JP3005064B2 - Liquid crystal composition, liquid crystal element having the same, display method and display device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal composition, a liquid crystal device using the same, and a display method using the same.
More specifically, the present invention relates to a display device, more specifically, a novel liquid crystal composition having improved response characteristics to an electric field, and a liquid crystal device used for a display device or a liquid crystal-light shutter using the same, and the liquid crystal device used for display. The present invention relates to a display device.

[0002]

BACKGROUND OF THE INVENTION The use of liquid crystals having bistability has been addressed by Clark and Lagerwell.
11) (JP-A-56-10721).
No. 6, US Pat. No. 4,367,924, etc.).

[0003] Bistable liquid crystals are generally chiral smectic C phase (SmC ^* phase) or H phase (SmH ^* phase).
Is used.

The ferroelectric liquid crystal has a bistable state composed of a first optically stable state and a second optically stable state with respect to an electric field. Are different, for example, the first for one electric field vector
The liquid crystal is oriented in the optically stable state, and the liquid crystal is oriented in the second optically stable state with respect to the other electric field vector. In addition, this type of liquid crystal takes one of the above two stable states in response to an applied electric field, and maintains the state when no electric field is applied (bistability).
Having.

[0005] In addition to the characteristic having bistability as described above, the ferroelectric liquid crystal has an excellent characteristic of high-speed response. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied electric field act directly to induce a transition of the alignment state.
It is 3 to 4 orders of magnitude faster than the response speed due to the effects of dielectric anisotropy and electric field.

As described above, the ferroelectric liquid crystal potentially has extremely excellent characteristics. By utilizing such characteristics, it is possible to solve many of the problems of the conventional TN type device. Improvement is obtained. In particular, application to high-speed optical shutters and high-density, large-screen displays is expected.

In the case where the above-described simple matrix display device is constituted by an element in which the ferroelectric liquid crystal layer is sandwiched between a pair of substrates, for example, JP-A-59-193426, JP-A-59-193427, and JP-A-59-193427. The driving methods disclosed in JP-A-60-156046 and JP-A-60-15647 can be applied.

FIGS. 4 and 5 are waveform diagrams of the driving method used in the embodiment of the present invention. FIG. 6 is a plan view of a ferroelectric liquid crystal panel 61 in which the matrix electrodes used in the present invention are arranged. 6, a scanning line 62 and a data line 63 are wired so as to cross each other, and a ferroelectric liquid crystal is arranged between the scanning line 62 and the data line 63 at the intersection.

In FIG. 4, S _S represents a selected scanning waveform applied to a selected scanning line, S _N represents a non-selected scanning waveform which is not selected, and I _S represents a selection information waveform applied to a selected data line. (black), I _N represents the non-selection information signal applied to the data line which is not selected (white). In the drawing, (I _S -S _S ) and (I _N -S _S ) are voltage waveforms applied to the pixels on the selected scanning line, and the pixels to which the voltage (I _S -S _S ) is applied are black. take the display state, the pixel voltage (I _N -S _S) is applied takes the display state of white.

FIG. 5 shows the driving waveforms shown in FIG. 4 and the time-series waveforms when the display shown in FIG. 7 is performed.

In the driving examples shown in FIGS. 4 and 5, the minimum application time Δt of the single polarity voltage applied to the pixels on the selected scanning line corresponds to the time of the writing phase t ₂ , and one line clear t ₁ The phase time is set to 2Δt.

The values of the parameters V _S , V _I and Δt of the drive waveforms shown in FIGS. 4 and 5 are determined by the switching characteristics of the liquid crystal material used.

FIG. 8 shows the transmittance T when the drive voltage (V _S + V _I ) is changed while a bias ratio described later is kept constant.
, Ie, the VT characteristic. Here, Δt = 50 μsec, bias ratio V _I / (V _I + V _S ) =
Fixed to 1/3. Positive side of Figure 8 is shown in FIG. 4 (I _N -S _S), the negative side waveform shown by (I _S -S _S) is applied.

Here, V ₁ and V ₃ are called an actual drive threshold voltage and a crosstalk voltage, respectively. Also, V ₂ <V ₁ <V ₃
At this time, ΔV = V ₃ −V ₁ is called a voltage margin, which is a voltage width in which matrix driving is possible. It can be said that V ₃ generally exists in driving the FLC display element. In particular,
A voltage value causing switching by V _B in the waveform of FIG. 4 (I _N -S _S). Of course, it is possible to increase the value of V ₃ by increasing the bias ratio, increasing the bias ratio corresponds to a large amplitude of a data signal, an increase in flickering in image quality, contrast Is undesirably caused.

According to 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 having a large ΔV is very advantageous for matrix driving.

At such a certain temperature, "black" and "white" are applied to the selected pixel depending on the two directions of the information signal.
And the width (drive voltage margin ΔV) of the upper and lower limits of the applied voltage at which the unselected pixel can maintain its “black” or “white” state. Is unique among liquid crystal materials.
In addition, since the driving margin is deviated by the change in the environmental temperature, it is necessary to set the driving voltage to an optimum value for the liquid crystal material and the environmental temperature in an actual display device.

However, when the display area of such a matrix display device is expanded for practical use, the difference in the environment in which the liquid crystal exists in each pixel (specifically, the difference in the temperature and the cell gap between the electrodes) is naturally large. Therefore, a liquid crystal having a small drive voltage margin cannot obtain a good image over the entire display area.

[0018]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional liquid crystal element, and is expected to be applied to a high-speed optical shutter, a high-density, large-screen display. In order for the device to be practical, it is easily aligned by a simple rubbing process, exhibits uniform monodomain alignment without defects, has a large driving voltage margin, and has a certain degree of temperature variation on the display area of the liquid crystal device. It is an object of the present invention to provide a liquid crystal composition having a wide driving temperature margin in which all pixels can be favorably driven in a matrix, a liquid crystal element using the liquid crystal composition, and a display device using the same.

[0019]

According to the present invention, there is provided a compound represented by the following general formula (I):

[0020]

[Outside 40] (However, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 18 carbon atoms, and these may have an alkoxy group having 1 to 12 carbon atoms as a substituent.
R ₁ and R ₂ are both non-optically active. Z ₁ is a single bond,

[0021]

[Outside 41] Is shown. And at least one liquid crystal compound represented by the following general formula (II)

[0022]

[Outside 42] (However, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 18 carbon atoms, and these are CH ₃ as a substituent.
O- group may have a C ₅ H ₁₁ O- group, or F-.
Z ₂ and Z ₃ are single bonds,

[0023]

[Outside 43] It is. A ₁ is -A ₂ -or -A ₂ -A _3- , wherein A _{2 and} A ₃ are

[0024]

[Outside 44] It is. And a liquid crystal composition containing at least one liquid crystal compound represented by the following general formula (III):

[0025]

[Outside 45] (However, R ₅ is a linear or branched alkyl group having 1 to 18 carbon atoms and may have a C ₆ H ₁₃ O— group as a substituent. Y is a single bond,

[0026]

[Outside 46] And a liquid crystal composition containing at least one liquid crystal compound represented by the formula: And a liquid crystal element and a display device in which the liquid crystal composition is disposed between a pair of electrode substrates.

Among the liquid crystal compounds represented by the general formula (I), preferred compounds include compounds represented by the following (Ia) to (Ib).

