystalline compounds are shown below. however,(
In formula m), the number of carbon atoms in the alkyl group represented by each R is 1 to
18, preferably 4-16, more preferably 6-12.

General formula (■−■) XR spectrum 2975° 1510° 1280° 1020° S2. S.

2925° 1470° 1240° i　oooo.

(Left below) is unidentified 2850, 1610゜1380, 1295゜1220, 1130゜810 cm -■) The following margin is one square cm -■) General formula (■-■) N N The following margin N N N N N N N N N N (3-i68) N The liquid crystal composition of the present invention has the above general formula (I) It can be obtained by mixing at least one compound represented by formula (n), at least one compound represented by the general formula (n), and one or more other liquid crystal compounds in appropriate proportions.

A liquid crystal composition for another purpose of the present invention can be obtained by further mixing at least one liquid crystal compound having negative dielectric anisotropy in an appropriate ratio to the above liquid crystal composition.

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.

[, -≧ (hereinafter blank) The compounding ratio of each of the liquid crystal compounds and one or more of the other liquid crystal compounds mentioned above, or a liquid crystal composition containing the same (abbreviated as liquid crystal material), is based on the present invention, per 100 parts by weight of the liquid crystal material. 1) It is preferable that each of the liquid crystalline compounds represented by (II) be 1 to 300 parts by weight, more preferably 2 to 100 parts by weight.

Furthermore, even when using two or more of the liquid crystal compounds represented by the general formula (1) or -sakatsu (I[) of the present invention, the proportions of the liquid crystal compounds with other liquid crystal materials may vary depending on the liquid crystal material as described above. Per 100 parts by weight, 1 to 500 parts by weight, more preferably 2 to 100 parts by weight of any or a mixture of two or more of the liquid crystalline compounds represented by the present invention - Sekuri (I) and - Sekuri (II). It is preferable to use parts by weight.

Furthermore, the weight ratio of the liquid crystalline compound represented by the general formula (I[) to the liquid crystalline compound represented by -Sakatsu (I) [-Sakatsu (I)/-Sakatsu (■)] is from 1/300 to 300/1. , preferably from 1/50 to 50/1.

When using two or more of each of the liquid crystalline compounds represented by the general formula (ri5, -Sabatsu (n), -Sabatsu (1)/-Sabatsu (n),
n) is from 11500 to 500/1, preferably 1
A ratio of 150 to 50/1 is desirable.

Further, the compounding ratio of the liquid crystal compound represented by -Keruretsu (1), the total amount of the liquid crystal compound represented by -Kakeru (n), and the above-mentioned liquid crystal material is -Kakeru (I) and -Kakeru (II) ), it is desirable that the amount of other liquid crystal materials be 2 to 600 parts by weight, preferably 4 to 200 parts by weight.

Furthermore, when using two or more of each of the liquid crystalline compounds represented by -Kabatsu (I) and -Kabatsu (n), -Kabatsu (I)
The total amount of the liquid crystal compound represented by the general formula (I) and the orientation ratio of the liquid crystal material described above are as follows:
-Per 100 parts by weight of the total amount of -Sakatsu (I) and -Sakatsu (n),
2 to 1000 parts by weight, preferably 4 parts by weight of the above-mentioned liquid crystal material
It is desirable to set it as 200 parts by weight.

Furthermore, the content of the component with negative dielectric anisotropy in the ferroelectric liquid crystal composition containing the component with negative dielectric anisotropy is 1
~98% by weight. In particular, when using a component with Δε<-2, the content of the component with Δε<-2 is desirably 1 to 70% by weight, preferably 1 to 60% by weight.

A liquid crystal compound represented by the general formula (1) and
) and the component with negative dielectric anisotropy in the ferroelectric liquid crystal composition of the present invention.
Contains ~100% by weight.

The dielectric anisotropy of the liquid crystalline compound having negative dielectric anisotropy used in the present invention is preferably 1ε1>2.

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

In FIG. 1, 1 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 are each made of In2O3゜SnO.
2 or ITO (Indium-Tin Oxid
A transparent electrode made of a thin film such as e) is coated. On top of this, a thin film of a polymer such as polyimide is rubbed with gauze or acetate flocked cloth to form an insulating alignment control layer that aligns the liquid crystals in the rubbing direction. Insulating materials such as silicon nitride, hydrogen-containing silicon carbide, silicon oxide, boron nitride, hydrogen-containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, and fluoride An inorganic insulating layer such as magnesium is formed, and then polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyvaraxyone, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin is formed on the insulating layer. An insulating orientation control layer may be formed of two layers, using an organic insulating material such as melamine resin, yurya resin, acrylic resin, or photoresist resin as the orientation control layer, or an insulating orientation control layer of an inorganic material or an organic insulating material. It may be a single layer of 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 using a solution in which an organic insulating substance is dissolved or its precursor solution (solvent 0.1 to 20% by weight, preferably 0.5% by weight). 2-10% by weight
) using a spinner coating method, dip coating method, screen printing method, spray coating method, roll coating method, etc.
It can be cured and formed under predetermined curing conditions (for example, under heating).

