JPH06239849A - Optically active compound, liquid crystal composition containing the same, liquid crystal element having the same composition and display method and display device using the same - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a ferroelectric liquid crystal element having low temperature-operating characteristics, high speed response, etc. CONSTITUTION:A compound of formula I [R1 is H, halogen, CN or 1-18C alkyl; A1 to A3 are formula II [P1 and P2 are H, halogen, CH3, etc.), etc.; X1 and X2 are single bond, CH2O, etc.; * is optically active; (m) and (n) are 0 or 1], e.g. optically active 5-decyl-[2-(4-tetrahydrofurfuryloxy)phenyl]pyrimidine. The compound of formula I is obtained by reacting a compound of formula III with a compound of the formula R1-(A1-X2-X2)m-A2-X2-A3-OH in the presence of a sodium hydride in a solvent [e.g. DMF]. The compound is a liquid crystalline compound having optically active tetrahydrofuran ring on side chain end and is used by combining with a light source, a driving circuit, etc., as the display element to provide the objective display device.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel optically active compound, a liquid crystal composition containing the same, a liquid crystal device and a display device using the same, and more specifically, a novel liquid crystal having improved response characteristics to an electric field. The present invention relates to a composition, a liquid crystal display element using the same, a liquid crystal element used for a liquid crystal-optical shutter, and a display device using the liquid crystal element for display.

[0002]

2. Description of the Related Art 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, M. Sch.
adt) and W. Helfri
ch) "Applied Physics Letters"
("Applied Physics Letter
s ") Vo.18, No.4 (1971.2.15)
P. 127-128 "Voltage Depend"
ent Optical Activity of a
Twisted Nematic liquid Cr
TN (Twisted Nem)
atic) type liquid crystal is used.

These are based on the dielectric alignment effect of liquid crystals, and utilize the effect that the average molecular axis direction is directed in a specific direction by an applied electric field due to the dielectric anisotropy of liquid crystal molecules. The optical response speed limit of these devices is said to be milliseconds, which is too slow for many applications.

On the other hand, in the application to a large flat panel display, the driving by the simple matrix system is the most effective in consideration of price, productivity and the like. The simple matrix method employs an electrode configuration in which a scan electrode group and a signal electrode group are arranged in a matrix, and in order to drive the scan electrode group, an address signal is sequentially and selectively selected and applied to the scan electrode group. Employs a time-division drive system in which a predetermined information signal is synchronized with an address signal and selectively applied in parallel.

However, when the above-mentioned TN type liquid crystal is adopted for the element of such a driving system, the scan electrode is selected and the signal electrode is not selected, or the scan electrode is not selected and the signal electrode is selected. An electric field is applied to a finite amount (so-called "half selection point").

If the difference between the voltage applied to the selection point and the voltage applied to the half selection point is sufficiently large and the voltage threshold value required to align the liquid crystal molecules perpendicularly to the electric field is set to an intermediate voltage value, The display element works normally,
When the number of scanning lines (N) is increased, the time (duty ratio) in which an effective electric field is applied to one selected point while scanning the entire screen (one frame) is reduced by 1 / N. Resulting in.

For this reason, the voltage difference as the effective value applied to the selected point and the non-selected point in the case of repeating scanning becomes smaller as the number of scanning lines increases, and as a result, the image contrast is lowered or Crosstalk is an inevitable drawback.

Such a phenomenon is caused by a liquid crystal having no bistability (a stable state in which liquid crystal molecules are aligned horizontally with respect to an electrode surface, and a vertical state only while an electric field is effectively applied). This is an essentially unavoidable problem that occurs when driving (that is, repeatedly scanning) using the temporal accumulation effect.

In order to improve this point, the voltage averaging method,
The two-frequency driving method and the multi-matrix method have already been proposed, but none of them is sufficient, and the increase in the screen size and the density of the display element is stopped because the number of scanning lines cannot be increased sufficiently. It is the current situation.

In order to improve the drawbacks of the conventional liquid crystal device, the use of a liquid crystal device having bistability is explained by Clark and Lagerwell.
11) (Japanese Patent Laid-Open No. 56-10721).
No. 6, the specification of US Pat. No. 4,367,924).

Bistable liquid crystals are generally chiral smectic C phase (SmC ^* phase) or H phase (SmH ^* phase).
A ferroelectric liquid crystal having is used.

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

In addition to the above-mentioned characteristic of having bistability, 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 the transition of the alignment state.
It is 3 to 4 orders faster than the response speed due to the effect of the dielectric anisotropy and the electric field.