[0028]

[Outside 47] (Wherein, R ₁ and R ₂ are as described above)

In the liquid crystal compound represented by the formula (I), preferred examples of R ₁ and R ₂ are (Ii) to (Ii).
(I-iii).

(Ii) an n-alkyl group having 1 to 16 carbon atoms

[0031]

[Outside 48] (However, m is an integer of 0 to 7 and n is an integer of 1 to 9, but is in the range of 2 ≦ m + n ≦ 14.)

[0032]

[Outside 49] (However, r is an integer of 0 to 7, and s is 0 or 1
It is. Also, t is an integer of 1 to 14, but 1 ≦ r + s
+ T ≦ 14. )

Among the liquid crystal compounds represented by the general formula (II), preferred compounds are the following (IIa) to (Ia).
Ie) Compounds of the formula

[0034]

[Outside 50] (In the formula, R ₃ , R ₄ , Z ₂ , and Z ₃ are as described above.)

Further, more preferred R ₃ and R ₄ are the following (I
Ii) to (II-iv).

(II-i) n- having 2 to 16 carbon atoms
An alkyl group, more preferably n- having 4 to 14 carbon atoms.
Alkyl group

[0037]

[Outside 51] (However, m 'is an integer of 0 to 7, and n' is an integer of 1 to 9. Further, it may be optically active.)

[0038]

[Outside 52] (However, r 'is an integer of 0 to 7, s' is 0 or 1, and t' is an integer of 1 to 14. It may be optically active.)

[0039]

[Outside 53] (However, p 'is 0 or 1, x' is an integer of 1 to 14. * indicates an asymmetric carbon.)

Among the compounds represented by the above general formula (III), preferred examples of the compound include the following formula (I)
Compounds represented by II-a) to (III-f) are included.

[0041]

[Outside 54]

Further, the above formulas (III-a) to (III)
Among the compounds represented by -f), particularly preferred examples of the compound include compounds represented by the formulas (III-a), (III-b) and (I-I).
II-c).

Further, the above formulas (III-a) to
Preferred examples of Z ₄ and Z ₅ in (III-f) include the following (III-i) to (III-v). (III-i) Z ₄ is a single bond, Z ₅ is -O-CH _2- (III-ii) Z ₄ is a single bond, Z ₅ is -COO-CH
_{2 - (III-iii) Z} 4 is a single bond, Z ₅ is -OCO- (III-iv) Z ₄ is -O-, Z ₅ is _{-O-CH 2 - (III-} v) Z 4 is -O -, Z ₅ is -COOCH ₂
−

A typical synthetic route of the liquid crystal compound represented by the general formula (I) is shown below.

[0045]

[Outside 55] (Wherein R ₁ , R ₂ and Z ₁ are as described above)

Next, typical synthesis examples of the liquid crystal compound represented by the general formula (I) are shown below.

Synthesis Example 1 (Synthesis of Compound No. 1-22)

[0048]

[Outside 56]

3.00 g (9.60 mmole) of 2- (4-hydroxyphenyl) -5-decylpyrimidine, 1.70 ml (9.74 mmole) of nonanoic acid and 100 ml of methylene chloride were dissolved in a 300 ml eggplant flask and dissolved at room temperature. While stirring, 2.00 g (9.69 mmole) of N, N'-dicyclohexcarbodiimide and 0.17 g of 4-pyrrolidinopyridine were sequentially added. Thereafter, the mixture was stirred at room temperature for 4 hours, and the precipitated N, N'-dicyclohexylurea was removed by filtration. The filtrate was evaporated to dryness under reduced pressure, and the residue was purified by silica gel column chromatography using toluene as an eluent, and recrystallized from an acetone-methanol mixed solvent to give 2- (4-
Nonanoyloxyphenyl) -5-decylpyrimidine (3.78 g, yield 87.0%) was obtained.

Phase transition temperature (° C.)

[0051]

[Outside 57]

Specific examples of the liquid crystal compound represented by formula (I) are shown below.

[0053]

[Outside 58]

[0054]

[Outside 59]

[0055]

[Outside 60]

[0056]

[Outside 61]

[0057]

[Outside 62]

[0058]

[Outside 63]

[0059]

[Outside 64]

[0060]

[Outside 65]

A typical synthetic route of the liquid crystal compound represented by the general formula (II) is shown below.

[0062]

[Outside 66]

[0063]

[Outside 67]

[0064]

[Outside 68]

[0065]

[Outside 69]

Next, typical synthetic examples of the liquid crystal compound represented by the general formula (II) are shown below.

Synthesis Example 2 5-hexylthiophene-2-carboxylic acid-4- (5-
Dodecyl-2-pyrimidinyl) phenyl (exemplary compound N
o. 2-53) Production

[0068]

[Outside 70]

I) Preparation of 2-hexanoylthiophene In a 5 l 5-neck flask, 187.3 g of thiophene (2.
23 mol), 300 g of n-hexanoyl chloride
(2.23 mol), 2.7 liters of dry benzene,
Cooled to below 0 ° C. Under stirring, SnCl ₄ 237.9
g (9.13 × 10 ^-1 mol) was added dropwise at 0 ° C. or lower over 1 hour. After stirring at the same temperature for 30 minutes, the mixture was reacted for 3 hours and 30 minutes while gradually returning to room temperature.

After completion of the reaction, 2 l of 10% HCl was added,
After stirring for 10 minutes, the benzene layer was washed with 10% HCl (50%).
0 ml × 3), water (500 ml × 3), 5% Na ₂ CO ₃
(500 ml × 3) and water (500 ml × 3). After drying over CaCl _{2, the} solvent was distilled off to obtain crude product 40.
8 g were obtained. This is distilled under reduced pressure under a nitrogen stream to obtain a purified product 3
13.4 g were obtained. (Yield 77.2%)

Ii) Production of 2-hexylthiophene 300 g (1.65 mol) of 2-hexanoylthiophene and hydrazine hydrate (60) were placed in a 10-liter five-necked flask.
%) And 5 l of diethylene glycol were added and reacted at 180 ° C. for 2 hours while distilling off excess water and hydrazine hydrate. Then cool to 110 ° C
313.7 g of OH was added, heated again, and reacted at 180 ° C. for 2 hours.

After completion of the reaction, the mixture was poured into 10 l of water, extracted with 1 PE (2 l × 2), washed with water (2 l × 4), dried with CaCl ₂ , and evaporated to obtain 285 g of a crude product.

This was distilled under reduced pressure under a nitrogen stream to obtain purified product 2
30 g were obtained. (83.0% yield)

Iii) Production of 5-hexylthiophene-2-carbaldehyde 173.7 g (2.38 mol) of N, N-dimethylformamide was placed in a 3 l 4-neck flask and cooled to 5 ° C. Next, 201.4 g (1.31 mol) of POCl _3.
Was added under stirring at 10 ° C. or less for 15 minutes. After stirring at the same temperature for 30 minutes, the temperature was returned to room temperature, and 200 g (1.19 mol) of 2-hexylthiophene was added dropwise over 10 minutes. After stirring at room temperature for 1 hour and 30 minutes, the mixture was heated to 60 ° C. and reacted for 2 hours.