The thickness of the insulating orientation control layer is usually 30 to 1 μm, preferably 30 to 3000, more preferably 50 to 1 μm.
000 people is suitable.

These two glass substrates 2 are kept at an arbitrary distance by a spacer 5. For example, using silica beads or alumina beads with a predetermined diameter as spacers, the glass substrate 2
There is a method in which the material is held between two sheets and the surrounding area 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 in which the ferroelectric liquid crystal is sealed is generally 0.5 to 20 μm, preferably 1 to 5 μm.

In addition, this ferroelectric liquid crystal has an S m C* phase (chiral smectic C phase) in a wide temperature range including room temperature (especially on the low temperature side), and when used as an element, the driving voltage margin and driving temperature A wide margin is desirable.

In addition, in order to exhibit good uniform alignment and obtain a monodomain state especially when used as an element, the ferroelectric liquid crystal has to undergo a transition from the tokiyoshi phase to the ch phase (cholesteric phase) - SmA phase (smectic A phase) - SmC *phase (chiral smectic C
It is desirable to have a phase transition series called phase).

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 transparent 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 In2O3, 5n02 or ITO (Indiu
A substrate (glass plate) coated with a transparent electrode made of a thin film such as m-Tin oxide), between which a liquid crystal molecular layer 22 is oriented perpendicular to the glass surface.
A liquid crystal of phase or SmH' phase is sealed. A thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 2
3 is the dipole moment (P±
)24. When a voltage higher than a certain threshold is applied between the electrodes on the substrates 21a and 21b, the helical structure of the liquid crystal molecules 23 is unraveled, and the liquid crystal molecules 23 are aligned in the direction such that all the dipole moments (P) 24 are directed in the direction of the electric field. can be changed. The liquid crystal molecules 23 have an elongated shape and exhibit refractive index anisotropy in the long axis direction and short axis direction,
Therefore, it is easily understood that, for example, if crossed Nicol polarizers are placed above and below a glass surface, a liquid crystal optical modulation element whose optical characteristics change depending on the polarity of applied voltage can be obtained.

The thickness of the liquid crystal cell preferably used in the optical modulation element of the present invention can be made sufficiently thin (for example, 10μ or less).As the liquid crystal layer becomes thinner in this way, as shown in FIG. Even when no electric field is applied, the helical structure of the liquid crystal molecules unravels, and the dipole moment Pa or pb takes either an upward (34a) or downward (34b) state. When an electric field Ea or Eb of different polarity above a certain threshold value is applied by the voltage applying means 31a and 31b as shown in FIG. Accordingly, the liquid crystal molecules are oriented in either the first stable state 33a or the second stable state 33b.

As mentioned above, there are two advantages to using such ferroelectricity 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 with reference to FIG. 3, for example, when the electric field Ea is applied, the liquid crystal molecules are oriented in a first stable state 33a, and this state remains stable even when the electric field is turned off. Furthermore, when an electric field Eb in the opposite direction is applied, the liquid crystal molecules are oriented to the second stable state 33b and change their orientation, but they remain in this state even after the electric field is turned off. Also, the electric field E
As long as a or Eb does not exceed a certain threshold, the respective previous orientations are maintained.

When a simple matrix display device is constructed using a device in which a ferroelectric liquid crystal material having such characteristics is sandwiched between a pair of substrates,
For example, Japanese Unexamined Patent Publication No. 59-193426, No. 59-19
Publication No. 342.7, Publication No. 60-156046 and Publication No. 6
The driving method disclosed in Japanese Patent No. 0-156047 and the like 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. A scanning line 52 and a data line 63 are marked on the panel 51 in FIG. 6 so as to cross each other, and a ferroelectric liquid crystal is arranged between the scanning line 52 and the data line 53 at the intersection. There is.

83 in FIG. 4(A) is the selection scanning waveform applied to the selected scanning line, SN is the non-selected scanning waveform that is not selected, and ■8 is the selection information waveform applied to the selected data line ( IN represents a non-selection information signal (white) applied to an unselected data line. Also, in the figure (I
s Ss) and (INSS) 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 voltage (INSS) is applied to the pixels on the selected scanning line.
) to which the pixel is applied assumes 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 1-line clear t1 phase is 2Δt. It is set to t.