After completion of the reaction, the reaction solution was poured into 5 l of ice water, extracted with chloroform (2 l × 3), washed with water (2 l × 6), and extracted with CaCl _2.
After drying and distilling off the solvent, the residue was distilled under reduced pressure under a nitrogen stream to obtain 199.2 g of a product. (Yield 85.0%)

Iv) Preparation of 5-hexylthiophene-2-carboxylic acid 5-hexylthiophene-2-carboxylic acid was placed in a 5 l four-necked flask.
90.0 g of carbaldehyde (4.59 × 10 ^-1 mo
l), 540 ml of ethanol, an aqueous solution of AgNO ₃ (Ag
171.0 g of NO ₃ and 540 ml of water) were added, and then an aqueous NaOH solution (91.8 g of NaOH, 270 m of water)
l) was added dropwise over 30 minutes at room temperature. Thereafter, the reaction was carried out for 1 hour and 30 minutes.

After completion of the reaction, the reaction mixture was filtered. The filtrate was acidified with 6N HCl, and the precipitated crystals were filtered to obtain a crude product. This was recrystallized with 50% aqueous ethanol to obtain 74.5 g of a purified product. (Yield 76.6%)

V) Preparation of 5-hexylthiophene-2-carboxylic acid chloride 1.0 g of 5-hexylthiophene-2-carboxylic acid
(4.72 × 10 ⁻³ mol) in 10 ml of thionyl chloride
Was added. After heating and stirring at 80 ° C for 4 hours, excess thionyl chloride was distilled off under reduced pressure to give 5-hexylthiophene-2-ene.
A carboxylic acid chloride was obtained.

Vi) Preparation of 4- (5-dodecyl-2-pyrimidinyl) phenyl 5-hexylthiophene-2-carboxylate 0.80 g of 4- (5-dodecyl-2-pyrimidinyl) phenol (2.36 × Pyridine 15 to 10 ^-3 mol)
Then, the mixture was cooled in an ice water bath. To this, 0.54 g of 5-hexylthiophene-2-carboxylic acid chloride (2.
36 × 10 ⁻³ mol) and reacted at room temperature for 5 hours. After completion of the reaction, the mixture was poured into 100 ml of water, acidified with concentrated hydrochloric acid, and then extracted with isopropyl ether (50 ml ×
3). Thereafter, washing with water was repeated until the washing liquid became neutral. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a crude product. This was purified by silica gel column chromatography (developing solution hexane / ethyl acetate = 10/1), and recrystallized from ethanol to obtain 0.38 g of a purified product. (Yield 30.2%)

Phase transition temperature (° C.)

[0081]

[Outside 71]

Synthesis Example 3 5-Dodecyl-2-thiophenecarboxylic acid 4- (4'-
Decylbiphenyl) ester (Exemplified Compound No. 2-2)
Production Example 2 of 3) Synthesis Example 2) 4'-decylbiphenyl-4-ol was used in place of 4- (5-dodecyl-2-pyrimidinyl) phenol in vi), and instead of 5-hexylthiophene-2-carboxylic acid chloride. 0.7 g of the title compound was obtained in the same manner as in Synthesis Example 2, except that 5-dodecylthiophene-2-carboxylic acid chloride was used. (Yield 73%)

Phase transition temperature (° C.)

[0084]

[Outside 72]

Specific examples of the liquid crystal compound represented by the general formula (II) are shown below.

[0086]

[Outside 73]

[0087]

[Outside 74]

[0088]

[Outside 75]

[0089]

[Outside 76]

[0090]

[Outside 77]

[0091]

[Outside 78]

[0092]

[Outside 79]

[0093]

[Outside 80]

[0094]

[Outside 81]

[0095]

[Outer 82]

[0096]

[Outside 83]

[0097]

[Outside 84]

[0098]

[Outside 85]

[0099]

[Outside 86]

[0100]

[Outside 87]

[0101]

[Outside 88]

The compounds represented by the general formula (III) are described, for example, in JP-A-63-22042 and JP-A-63-12.
No. 2651, and the like.

A typical synthesis example is shown below.

Synthesis Example 5 (Synthesis of Compound No. 3-28) 1.00 g of p-2-fluorooctyloxyphenol
(4.16 mM) in 10 ml of pyridine and 5 ml of toluene
And a solution prepared by dissolving 1.30 g (6.00 mM) of trans-4-n-pentylcyclohexanecarboxylic acid chloride in 5 ml of toluene was prepared at 5 ° C.
It was dropped in 0 minutes. After the dropwise addition, the mixture was stirred at room temperature overnight to obtain a white precipitate.

After completion of the reaction, the reaction product was extracted with benzene,
After washing the benzene layer with distilled water, the benzene layer was dried over magnesium sulfate, and benzene was distilled off.
The product was further purified using silica gel column chromatography, and further recrystallized from ethanol / methanol to obtain trans-4-n-pentylcyclohexanecarboxylic acid-
p-2-fluorooctyloxyphenyl ester
20 g (2.85 mM) were obtained. (68.6% yield).

NMR data (ppm) 0.83 to 2.83 ppm (34H, m) 4.00 to 4.50 ppm (2H, q) 7.11 ppm (4H, s) IR data (cm ⁻¹ ) 3456, 2928 , 2852, 1742, 1508,
1470, 1248, 1200, 1166, 1132,
854.

Phase transition temperature (° C.)

[0108]

[Outside 89] (Here, S ₃ , S ₄ , S ₅ , and S ₆ indicate phases having a higher degree of order than SmC ^* .)

Synthesis Example 6 (Synthesis of Compound No. 3-85) In a vessel sufficiently purged with nitrogen, 0.40 g (3.0 mmol) of (-)-2-fluoroheptanol and 1.00 g (13 mmol) of dry pyridine were placed. ) And stirred for 30 minutes under ice cooling. 0.69 g (3.6 mmol) of p-toluenesulfonic acid chloride was added to the solution, and stirring was continued for 5 hours. After completion of the reaction, 1N HCl (10 ml) was added, extraction was performed twice with methylene chloride (10 ml), and the extract was washed once with distilled water (10 ml). The obtained methylene chloride solution is dried by appropriately adding anhydrous sodium sulfate, and then the solvent is distilled off to obtain (+)-2-fluoroheptyl p.
0.59 g of toluenesulfonic acid ester (2.0 mm
ol).

The yield is 66%. The specific rotation and IR data of the product are as follows. Specific rotation [α] ^26.4 _D + 2.59 ° (c = 1, CHC
l ₃ ). Specific rotation [α] ^23.6 ₄₃₅ + 9.58 ° (c = 1, CHC
l ₃ ).

IR (cm ^-1 ): 2900, 2850, 1600, 1450, 1350,
1170, 1090, 980, 810, 660, 55
0.

The (+)-2-fluoroheptyl p-toluenesulfonic acid ester 0.4 obtained as described above was obtained.
3 g (1.5 mmol) and 0.28 g of 5-octyl-2- (4-hydroxyphenyl) pyrimidine (1.0 mm
ol) and 0.2 ml of 1-butanol was added and stirred well. 1.0 ml of 1-butanol was added to the solution in advance.
An alkali solution prepared by dissolving 0.048 g (1.2 mmol) of sodium hydroxide in the resulting solution was quickly poured, and the mixture was refluxed for 5 hours and a half. After completion of the reaction, 10 ml of distilled water was added, extraction was performed once each with 10 ml and 5 ml of benzene, and anhydrous sodium sulfate was appropriately added to the extract, followed by drying. After drying, the solvent is distilled off, and the desired product (+)-
0.17 g of 5-octyl-2- [4- (2-fluoroheptyloxy) phenyl] pyridine (0.43 mmol
1) was obtained.

The yield was 43%, and the following specific rotation and IR data were obtained. Specific rotation [α] ^25.6 _D + 0.44 ° (c = 1, CHC
l ₃ ). Specific rotation [α] ^22.4 ₄₃₅ + 4.19 ° (c = 1, CHC
l ₃ ).

IR (cm ^-1 ): 2900, 2850, 1600, 1580, 1420,
1250, 1160, 800, 720, 650, 55
0.

Specific examples of the liquid crystal compound represented by formula (III) are shown below.

[0116]

[Outside 90]

[0117]

[Outside 91]

[0118]

[Outside 92]

[0119]

[Outside 93]

[0120]

[Outside 94]

[0121]

[Outside 95]

[0122]

[Outside 96]

[0123]

[Outside 97]

[0124]

[Outside 98]

[0125]

[Outside 99]

[0126]

[Outside 100]

[0127]

[Outside 101]

[0128]

[Outside 102]

[0129]

[Outside 103]

[0130]

[Outside 104]

In the liquid crystal composition, the total of the liquid crystal compounds represented by the general formulas (I) and (II) of the present invention is 1 to
90% by weight, preferably 2-80% by weight, more preferably 4-80% by weight is contained. In addition, the general formula (I) and the general formula (II) are 100: 1 to 1:10
0, preferably 70: 1 to 1:70, more preferably 3
It is desirable to make it contain at a ratio of 0: 1 to 1:30.

Further, the compounds represented by the general formulas (I) and (I)
The liquid crystal represented by formula (I) or (II) of the present invention occupies in the liquid crystal composition obtained by mixing two or more of one or both of the liquid crystal compounds represented by I). It is desirable that the ratio of the sex compound is the ratio described above.

Further, the compounds represented by the general formulas (I) and (I)
The total content of I) and the liquid crystal compound represented by the general formula (III) is preferably 1 to 99% by weight, preferably 4 to 90% by weight, more preferably 6 to 80% by weight. In addition,
The general formulas (I) and (II) and the general formula (II)
I) is from 1:30 to 100: 1, preferably 1:20
To 50: 1, more preferably 1:10 to 30: 1. Here, the ratio of the general formula (I) to the general formula (II) is as described above.

Further, when one or more of the liquid crystal compounds represented by the general formula (I), the general formula (II) and the general formula (III) of the present invention are used, or a mixture of two or more thereof is obtained. The ratio of the liquid crystal compound represented by the general formula (I), the general formula (II), or the general formula (III) of the present invention in the liquid crystal composition is as described above.

Further, the liquid crystal composition according to the present invention exhibits ferroelectricity. Further, it is a chiral smectic phase represented by the liquid crystal composition.

Other liquid crystal compounds used in the present invention are shown below by formulas (IV) to (VIII).

[0137]

[Outside 105] (However, R ₁ ′ and R ₂ ′ are a linear or branched alkyl group having 1 to 18 carbon atoms, and one or two or more non-adjacent —CH ₂ — groups in the alkyl group are

[0138]

[Outer 106] And Z ₁ ′, Z ₂ ′
When direct binding to -CH ₂ - one except group or two or more -CH ₂ - group,

[0139]

[Outside 107] And at least one of R ₁ ′ and R ₂ ′ is optically active.

[0140]

[Outside 108] And a ₁ and b ₁ are 0, 1 or 2, and a ₁ + b ₁ is 1 or 2. )

[0141]

[Outside 109] (However, R ₃ ′ and R ₄ ′ are a linear or branched alkyl group having 1 to 18 carbon atoms, and one or two or more non-adjacent —CH ₂ — groups in the alkyl group are

[0142]

[Outside 110] And Z ₃ ′, Z ₄ ′
When direct binding to -CH ₂ - one except group or two or more -CH ₂ - group,

[0143]

[Outside 111] May be replaced by

[0144]

[Outside 112] Both X ₁ ′ and X ₂ ′ are not single bonds.

[0145]

[Outside 113] Y ₁ ′ is a hydrogen atom, a halogen atom, CH ₃ or CF ₃ . )

[0146]

[Outside 114] (However, R ₅ ′ and R ₆ ′ are a linear or branched alkyl group having 1 to 18 carbon atoms, and one or two or more non-adjacent —CH ₂ — groups in the alkyl group are

[0147]

[Outside 115] And one or more —C except a —CH ₂ — group directly bonded to Z ₅ ′, Z ₆ ′
The H ₂ — group is

[0148]

[Outside 116] May be replaced by

[0149]

[Outside 117] Or a single bond,

[0150]

[Outside 118] A ₂ ′ and A ₃ ′ are not single bonds.

[0151]

[Outside 119] When A ₂ ′ is a single bond, X ₃ ′ is a single bond, and when A ₃ ′ is a single bond, X ₄ ′ is a single bond. Y ₂ ′, Y ₃ ′, Y ₄ ′
Is a hydrogen atom, a halogen atom, CH ₃ or CF ₃ . )

[0152]

[Outside 120] (However, R ₇ ′ and R ₈ ′ are a linear or branched alkyl group having 1 to 18 carbon atoms, and one or two or more non-adjacent —CH ₂ — groups in the alkyl group are

[0153]

[Outside 121] And one or more —C except —CH ₂ — groups directly bonded to Z ₇ ′ and Z ₈ ′
The H ₂ — group is

[0154]

[Outside 122] May be replaced by

[0155]

[Outside 123]

[0156]

[Outside 124] a _3, b ₃ is 0 or 1 but, a _3, b ₃ are never both zero. )

[0157]

[Outside 125] (Wherein, R ₉ 'is a straight or branched alkyl group having 1 to 18 carbon atoms, R _10' represents a linear or branched alkyl group having 1 to 16 carbon atoms .A ₅ ′

[0158]

[Outside 126]

[0159]

[Outside 127] —O—CH ₂ CH ₂ —. C ^* represents an optically active asymmetric carbon atom. )

Preferred compounds of the formulas (IV) to (VIII) include (IVa) to (VIIIe).

[0161]

[Outside 128]

[0162]

[Outside 129]

[0163]

[Outside 130]

Further, in the ferroelectric liquid crystal device according to the present invention, the liquid crystal layer exhibiting ferroelectricity can be obtained by converting the liquid crystal composition exhibiting a chiral smectic phase prepared as described above into an isotropic liquid temperature in vacuum. It is preferable to heat, fill in the element cell, and gradually cool to form a liquid crystal layer and return to normal pressure.

FIG. 1 is a schematic sectional view showing an example of a liquid crystal device having a chiral smectic liquid crystal layer according to the present invention for explaining the structure of a crystal device utilizing ferroelectricity.

In FIG. 1, reference numeral 1 denotes a chiral smectic liquid crystal layer, 2 denotes a glass substrate, 3 denotes a transparent electrode, 4 denotes an insulating orientation control layer, 5 denotes a spacer, 6 denotes a lead wire, 7 denotes a power source, 8 denotes a deflection plate, Reference numeral 9 denotes a light source.