Now, each parameter V, , V of the drive waveform shown in FIG.
, , Δt is 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 drive voltage (Vs+V+) is changed while keeping the bias ratio, which will be described later, constant. Here, △t=50 μs, bias ratio V+ /
(V+ +Vs) = l/3 is fixed. 7th
The positive side of the figure is shown in Figure 4 (IN-3s), and the negative side is (I
s Ss) is applied. Here vl,
v3 is called an actual drive threshold voltage and a crosstalk voltage (also called a switching failure voltage because it is reversed when VSVI exceeds V). However, V2<V
, <Va) Also, ΔV=(V3 Vl) is called a voltage margin, and is a voltage width that allows matrix drive. It can be said that v3 exists in boat fishing due to the FLC matrix drive. Specifically, it is the voltage value that causes switching due to ve in the waveform of FIG. 4(A) (IN SS). Of course, it is possible to increase the value of v3 by increasing the bias ratio, but increasing the bias ratio means increasing the amplitude of the information signal, which reduces flickering in terms of image quality. This is undesirable as it increases the bias ratio and decreases the contrast.In our study, the bias ratio is 1/3 to 1/4.
The degree was 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 a selected pixel depending on the two directions of the information signal, and non-selected pixels can write the "black" state into the selected pixel.
Or the upper and lower limits of the applied voltage that can maintain the "white" state and their widths (drive voltage margin △V)
is different and unique among liquid crystal materials. The drive margin also decreases due to changes in the environmental temperature (because
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 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.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, 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-
I created A.

Exemplified Compound No., Structural Formula: Exemplary Compounds 1-5 and 2-6 were mixed with the liquid crystal composition 1-A in the following parts by weight to obtain a liquid crystal composition 1-B.

Exemplary Compound No. Structural Formula % Formula % Next, optical responses were observed using cells prepared using these liquid crystal compositions according to the following procedure.

Two glass plates with a thickness of 1 mm and 1 mm were prepared, an ITO film was formed on each glass plate to create a voltage application electrode, and SiO2 was further vapor-deposited thereon to form an insulating layer.

On this substrate, a polyimide resin precursor [Toshi ■ 5P-51
0] 1.0% dimethylacetamide solution at 30 revolutions
Coating was performed for 15 seconds using a 00r, p, m spinner. After the film was formed, a heating condensation firing process was performed at 300° C. for 60 minutes. The thickness of the coating film at this time was about 120 people.

This fired coating was rubbed with acetate flocked cloth, then washed with isopropyl alcohol solution, and silica beads with an average particle size of 1.5 μm were sprinkled on one glass plate. so that they are parallel to each other, and apply adhesive sealant [Rixon Bond (
Glass plates were glued together using Nisso (Japanese) and dried by heating at 1000C for 60 minutes to create a cell. The cell thickness of this cell was measured using a Bereck phase plate and was approximately 1
- It was 5 μm.

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 △v with the driving waveform (1/3 bias) shown in FIG.
(V3 V, ) was measured. The results are shown below (
Note that △t is set to be V 2 # 15V).

10°C 25°0 40°C Drive voltage margin 12. OV 12.5V
9.5V (setting at measurement △t) (735u
5ec) (225u 5ec) (90u 5e
c) Further, when the voltage was set to the median value of the drive voltage margin at 25°C and the measurement temperature was changed, the driveable temperature difference (hereinafter referred to as drive temperature margin) was ±3.4°C.

Furthermore, the contrast during this drive at 25°C is 10
It was hot.

Comparative Example 1 Liquid crystal composition 1 in which only exemplary compound No. 2-6 was mixed with 1-A without mixing exemplary compound No. 1-5 of liquid crystal composition 1-B used in Example 1. Liquid crystal composition 1-D in which only exemplary compound No. 1-5 was mixed with 1-A without mixing -C and exemplary compound No. 2-6
It was created.

Instead of using liquid crystal composition 1-B, liquid crystal composition 1-A,
A ferroelectric liquid crystal device was prepared in the same manner as in Example 1, except that 1-C and 1-D were injected into the cell, and the driving voltage margin ΔV was measured.The results are shown below. .

Drive voltage margin (measurement setting △t) 10℃ 25℃40℃ 1-A 9. OV 9.5V 8
．． 5V (1050μ5ec) (280μ5ec)
(78μ5ec) 1-CIo, 5V 10
．． 5V 9.0V (895μ5ec) (
255μ5ec) (76μ5ec) 1-D
Io, 5V lO, 5V 9.0V (
900μ5ec) (260μ5ec) (7
7μ5ec) Furthermore, the driving temperature margin at 25℃ is ±2.2℃ at l-A,! ±2.6℃ at −C,! -D was ±2.5°C.

As is clear from Example 1 and Comparative Example 1, the ferroelectric liquid crystal element containing the liquid crystal composition 1-B according to the present invention has a wider driving margin and is less susceptible to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

Example 2 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal composition 2-
I created A.

Exemplary compound no.

Structural formula % Formula % Exemplary compound 1-5゜2- for this liquid crystal composition 2-A
6 in the following parts by weight, respectively, to prepare liquid crystal composition 2-B.
I got it.

Exemplary compound no.

A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that structural formula liquid crystal composition 1-B was replaced with this liquid crystal composition 2-B.
The driving voltage margin ΔV was measured in the same manner as in Example 1, and the switching state and the like were observed.

The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10℃ 25℃ 40℃ Drive voltage margin 12.5V 13. OV 10.
OV (Measurement setting △t) (700μ5ec)
(210p 5ec) (90μ5ec) Furthermore, 2
The driving temperature margin at 5°C was ±3.6°C. Further, the contrast during this driving at this temperature was 9.

Comparative Example 2 Liquid crystal composition 2 in which only exemplary compound No. 2-6 was mixed with 2-A without mixing exemplary compound No. 1-5 of liquid crystal composition 2-H mixed in Example 2. Liquid crystal composition 2-D in which only exemplary compound No. 1-5 was mixed with 2-A without mixing -C and exemplary compound No. 2-6
It was created.

Instead of using liquid crystal composition 1-B, liquid crystal composition 2-A,
A ferroelectric liquid crystal device was prepared in the same manner as in Example 1, except that 2-C and 2-D were injected into the cell, and the driving voltage margin ΔV was measured.The results are shown below. .

Drive voltage margin (setting △t during measurement) 10℃ 25℃ 40℃2-A
Io, 5V 10.5V 8.5
V (1200μ5ec) (330μ5ec)
(98μ5ec)2-C11,OV
11.5V 9.0V (1060μ5ec
) (320μ5ec) (96μ5ec)
2-D 10.5V 10.5V
8.5V (1020μ5ec) (300μ
5ec) (915μ5ec) Furthermore, the driving temperature margin at 25℃ is ±2.5℃ at 2-A, 2-
It was ±2.8°C for C and ±2.5°C for 2-D.

As is clear from Example 2 and Comparative Example 2, the ferroelectric liquid crystal element containing the liquid crystal compound 2-B according to the present invention has a wider drive margin, and is less susceptible to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

, etc. (blank below) Example 3 Liquid crystal composition 2-A used in Example 2 was mixed with 1 part of the exemplified compounds shown below to prepare liquid crystal composition 3-A. I got a B.

Exemplary Compound No. Structural Formula A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that this compound was used, and the drive 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.

10°C 25°0 40°C drive! Pressure?
-Jin 12. OV 13. OV10
．． 5V (setting △t during measurement) (720μ5ec)
(210μ5ec) (92μ5ec) 25 more
The driving temperature margin in °C was ±3.4 °C.

Also, the contrast during this drive at this temperature is 8
Met.

Comparative Example 3 Liquid crystal composition 3 in which only exemplary compound No. 1-20 was mixed with 2-A without mixing exemplary compound No. 2-14 of liquid crystal composition 3-H used in Example 3. Liquid crystal composition 3-D in which only exemplary compound No. 2-14 was mixed with 2-A without mixing -C and exemplary compound No. 1-20
It was created.

Instead of using liquid crystal composition 1-B, liquid crystal composition 2-A,
A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that 3-C and 3-D were injected into the cell, and the driving voltage margin ΔV was measured. The results are shown below.

Drive voltage margin (measurement setting △t) 10℃ 25℃ 40℃2-A I
o, 5V 10.5V 8.5V (
1200a 5ec) (330u 5ec)
(98u 5ec)3-C11,5V 1
0.5V 8.5V (1050μ5ec)
(330μ5ec) (98μ5ec) 3-D
12. OV 11. OV 9.
0V (1000a 5ee) (310a 5ee)
) (95tt 5ee) Furthermore, the driving temperature margin at 25℃ is ±2.5℃ for 2-A and ±2 for 3-C.
．． It was ±2.7°C at 5°C and 3-D.

As is clear from Example 3 and Comparative Example 3, the ferroelectric liquid crystal element containing the liquid crystal composition 3-B according to the present invention has a wider driving margin and is less susceptible to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

(The following is a blank space) Example 4 The following exemplified compounds were mixed with the liquid crystal composition 2-A used in Example 2 in the parts by weight shown below to obtain a liquid crystal composition 4-B.

Exemplary Compound No. Structural Formula A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that this compound was used, and the drive 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.

10℃ 25℃ 40℃ Drive voltage margin 12.5V 13. OV 9.5
V (setting at measurement △t) (760μ5ec) (
210p 5ec) (72μ5ec) further 25℃
The driving temperature margin was ±3.6°C. Also, the contrast during this drive at this temperature is 11
Met.