Each of the two glass substrates 2 has In ₂
A transparent electrode 3 made of a thin film such as O ₃ , SnO _2, or ITO (Indium-Tin Oxide) is covered. On top of that, a thin film of a polymer such as polyimide is rubbed with a gauze, an acetate flocking cloth or the like to form an insulating alignment control layer for arranging liquid crystals in the rubbing direction. Also, 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, inorganic oxides such as titanium oxide and magnesium fluoride Form a material insulating layer, on which polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyparaxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, Organic insulating materials such as urea resin, acrylic resin and photoresist resin are used as orientation control layers.
The insulating orientation control layer may be formed of two layers, or may be a single layer of an inorganic insulating orientation control layer or an organic insulating orientation control layer. If the insulating orientation control layer is inorganic, it can be formed by vapor deposition or the like. If organic, it can be formed by dissolving an organic insulating material or its precursor solution (0.1 to 20% by weight, preferably 0 to 20% by weight in a solvent). .2 to 10% by weight) by spinner coating method, dip coating method, screen printing method, spray coating method, roll coating method and the like, and cured under predetermined curing conditions (for example, under heating) to form. be able to.

The thickness of the insulating orientation control layer is usually 30.degree.
μm, preferably 40 ° to 3000 °, more preferably 40 ° to 1000 °.

The two glass substrates 2 are kept at an arbitrary interval by the 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 with a sealing material, for example, an epoxy-based adhesive. In addition, a polymer film or glass fiber may be used as a spacer. A liquid crystal exhibiting ferroelectricity is sealed between the two glass substrates.

The chiral smectic liquid crystal layer 1 in which the chiral smectic liquid crystal is sealed generally has a thickness of 0.5 to 20.
μm, preferably 1 to 5 μm.

The ferroelectric liquid crystal has an SmC ^* phase (chiral smectic C phase) in a wide temperature range including room temperature (especially at a low temperature side). A wide margin is desired.

In order to exhibit good uniform orientation and obtain a mono-domain state, particularly in the case of a device, the ferroelectric liquid crystal must have an isotropic phase to a Ch phase (cholesteric phase).
It is desirable to have a phase transition system example of SmA (smectic phase) -SmC ^* (chiral smectic C phase).

[0173] The transparent electrode 3 is connected to an external power supply 7 by a lead wire.

A polarizing plate 8 is attached to the outside of the glass substrate 2.

Since FIG. 1 is a transmission type, a light source 9 is provided.

FIG. 2 schematically illustrates an example of a cell for explaining the operation of a liquid crystal device utilizing ferroelectricity.
Reference numerals 21a and 21b denote substrates (glass plates) each covered with a transparent electrode made of a thin film such as In ₂ O ₃ , SnO ₂ or ITO (Indium-Tin Oxide), between which the liquid crystal molecule layer 22 is perpendicular to the glass surface. The liquid crystal of the SmC ^* phase or SmH ^* phase, which is oriented so that A bold line 23 represents a liquid crystal molecule, and the liquid crystal molecule 23 has a dipole moment (P⊥) 24 in a direction perpendicular to the molecule. Substrate 21a
When a voltage equal to or greater than a certain threshold is applied between the electrodes on the electrodes 21b and 21b, the helical structure of the liquid crystal molecules 23 is unwound, and the liquid crystal molecules 23 change the orientation direction so that the dipole moment (P⊥) 24 is all directed to the electric field direction. be able to. Liquid crystal molecules 23
Has an elongated shape and exhibits refractive index anisotropy in the major axis direction and the minor axis direction.Therefore, for example, if crossed Nicol polarizers are placed above and below the glass surface, the optical characteristics will vary depending on the polarity of the applied voltage. To become a changing liquid crystal optical modulator,
It is easily understood.

The liquid crystal cell preferably used in the optical modulation element of the present invention can have a sufficiently small thickness (for example, 10 μm or less). As shown in FIG. 3, as the liquid crystal layer becomes thinner, the helical structure of the liquid crystal molecules is released even when no electric field is applied, and the dipole moment Pa or Pb thereof is directed upward (34a) or downward (34b). Take either of the states. When an electric field Ea or Eb having a different polarity or more than a certain threshold is applied to such a cell by the voltage applying means 31a and 31b as shown in FIG. 3, the dipole moment is directed upward corresponding to the electric field vector of the electric field Ea or Eb. 34a or the downward direction 34b, and accordingly, the liquid crystal molecules are in the first stable state 3
3a or the second stable state 33b.

As described above, there are two advantages of using such a ferroelectric property as an optical modulation element.

The first is that the response speed is extremely fast, and the second is that the orientation of the liquid crystal molecules has bistability. The second point will be further described with reference to FIG. 3, for example. When an electric field Ea is applied, the liquid crystal molecules are oriented to a first stable state 33a. This state is stable even when the electric field is turned off.
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 the direction of the molecules.
Again, this state remains even when the electric field is turned off. Also, as long as the applied electric field Ea or Eb does not exceed a certain threshold,
Each is also maintained in the previous alignment state.

By using the liquid crystal element of the present invention in a display panel section and employing a data synchronizing means by a data format and image signal having scanning line address information shown in FIG. 9 and FIG. To achieve.

In the figure, reference numerals are as follows. DESCRIPTION OF SYMBOLS 101 Ferroelectric liquid crystal display device 102 Graphics controller 103 Display panel 104 Scan line drive circuit 105 Information line drive circuit 106 Decoder 107 Scan signal generation circuit 108 Shift register 109 Line memory 110 Information signal generation circuit 111 Drive control circuit 112 GCPU 113 Host CPU 114 VRAM

The generation of image information is performed by the graphics controller 102 on the main unit side, and is shown in FIGS.
Are transferred to the display panel 103 according to the signal transfer means shown in FIG. The graphics controller 102
PU (Central Processing Unit, hereinafter abbreviated as GCPU112)
And VRAM (image information storage memory) 114 as a core,
It is responsible for management and communication of image information between the host CPU 113 and the liquid crystal display device 101, and the control method of the present invention is mainly realized on the graphics controller 102.

A light source is arranged on the back surface of the display panel.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples, all “parts” indicate “parts by weight”.

[0185]

Example 1 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition A.

[0186]

[Outside 131]

[0187]

[Outside 132]

Further, the following exemplary compounds were mixed with the liquid crystal composition A in the following parts by weight, respectively, to prepare a liquid crystal composition 1-A.

[0189]

[Outside 133]

Next, the optical response was observed using cells prepared from these liquid crystal compositions according to the following procedure.

Prepare two 0.7 mm thick glass plates,
The ITO film is formed on each of the glass plate, to create a voltage application electrode, and an insulating layer is further deposited SiO ₂ thereon. A silane coupling agent [KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.] 0.2% isopropyl alcohol solution was rotated on a glass plate at 2000 rpm. p. 1 with m spinner
The coating was performed for 5 seconds to perform a surface treatment. Thereafter, a heat drying treatment was performed at 120 ° C. for 20 minutes.

Further, a polyimide resin precursor [Toray Co., Ltd. SP-
510] 1.0% dimethylacetamide solution at 3000 rpm. p. m for 15 seconds.
After the film formation, a heat condensation baking treatment was performed at 300 ° C. for 60 minutes. At this time, the thickness of the coating film was about 120 °.

The baked film was subjected to a rubbing treatment with an acetate flocking cloth, and then washed with an isopropyl alcohol solution. The rubbing treatment axes were made parallel to each other, the glass plates were bonded together using an adhesive sealant [Rixon Bond (Chisso Corporation)], and heated and dried at 100 ° C. for 60 minutes to form cells. The cell thickness of this cell was about 1.5 μm when measured with a Berek phase plate.