Comparative Example 4 Liquid crystal composition 4 in which only exemplary compound No. 1-10 was mixed with 2-A without mixing exemplary compound No. 2-18 of liquid crystal composition 4-B used in Example 4. Liquid crystal composition 4-D was prepared by mixing only exemplary compound No. 2-18 with 2-A without combining -C and exemplary compound No. 1-10t-fi.

Instead of using liquid crystal composition 1-B, liquid crystal composition 2-A,
A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that 4-C and 4-D were injected into the cell, and the driving voltage margin ΔV was measured. The results are shown below.

Drive voltage margin (setting △t during measurement) 10℃ 25℃ 40℃ 2-A 9. OV9.5V
8.5V (1000μ5ec) (265μ5ec)
(75μ5ec) 4-CIo, 5V 1
0. OV 8.2V (880μ5ec)
(240usec) (75μ5ec) 4-D
Io, 5V 10. OV 8.5
V (910μ5ec) (245p 5ec)
(75μ5ec) Furthermore, the driving temperature margin at 25℃ is ±2.3℃ for 2-A, ±2.7℃ for 4-C,
-D was ±2.5°C.

As is clear from Example 4 and Comparative Example 4, the ferroelectric liquid crystal element containing the liquid crystal composition 4-B according to the present invention has a wider driving margin and is less susceptible to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

Example 5 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal composition 5-A.

c4HgOCI 2CI , O@-Coo@@-COO
C,+(,.

(Margin below) C+oH110@-CODGQC,)I,.

Exemplary compound no.

Structural formula: Exemplary compounds 1-20 and 2-14 were mixed with the liquid crystal composition 5-A in the following parts by weight, respectively, to obtain liquid crystal compositions 5 and -B.

Exemplary compound no.

A ferroelectric liquid crystal element was prepared in the same manner as in Example 1 except that structural formula liquid crystal composition 1-B was replaced with this liquid crystal composition 5-B.
The driving voltage margin ΔV was measured in the same manner as in Example 1, and the switching state and the like were observed.

The uniform alignment within this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10℃ 25℃ 40℃ Drive voltage margin! 0.7V 11. O.V.
7.2V (setting at measurement △t) (300μ5
ec) (90μ5ec) (35μ5ec) Furthermore, the driving temperature margin at 25℃ is ±2.9℃
Met. Further, the contrast during this driving at this temperature was 9.

Comparative Example 5 Liquid crystal composition 5 in which only exemplary compound No. 1-20 was mixed with 5-A without mixing exemplary compound No. 2-14 of liquid crystal composition 5-B mixed in Example 5. - C and
Liquid crystal composition 5 in which only exemplary compound No. 2-14 was mixed with 5-A without mixing exemplary compound No. 1-20
-D was created.

Liquid crystal composition instead of using liquid crystal composition 1-B! 5-A
, 5-C and 5-D were injected into the cell, a ferroelectric liquid crystal device was prepared in the same manner as in Example 1, and the driving voltage margin ΔV was measured.The results are shown below. show.

Drive voltage margin (measurement setting △t) 10℃ 25℃ 40℃5-A
8. OV 8. OV 6.0V (
400μ5ec) (110p 5ec)
(40μ5ec)5-C8, OV 8.5
V 6.2V (3601, tsec)
(100μ5ec) (35μ5ec)5-D
8. OV 8.7V 6.
0V (330μ5ec) (100μ5ec)
(35μ5ec) Furthermore, the driving temperature margin at 25℃ is ±1.9℃ for 5-A and ±2.1℃ for 5-C.
It was ±2.2°C at 5-D.

As is clear from Example 5 and Comparative Example 5, the ferroelectric liquid crystal element containing the liquid crystal composition 5-B according to the present invention has a wider driving margin and is less susceptible to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

Example 6 Liquid crystal composition 5-A used in Example 5 was mixed with the following exemplified compounds in the weight parts shown below to obtain liquid crystal composition 6-B.

Exemplary Compound No. Structural Formula Using this, a ferroelectric liquid crystal device was prepared in the same manner as in Example 1, the drive 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.

10℃ 25℃ 40℃ Drive voltage margin lO, 2V 10.6V 7. O
V (Measurement setting △t) (310p 5ec)
(95μ5ec) (35μ5ec) further 25℃
The driving temperature margin was ±2.8°C. Also, the contrast during this drive at this temperature is 10
Met.

Comparative Example 6 Exemplary compound No. of liquid crystal composition 6-B used in Example 6. For 5-A without mixing 2-18, liquid crystal composition 6-C mixed with only exemplified compound No. 1-10 and for 5-A without mixing exemplified compound No. 1-10 A liquid crystal composition 6-D was prepared by mixing only exemplary compound No. 2-18.

Instead of using liquid crystal composition 1-B, liquid crystal composition 5-A,
A ferroelectric liquid crystal device was prepared in the same manner as in Example 1, except that 6-C and 6-D were injected into the cell, and the driving voltage margin ΔV was measured.The results are shown below. .

Drive voltage margin (setting △t during measurement) io℃ 25℃ 40℃ 2-A 8. OV 8. O.V.
6.0V (400μ5ec) (110μ5ec)
(40μ5ec)6-C8,OV8.
5V 6.1V (360μ5ec) (1
00μ5ec) (40μ5ec)6-D
8. OV 8.5V 6.0V (35
0μ5ec) (100At5ec) (40
μ5ec) Furthermore, the driving temperature margin at 25℃ is
5-Ate+1.9°C, 6-Ct'+2.1°C, 6-D+-2.1°C.

As is clear from Example 6 and Comparative Example 6, the ferroelectric liquid crystal element containing the liquid crystal composition 6-B according to the present invention has a wider driving margin and is less susceptible to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

Example 7 Liquid crystal composition 5-B used in Example 5 and Comparative Example 5.

A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that 5-C, 5-D, and 15-A were made using only polyimide resin without using 5i02. The driving voltage margin was measured in the same manner as in Example 1. The results are shown below.

Drive voltage margin (setting △t during measurement) 10℃ 25℃ 40℃ 5-B lO, 9V 11.3V
7.7V (290μ5ec) (90μ5e
c) (40μ5ec)5-C8,OV
8.7V 6.4V (340μ5ec)
(100μ5ec) (40μ5ec)5-D
8.2V 8.7V 6.2V
(320μ5ec) (100μ5ec) (
40μ5ec) 5-A 8-2V
8.3V 6.3V (370μ5ec)
(1001t 5ec) (40μ5ec) Furthermore, the driving temperature margin at 25℃ is 5-B ±3
．． 1°C 5-C ±2.2°C 5-D ±2.3°C 5-A ±2.0°C.

As is clear from Example 7, even when the element configuration is changed, the element containing the ferroelectric liquid crystal composition 5-B according to the present invention has the same performance as in Example 5 compared to the element containing other liquid crystal compositions. The drive margin is wide, and the ability to maintain good images despite changes in environmental temperature and variations in cell gap is excellent.

Examples 8 to 13 In place of the exemplified compounds and liquid crystal compositions used in Example 1.2.5, each part by weight of the exemplified compounds and liquid crystal compositions shown in Table 1 was used to prepare 8-B-13-B. A liquid crystalline composition was obtained. A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except for using these, and the drive margin at 25° C. was measured in the same manner as in Example 1, and the switching state and the like were observed.

Uniform alignment within each liquid crystal element produced was good;
A monodomain state was obtained. The measurement results are shown in Table 1.

Example 14 Liquid crystal composition 14-B was obtained by mixing the following exemplified compounds in the weight parts shown below with respect to liquid crystal composition 1-B used in Example 1.

A ferroelectric liquid crystal element was prepared in the same manner as in Example 1, except that a liquid crystal composition of Exemplified Compound Nα Structural Formula: 2 parts by weight was used, and the drive voltage margin ΔV was measured.

10℃ 4℃40℃ Drive voltage margin 11.5V 12.5V
9.5V (setting △V during measurement) (770μ5
ec) (250 μ5 ec) (90 μ5 ec) Furthermore, using the above liquid crystal element, the tilt angle was measured under crossed Nicols at 25° C., and found to be 8.2°. Next, the tilt angle was measured while applying a ±8v square wave at a frequency of 60 KHz, and found to be 13.1°. When the transmittance was measured at this time, it was 13.5%. At the same time, the contrast ratio was measured and found to be 68:1.

Comparative Example 14 Instead of Liquid Crystal Composition 1-B, Liquid Crystal Composition 14-C was prepared by adding the aforementioned Na3-10 compound to Liquid Crystal Composition 1-A in the same ratio as in Example 14.

Ferroelectric liquid crystal elements were prepared using these liquid crystal compositions 14-C, 1-A, and 1-B in the same manner as in Example 1, and the driving voltage margin ΔV was measured.

Furthermore, the tilt angle was measured in the same manner as in Example 14. The results are shown below.

Drive voltage margin (measurement setting △t) 10℃ 25℃ 40℃1-A
9. OV9.5V
8.5V (1050μ5ec) (280μ5e
c) (78μ5ec)1-B 12
．． OV 12.5V 9.5
V (735μ5ec) (225μ5ec)
(90μ5ec)14-C8,OV
9. OV 9.0V (1300u 5ec
) (310a 5ec) (83μ5ec
) Tilt angle (25℃) Initial tilt angle When AC stabilizing (no electric field) (When applying 60KHz, ±8V square wave) 1-A 7.5° 7.8° 1-B
7.6° 7.8614-C7,
7° 13.3° As is clear from Example 14 and Comparative Example 14, by mixing a liquid crystal compound with negative dielectric anisotropy with the liquid crystal composition according to the present invention, the driving margin was widened and Furthermore, it has been found that when used in a display method based on AC stabilization effect, the display characteristics are significantly improved.