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

Using this ferroelectric liquid crystal element, a driving voltage margin ΔV (V ₃ −V ₁ ) was measured with the driving waveform (1/3 bias ratio) shown in FIG. The results are shown below. (Note that Δt is set so that V ₁ ≒ 15 V)

[0196]

[Outside 134]

Further, when the voltage is set at the center value of the drive voltage margin at 25 ° C. and the measured temperature is changed,
The driveable temperature difference (hereinafter referred to as a drive temperature margin) was ± 4.2 ° C.

The contrast at the time of this driving at 25 ° C. was 10.3.

Comparative Example 1 Of the liquid crystal composition 1-A used in Example 1, Exemplified Compound No. Without mixing 2-46 and 2-53, Compound A. 1-AI and Exemplified Compound No. 1-17 were mixed in the same parts by weight as in Example 1.
Compound A. No. 1-13 and 1-22 were mixed with A for Exemplified Compound No. Liquid crystal composition 1 containing only 2-46 and 2-53
-All was made.

A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that the liquid crystal compositions A, 1-AI and 1-AII were injected into the cell instead of using the liquid crystal composition 1-A. Then, the drive voltage margin ΔV was measured.

[0201]

[Outside 135]

Further, the drive temperature margin at 25 ° C. was A ± 1.4 ° C. 1-AI ± 2.6 ° C. 1-AII ± 3.4 ° C.

As is clear from Example 1 and Comparative Example 1,
The driving temperature margin of the ferroelectric liquid crystal element containing the liquid crystal composition 1-A according to the present invention is wider, and it is excellent in the ability to maintain an image well against changes in environmental temperature and cell gap variation. I have.

Example 2 In place of the exemplary compound used in Example 1, the following exemplary compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition 2-A.

[0205]

[Outside 136]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that this liquid crystal composition was used.
The drive voltage margin and the drive temperature margin were measured in the same manner as described above.

The measurement results are shown below.

[0208]

[Outside 137]

Comparative Example 2 Of the liquid crystal composition 2-A used in Example 2, Exemplified Compound No. Without mixing 2-46 and 2-53, Compound A. 1-13, 1-22, 3-28, 3-
83 and 3-87 alone in the same parts by weight as in Example 1 were mixed with 2-AI and Exemplified Compound No. Compound A. No. 1-13 and 1-22 were mixed with A for Exemplified Compound No. 2-46, 2-
Liquid crystal composition 2-AII was prepared by mixing only 53, 3-28, 3-83, and 3-87.

A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 except that the liquid crystal compositions A, 2-AI, and 2-AII were injected into the cell instead of using the liquid crystal composition 2-A. Then, the drive voltage margin ΔV was measured.

Drive voltage margin (set at measurement time Δt)

[0212]

[Outside 138]

Further, the drive temperature margin at 25 ° C. was A ± 1.4 ° C. 2-AI ± 2.4 ° C. 2-AII ± 2.8 ° C.

As is clear from Example 2 and Comparative Example 2,
The driving temperature margin of the ferroelectric liquid crystal element containing the liquid crystal composition 2-A according to the present invention is wider, and it is excellent in the ability to keep an image good against environmental temperature changes and cell gap variations. I have.

Example 3 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition B.

[0216]

[Outside 139]

[0219]

[Outside 140]

Further, the following exemplary compounds were mixed with the liquid crystal composition B in the following parts by weight, respectively, to prepare a liquid crystal composition 3-B.

[0219]

[Outside 141]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that this liquid crystal composition was used.
The drive voltage margin and the drive temperature margin were measured in the same manner as described above.

The measurement results are shown below.

[0222]

[Outside 142]

Comparative Example 3 Of the liquid crystal composition 3-B used in Example 3, Exemplified Compound No. Without mixing 2-23, 2-70 and 2-91,
B to Exemplified Compound No. 1-1, 1-20, 1-3
6 mixed only in the same parts by weight as in Example 3
And Exemplified Compound No. Exemplified Compound No. to B without mixing 1-1, 1-20, and 1-36. 2-23, 2-7
A liquid crystal composition 3-BII was prepared by mixing only 0,2-91.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 3 except that the liquid crystal compositions B, 3-BI, and 3-BII were injected into the cell instead of using the liquid crystal composition 3-B. Then, the drive voltage margin ΔV was measured.

[0225]

[Outside 143]

Further, the drive temperature margin at 25 ° C. was B ± 2.0 ° C. 3-BI ± 2.5 ° C. 3-BII ± 3.2 ° C.

As is clear from Example 3 and Comparative Example 3,
The driving temperature margin of the ferroelectric liquid crystal element containing the liquid crystal composition 3-B according to the present invention is wider, and the ferroelectric liquid crystal element is more excellent in the ability to maintain an image well against changes in environmental temperature and cell gap variation. I have.

Example 4 In place of the exemplary compound used in Example 3, the following exemplary compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition 4-B.

[0229]

[Outside 144]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 1 except that this liquid crystal composition was used.
The drive voltage margin and the drive temperature margin were measured in the same manner as described above.

The measurement results are shown below.

[0232]

[Outside 145]

Comparative Example 4 Of the liquid crystal composition 4-B used in Example 4, Exemplified Compound No. Without mixing 2-23, 2-70 and 2-91,
B to Exemplified Compound No. 1-1, 1-20, 1-3
4-BI mixed with Exemplified Compound No. 6,3-37,3-80,3-93 only in the same parts by weight as in Example 4. 1
Compound No. -1, 1-20 and 1-36 were mixed with B without mixing Exemplified Compound No. 2-23, 2-70, 2-91, 3-3
Liquid crystal composition 4- in which only 7,3-80,3-93 is mixed
BII was made.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 4, except that the liquid crystal compositions B, 4-BI and 4-BII were injected into the cell instead of using the liquid crystal composition 4-B. Then, the drive voltage margin ΔV was measured.

[0235]

[Outside 146]

Further, the drive temperature margin at 25 ° C. was B ± 2.0 ° C. 4-BI ± 2.1 ° C. 4-BII ± 3.0 ° C.

As is clear from Example 4 and Comparative Example 4,
The driving temperature margin of the ferroelectric liquid crystal element containing the liquid crystal composition 4-B according to the present invention is wider, and it is excellent in the ability to maintain an image well against changes in environmental temperature and cell gap variation. I have.

Example 9 Except that a 1.5% dimethylacetamide solution of the polyimide resin precursor used in Example 1 was replaced with a 2% aqueous solution of polyvinyl alcohol resin [PVA-117 manufactured by Kuraray Co., Ltd.] A ferroelectric liquid crystal element is created by the method of
The optical response speed was measured in the same manner as in Example 1.

The result is shown below.

[0240]

[Outside 147]

Example 10 A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 1 except that the alignment control layer was formed using only the polyimide resin without using the SiO ₂ used in Example 1. The optical response speed was measured in the same manner as in Example 1.

The results are shown below.

[0243]

[Outside 148]

Examples 11 to 26 In place of the exemplified compounds and the liquid crystal compositions used in Example 1 or the exemplified compounds and the liquid crystal compositions used in Example 5, the exemplified compounds and the liquid crystal compositions shown in Table 1 were weighed. 11-A, 12-A, 13-A, 14-A, 15
-A, 16-A, 17-A, 18-A, 19-B, 20
-B, 21-B, 22-B, 23-B, 24-B, 25
-B and 26-B liquid crystal compositions were obtained. Except for using these, a liquid crystal element was prepared in the same manner as in Example 1, and
The driving voltage margin and the driving temperature margin were measured in the same manner as in Example 1, and the switching state and the like were observed.