Example 15 Liquid crystal composition 15-B used in Example 1 was mixed with the following exemplified compounds in the weight parts shown below to obtain liquid crystal composition 15-B.

Exemplary compounds Structural formula Parts by weight (
Blank space below) Exemplary compound Nα Structural formula A ferroelectric liquid crystal device was prepared in the same manner as in Example 1, except that this liquid crystal composition was used, and the drive voltage margin ΔV was determined in the same manner as in Example 1. It was measured.

10°C 25°C 40°C Drive voltage margin 12. OV 12. OV10
．． OV (setting △V during measurement) (745μ5ec)
(240 μ5 ec) (90 μ5 ec) Furthermore, when the tilt angle was measured under crossed Nicols at 25° C. using the above liquid crystal element, it was 8.5°. Next 60K
When the tilt angle was measured while applying a square wave of ±8 V at a frequency of Hz, it was found to be 13.0°. When the transmittance was measured at this time, it was 13.7%. At the same time, the contrast was 61:l.

Comparative Example 15 Instead of liquid crystal composition 1-B, liquid crystal composition 1-A was added with the above (
7) Nn3-90. 3-12. 3-122. 3-
70. Liquid crystal composition 15- containing the compound 3-1073-111.3-167 in the same ratio as Example 15
Created C.

Using these liquid crystal compositions 15-C, i-A, and 1-B, ferroelectric liquid crystal elements were prepared in the same manner as in Example 1, and the driving voltage margin ΔV was measured.

Furthermore, the tilt angle was measured in exactly the same manner as in Example 14. The results are shown below.

Drive voltage margin (setting △V during measurement) 10°0 25℃ 40℃1-A
9. OV 9.5V 8.
5V (1050 μsec) (280 μsec
) (78 μsec) 1, - B 1
2. OV 1 2.5V 9.5V (
735μsec) (225μsec) (g
□μsec) 8, 5V 9. O.V.
9. OV (1170, CZ sec) (32
0 1t sec) (85 μsec) Tilt angle (25°C) Initial tilt angle At AC stabilization (no electric field) (When applying 60 KHz, ±8v square wave) 1-A 7.5° 7.8.

1-B 7.6° 7 8.

8.3° 13.0.

As is clear from Example 15 and Comparative Example 15, by mixing a liquid crystal compound with negative dielectric anisotropy into the liquid crystal composition of the present invention, the driving voltage margin was widened and
Furthermore, it has been found that when used in a display method based on AC stabilization effect, the display characteristics are significantly improved.

As is clear from Examples 8 to 15, the ferroelectric liquid crystal elements containing liquid crystal compositions 8-B to 15-B according to the present invention have wide driving margins and are resistant to changes in environmental temperature and variations in cell gap. It has an excellent ability to maintain good image quality.

Further, as is clear from Examples 14 and 1.5, when the ferroelectric liquid crystal elements containing the liquid crystal compositions 14-B and 15-B according to the present invention are used in a display method based on the AC stabilization effect, the display characteristics has been significantly improved.

〔Effect of the invention〕

The device containing the ferroelectric liquid crystal composition of the present invention has good switching characteristics and a wide drive voltage margin (even if there is a certain degree of temperature variation in the display area of the device, all pixels can be maintained at 7 trix). A liquid crystal element with a wide driving temperature margin can be obtained.

Furthermore, by containing a liquid crystalline compound having negative dielectric anisotropy in the ferroelectric liquid crystal composition having the specific compound of the present invention, in addition to having the above-mentioned characteristics, display by an AC stabilizing effect can be achieved. A liquid crystal element with significantly improved characteristics can be obtained.

[Brief explanation of drawings]

Figure 1 is a schematic cross-sectional view of an example of a liquid crystal display element using ferroelectric liquid crystal, and Figures 2 and 3 schematically represent an example of an element cell to explain the operation of a ferroelectric liquid crystal element. A perspective view, FIG. 4 is a waveform diagram of the driving method used in the examples, FIG. 5 is a plan view of a ferroelectric liquid crystal panel with matrix electrodes arranged, and FIG. 6 is shown in FIG. 4 (B). Figure 7 is a schematic diagram of the display pattern when actual driving is performed using time-series driving waveforms.
Figure 8 shows the change in transmittance when the driving voltage is changed, that is, the V-T characteristic diagram.
FIG. In Fig. 1, 1... Ferroelectric liquid crystal layer 2...
......Glass substrate 3...
......Transparent electrode 4...
...Insulating orientation control layer 5 ......
・・・・・・Spacer 6・・・・・・・・・・・・・・・
・・・・・・Lead wire 7・・・・・・・・・・・・・・・
・・・・・・Power supply 8・・・・・・・・・・・・・・・・・・
・・Polarizing plate 9・・・・・・・・・・・・・・・・・・・
Light source ■0・・・・・・・・・・・・・・・・・・Incoming light I・・・・・・・・・・・・・・・・・・Transmitted light In Fig. 2, 1a 1b In Figure 3, 1a Substrate Substrate Ferroelectric liquid crystal layer Liquid crystal molecule dipole moment (on P) Voltage application means 1b 3a 3b 4a 341] a b Voltage application means First stable state Second stable state Upward dipole Child moment: Downward dipole moment: Upward electric field: Downward electric field (A) S. vb group inasa awesome O ΔΣ'1ste lameter toteru (4 bugs ~)