The uniform monodomain alignment in each of the prepared liquid crystal elements was good.

Table 1 shows the measurement results.

[0247]

[Table 1]

[0248]

[Table 2]

As is clear from Examples 11 to 26, the liquid crystal device containing the liquid crystal composition according to the present invention shows good alignment, has a wide driving voltage margin and a wide driving temperature margin, and exhibits a change in environmental temperature. Also, it is excellent in the ability to keep an image good with respect to variations in cell gap.

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

As is evident from this, the use of the liquid crystal composition according to the present invention can be expected to bring the ferroelectricity of the liquid crystal element to practical use at an early stage.

[0252]

The liquid crystal device using the liquid crystal composition of the present invention has good switching characteristics, a large driving voltage margin, and even if there is a certain degree of temperature variation in the display area of the liquid crystal device, all the pixels can be used. A liquid crystal element with a wide driving temperature margin for good matrix driving can be obtained.

A display device in which the liquid crystal element of the present invention is used as a display element in combination with a light source, a driving circuit, and the like is a favorable device.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal element using a liquid crystal exhibiting a chiral smectic phase.

FIG. 2 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 3 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 4 is a waveform diagram of a driving method used in Examples and the like.

FIG. 5 is a waveform diagram of a driving method used in Examples and the like.

FIG. 6 is a plan view of a liquid crystal panel on which matrix electrodes are arranged.

FIG. 7 is a schematic diagram of a display pattern when actual driving is performed with the time-series driving waveform shown in FIG.

FIG. 8 is a graph showing a change in transmittance when a drive voltage is changed (VT characteristic diagram).

FIG. 9 is a block diagram showing a liquid crystal display device having a liquid crystal element using ferroelectricity and a graphics controller.

FIG. 10 is a timing chart of image information communication between the liquid crystal display device and the graphics controller.

[Explanation of symbols]

 Reference Signs List 1 liquid crystal layer having chiral smectic phase 2 glass substrate 3 transparent electrode 4 insulating alignment control layer 5 spacer 6 lead wire 7 power supply 8 polarizing plate 9 light source Io incident light I transmitted light 21a substrate 21b substrate 22 having chiral smectic phase Liquid crystal layer 23 Liquid crystal molecules 24 Dipole moment (P⊥) 31a Voltage applying means 31b Voltage applying means 33a First stable state 33b Second stable state 34a Upward dipole moment 34b Downward dipole moment Ea Upward electric field Eb Downward electric field 61 Liquid crystal panel 62 Scanning electrode group 63 Information electrode group 101 Ferroelectric liquid crystal display device 102 Graphics controller 103 Display panel 104 Scan line drive circuit 105 Information line drive circuit 106 Decoder 107 Scan signal generation circuit 108 Shift register 1 09 Line memory 110 Information signal generation circuit 111 Drive control circuit 112 GCPU 113 Host CPU 114 VRAM

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuharu Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 19 / 42 C09K 19/34

Claims (42)