Claims (6)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, R_1 is a linear or branched alkyl group that may have a substituent of C_1 to C_1_8. , R_2
is a linear or branched alkyl group that may have substituents C_1 to C_1_4, X_1 and X_2 are single bonds,
-O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, m is 0 to 7, n is 0 or 1), and at least one of the following general formulas (II) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (However, , R_3, R_4 are linear or branched alkyl groups that may have substituents of C_1 to C_1_8, X_3, X_4 are single bonds, -O-, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, Y_1 is -CH
_2O- or -OCH_2-, p and q are 1 or 2), and further contains at least one liquid crystalline compound having negative dielectric anisotropy (Δε). Characteristic ferroelectric chiral smectic liquid crystal composition. (2) The liquid crystal compound with negative dielectric anisotropy is Δε<−2
The ferroelectric chiral smectic liquid crystal composition according to claim 1. (3) The liquid crystal compound with negative dielectric anisotropy is Δε<−5
3. The ferroelectric chiral smectic liquid crystal composition according to claim 2. (4) The liquid crystal compound with negative dielectric anisotropy is Δε<−1
4. The ferroelectric chiral smectic liquid crystal composition according to claim 3, wherein the ferroelectric chiral smectic liquid crystal composition is 0. (5) Claim 1, wherein the liquid crystalline compound having negative dielectric anisotropy is selected from compounds represented by the following general formulas (III-[1]) to (III-[5]). The ferroelectric chiral smectic liquid crystal composition according to item 4. General formula (III-[1]) ▲Mathematical formulas, chemical formulas, tables, etc.▼ [R_a, R_b are linear or branched alkyl groups that may have substituents, X_a, X_d are single bonds, -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼,
X_b, X_c are single bonds, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_
2CH_2-, A_a, A_b are single bonds, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (trans), ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
(Trans/Trans), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Trans), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ If A_a and A_b are both single bonds, X_b, X_c
is a single bond, and X_a and X_d are both single bonds or both -O-, or X_a is ▲There is a mathematical formula, chemical formula, table, etc.▼ and X_d is ▲There is a mathematical formula, chemical formula, table, etc. It is ▼. Y_a and Y_b are a cyano group, halogen, and hydrogen; however, Y_a and Y_b cannot be hydrogen at the same time. ] General formula (
III-[2]) ▲Mathematical formulas, chemical formulas, tables, etc.▼ [R_e, R_f are linear or branched alkyl groups that may have substituents, X_e, X_h are single bonds, -O- ,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,
X_f, X_g have ▲mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, single bond, A_e,
A_f has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, single bond, but A_e, A
__f cannot be a single bond at the same time. ] General formula (III-[
3]) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [A_i is a single bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, A_j is a single bond, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_i, R_j are linear or branched alkyl groups that may have substituents, however, when A_j is a single bond, it is a linear alkyl group, and Z_1 is -O Or S, X_i, X_k 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.▼, X_j is a single bond,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, -CH_2O-, -OCH_2-,
However, when A_j is a single bond, X_i is a single bond, and A
When __j is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, then X_j is not a single bond, and when A_j is a single bond, X_k is a single bond. ] General formula (III-[4]) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [R_l, R_m are linear or branched alkyl groups that may have substituents, A_l, A_m are single bonds, ▲ There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, but A
_k and A_l cannot be a single bond at the same time. X_l is a single bond, -O-, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, X_m is a single bond, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas,
Chemical formulas, tables, etc. are available▼, -CH_2O-, -OCH
_2-, -CH_2CH_2-, -C≡C-] General formula (III-[5]) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R_n, R_o are linear or branched chains that may have substituents The alkyl group, X_n,
X_o, X_p are single bonds, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_
2O-, -OCH_2-, -CH_2CH_2-, A_n, A_p are single bonds, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, A_o is ▲ mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, Z_2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼] (6) A liquid crystal device comprising the ferroelectric chiral smectic liquid crystal composition according to claim 1 disposed between a pair of electrode substrates.