(57) [Claims] 1. The following general formula (I): (However, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 18 carbon atoms, and these may have an alkoxy group having 1 to 12 carbon atoms as a substituent.
R ₁ and R ₂ are both non-optically active. Z ₁ is a single bond. Is shown. )) And at least one liquid crystal compound represented by the following general formula (II): (However, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 18 carbon atoms, and these are CH ₃ as a substituent.
O- group may have a C ₅ H ₁₁ O- group, or F-.
Z ₂ and Z ₃ are single bonds. It is. A ₁ is -A ₂ -or -A ₂ -A _3- , wherein A _{2 and} A ₃ are It is. A liquid crystal composition comprising at least one liquid crystal compound represented by the formula (1): 2. The following general formula (III): (However, R ₅ is a linear or branched alkyl group having 1 to 18 carbon atoms and may have a C ₆ H ₁₃ O— group as a substituent. Y is a single bond; ] The liquid crystal composition according to claim 1, further comprising at least one liquid crystal compound represented by the formula: 3. The liquid crystal composition according to claim 1, wherein the liquid crystal compound represented by the general formula (I) is a compound represented by the following (Ia) or (Ib). [Outside 8] (However, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 18 carbon atoms, and these may have an alkoxy group having 1 to 12 carbon atoms as a substituent.
R ₁ and R ₂ are both non-optically active. ) 4. The liquid crystal composition according to claim ₁ , wherein R ₁ and R ₂ in the liquid crystal compound represented by the general formula (I) are represented by (Ii) to (I-iii). (Ii) an n-alkyl group having 1 to 16 carbon atoms (However, m is an integer of 0 to 7 and n is an integer of 1 to 9, but is in the range of 2 ≦ m + n ≦ 14.) (However, r is an integer of 0 to 7, and s is 0 or 1
It is. Also, t is an integer of 1 to 14, but 1 ≦ r + s
+ T ≦ 14. ) 5. The liquid crystal composition according to claim 1, wherein the liquid crystalline compound represented by the general formula (II) is a compound represented by the following formulas (IIa) to (IIe). [Outside 11] (However, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 18 carbon atoms, and these are CH ₃ as a substituent.
O- group may have a C ₅ H ₁₁ O- group, or F-.
Z ₂ and Z ₃ are single bonds, It is. ) 6. The liquid crystal composition according to claim 1, wherein in the general formula (II), R ₃ and R ₄ are selected from the following (II-i) to (II-iv). (II-i) an n-alkyl group having 2 to 16 carbon atoms (However, m 'is an integer of 0 to 7, and n' is an integer of 1 to 9.) (However, r 'is an integer of 0 to 7, s' is 0 or 1, and t' is an integer of 1 to 14.) (However, p 'is 0 or 1, x' is an integer of 1 to 14. * indicates an asymmetric carbon.) 7. The liquid crystal composition according to claim 2, wherein the compound represented by the general formula (III) is a compound represented by the following formulas (III-a) to (III-f). [Outside 16] (Where R ₅ is a linear or branched alkyl group having 1 to 18 carbon atoms; Z ₄ is a single bond; 8. The compound of the above formulas (III-a) to (III-
is Z _4, Z ₅ in f), the following (III-i) ~ (II
The liquid crystal composition according to claim 7, which is Iv). (III-i) Z ₄ is a single bond, Z ₅ is _{-O-CH 2 - (III-} ii) Z 4 is a single bond, Z ₅ is _{-COO-CH 2 - (III-} iii) Z 4 is a single bond , Z ₅ is —OCO— (III-iv) Z ₄ is —O—, Z ₅ is —O—CH ₂ — (III-v) Z ₄ is —O—, and Z ₅ is —COOCH ₂ —. 9. The liquid crystal composition according to claim 1, comprising 1 to 90% by weight of the liquid crystal compound represented by the general formulas (I) and (II) based on the liquid crystal composition. 10. The liquid crystal composition according to claim 1, comprising 2 to 80% by weight of the liquid crystal compound represented by the general formulas (I) and (II) based on the liquid crystal composition. 11. The liquid crystal composition according to claim 1, comprising 4 to 80% by weight of the liquid crystal compound represented by the general formulas (I) and (II) based on the liquid crystal composition. 12. The liquid crystal composition according to claim 2, comprising 1 to 99% by weight of the liquid crystal compound represented by the general formula (I), the general formula (II) and the general formula (III). object. 13. The liquid crystal composition according to claim 2, wherein the liquid crystal compound represented by the general formulas (I), (II) and (III) is contained in an amount of 4 to 90% by weight based on the liquid crystal composition. object. 14. The liquid crystal composition according to claim 2, wherein the liquid crystal compound represented by the general formulas (I), (II) and (III) is contained in an amount of 6 to 80% by weight based on the liquid crystal composition. object. 15. The liquid crystal composition according to claim 1, wherein the liquid crystal composition has a chiral smectic phase. 16. A liquid crystal device comprising the liquid crystal composition according to claim 1 disposed between a pair of electrode substrates. 17. The liquid crystal device according to claim 16, wherein an alignment control layer is further provided on the electrode substrate. 18. The liquid crystal device according to claim 17, wherein the alignment control layer is a rubbed layer. 19. The liquid crystal display according to claim 1, wherein the liquid crystal is released from the helix.
17. The liquid crystal device according to claim 16, wherein a distance between the pair of electrode substrates is set and arranged. 20. A display device having the liquid crystal element according to claim 16. 21. The display device according to claim 20, further comprising a driving circuit for driving a liquid crystal element. 22. The display device according to claim 20, further comprising a light source. 23. A display using a liquid crystal composition containing at least one liquid crystal compound represented by the following general formula (I) and at least one liquid crystal compound represented by the following general formula (II): Method. [Outside 18] (However, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 18 carbon atoms, and these may have an alkoxy group having 1 to 12 carbon atoms as a substituent.
R ₁ and R ₂ are both non-optically active. Z ₁ is a single bond, Is shown. [Outside 20] (However, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 18 carbon atoms, and these are CH ₃ as a substituent.
O- group may have a C ₅ H ₁₁ O- group, or F-.
Z ₂ and Z ₃ are single bonds, It is. A ₁ is -A ₂ -or -A ₂ -A _3- , wherein A _{2 and} A ₃ are It is. ) 24. The liquid crystal composition further comprising the following general formula (III): (However, R ₅ is a linear or branched alkyl group having 1 to 18 carbon atoms, and may have a C ₆ H ₁₃ O— group as a substituent. Y is a single bond; ] The display method according to claim 23, comprising at least one liquid crystal compound represented by the formula: 25. The display method according to claim 23, wherein the liquid crystalline compound represented by the general formula (I) is a compound represented by the following (Ia) or (Ib). [Outside 25] (However, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 18 carbon atoms, and these may have an alkoxy group having 1 to 12 carbon atoms as a substituent.
R ₁ and R ₂ are both non-optically active. ) 26. The display method according to claim 23, wherein R ₁ and R ₂ in the liquid crystal compound represented by the general formula (I) are represented by (Ii) to (I-iii). (Ii) an n-alkyl group having 1 to 16 carbon atoms (Where m is an integer of 0 to 7 and n is an integer of 1 to 9, but is in the range of 2 ≦ m + n ≦ 14.) (However, r is an integer of 0 to 7, and s is 0 or 1
It is. Also, t is an integer of 1 to 14, but 1 ≦ r + s
+ T ≦ 14. ) 27. The display method according to claim 23, wherein the liquid crystalline compound represented by the general formula (II) is a compound represented by the following formulas (IIa) to (IIe). [Outside 28] (However, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 18 carbon atoms, and these are CH ₃ as a substituent.
O- group may have a C ₅ H ₁₁ O- group, or F-.
Z ₂ and Z ₃ are single bonds, It is. ) 28. The display method according to claim 23, wherein, in the general formula (II), R ₃ and R ₄ are selected from the following (II-i) to (II-iv). (II-i) an n-alkyl group having 2 to 16 carbon atoms (However, m 'is an integer of 0 to 7, and n' is an integer of 1 to 9.) (However, r 'is an integer of 0 to 7, s' is 0 or 1, and t' is an integer of 1 to 14.) (However, p 'is 0 or 1, x' is an integer of 1 to 14. * indicates an asymmetric carbon.) 29. The display method according to claim 24, wherein the compound represented by the general formula (III) is a compound represented by the following formulas (III-a) to (III-f). [Outside 33] (Where R ₅ is a linear or branched alkyl group having 1 to 18 carbon atoms; Z ₄ is a single bond; 30. The compounds of the above formulas (III-a) to (III-
is Z _4, Z ₅ in f), the following (III-i) ~ (II
30. The display method according to claim 29, which is Iv). (III-i) Z ₄ is a single bond, Z ₅ is _{-O-CH 2 - (III-} ii) Z 4 is a single bond, Z ₅ is _{-COO-CH 2 - (III-} iii) Z 4 is a single bond , Z ₅ is —OCO— (III-iv) Z ₄ is —O—, Z ₅ is —O—CH ₂ — (III-v) Z ₄ is —O—, and Z ₅ is —COOCH ₂ —. 31. The display method according to claim 23, wherein the liquid crystal compound represented by the general formulas (I) and (II) is contained in an amount of 1 to 90% by weight based on the liquid crystal composition. 32. The display method according to claim 23, wherein the liquid crystal compound represented by the general formulas (I) and (II) is contained in an amount of 2 to 80% by weight based on the liquid crystal composition. 33. The display method according to claim 23, wherein the liquid crystal compound represented by the general formulas (I) and (II) is contained in an amount of 4 to 80% by weight based on the liquid crystal composition. 34. The display method according to claim 24, wherein the liquid crystal compound represented by the general formulas (I), (II) and (III) is contained in an amount of 1 to 99% by weight based on the liquid crystal composition. . 35. The display method according to claim 24, wherein the liquid crystal compound represented by the general formulas (I), (II) and (III) is contained in an amount of 4 to 90% by weight based on the liquid crystal composition. . 36. The display method according to claim 24, wherein the liquid crystal compound represented by the general formulas (I), (II) and (III) is contained in an amount of 6 to 80% by weight based on the liquid crystal composition. . 37. The display method according to claim 23, wherein the liquid crystal composition has a chiral smectic phase. 38. A liquid crystal composition comprising at least one liquid crystal compound represented by the following general formula (I) and at least one liquid crystal compound represented by the following general formula (II): A display method using a liquid crystal element provided between substrates. [Outside 35] (However, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 18 carbon atoms, and these may have an alkoxy group having 1 to 12 carbon atoms as a substituent.
R ₁ and R ₂ are both non-optically active. Z ₁ is a single bond. Is shown. [Outside 37] (However, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 18 carbon atoms, and these are CH ₃ as a substituent.
O- group may have a C ₅ H ₁₁ O- group, or F-.
Z ₂ and Z ₃ are single bonds, It is. A ₁ is -A ₂ -or -A ₂ -A ₃ , wherein A _{2 and} A ₃ are It is. ) 39. The display method according to claim 38, wherein an alignment control layer is further provided on the electrode substrate. 40. The display method according to claim 39, wherein the alignment control layer is a rubbed layer. 41. The liquid crystal device according to claim 1, wherein the spiral of the liquid crystal is released.
39. The display method according to claim 38, wherein an interval between the pair of electrode substrates is set and arranged. 42. The display method according to claim 38, wherein the display is performed by electrically driving the liquid crystal composition.