As described above, the ferroelectric liquid crystal potentially has extremely excellent characteristics, and by utilizing such characteristics, many of the problems of the conventional TN type element described above are solved. A fairly substantial improvement is obtained. In particular, it is expected to be applied to high-speed optical optical shutters, high-density, large-screen displays. For this reason, research has been conducted extensively on liquid crystal materials with ferroelectricity, but the ferroelectric liquid crystal materials developed to date have sufficient characteristics for use in liquid crystal elements, including low-temperature operating characteristics and high-speed response characteristics. It is hard to say that it has.

Between the response time τ, the magnitude Ps of spontaneous polarization and the viscosity η, the following equation (II)

[0016]

[Outside 35] (However, E is an applied electric field). Therefore, in order to increase the response speed, there are methods of (a) increasing the magnitude Ps of spontaneous polarization (b) decreasing the viscosity η (c) increasing the applied electric field E. However, the applied electric field has an upper limit because it is driven by an IC or the like, and it is desirable that the applied electric field be as low as possible. Therefore, it is actually necessary to reduce the viscosity η or increase the value of the spontaneous polarization magnitude Ps.

Generally, in a ferroelectric chiral smectic liquid crystal compound having a large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is also large, and there is a tendency that there are many restrictions on the device structure capable of assuming a bistable state. Further, even if the spontaneous polarization is unnecessarily increased, the viscosity tends to increase accordingly, and as a result, the response speed may not be so fast.

When the temperature range used as an actual display is, for example, about 5 to 40 ° C., the change in response speed is generally about 20 times, which exceeds the limit of adjustment by the drive voltage and frequency. The current situation.

As described above, in order to put the ferroelectric liquid crystal device into practical use, a liquid crystal exhibiting a large chiral smectic phase having large spontaneous polarization, low viscous high-speed response, and small temperature dependence of response speed. A composition is required.

Further, the liquid crystal composition has spontaneous polarization, chiral smectic C pitch, Ch pitch, and liquid crystal phase for uniform switching of the display, good viewing angle characteristics, low temperature storability, and reduction of load on the driving IC. It is necessary to optimize the temperature range, optical anisotropy, tilt angle, dielectric anisotropy and the like.

[0021]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an effective liquid crystal compound, a liquid crystal composition containing the same, and particularly a ferroelectric chiral compound so that the above-mentioned ferroelectric liquid crystal device can be put to practical use. An object of the present invention is to provide a liquid crystal composition exhibiting a smectic phase, and a liquid crystal element and a display device using the liquid crystal composition.

[0022]

Means for Solving the Problems The present invention is an optically active compound (liquid crystalline compound) characterized by having an optically active tetrahydrofuran ring at a side chain terminal, and in particular, the present invention has the following general formula: It is an optically active compound represented by (I).

[0023]

[Outside 36] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-,

[0024]

[Outside 37] May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN.

M and n are independently 0 or 1. A ₁ , A ₂ and A ₃ are

[0026]

[Outside 38] Each is independently selected. However, P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN.

X _{1 and} X ₂ are single bonds,

[0028]

[Outside 39] * Indicates that it is optically active. )

The present invention also provides a liquid crystal composition containing at least one kind of the optically active compound, and a liquid crystal element and a display device in which the liquid crystal composition is arranged between a pair of electrode substrates. Is.

Among the optically active compounds represented by the above formula (I), preferred compounds include (Ia) to (Ij).

[0031]

[Outside 40] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-,

[0032]

[Outside 41] May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN.

A ₁ , A ₂ and A ₃ are

[0034]

[Outside 42] Each is independently selected. P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN.

* Indicates that it is optically active. )

Of the compounds represented by the above general formulas (Ia) to (Ij), more preferred are (Iaa) to
(Ija) may be mentioned.

[0037]

[Outside 43]

[0038]

[Outside 44]

[0039]

[Outside 45] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-,

[0040]

[Outside 46] May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN.

P ₁ and P ₂ are H, halogen, CH ₃ , CF ₃ ,
Indicates CN. ) In the compounds represented by the above general formulas, preferable R ₁ is selected from the following (1) to (4). _{(1) -X 3 -C 1 H} 2l + 1 -n ( where, l is an integer of 3-12.) (2)

[0042]

[Outside 47] (However, m is an integer of 0 to 6, and n is an integer of 1 to 8.
It may also be optically active. ) (3)

[0043]

[Outside 48] (However, r is an integer of 0 to 6, s is 0 or 1, and t is 1 to
Indicates an integer of 12. It may also be optically active. ) (4)

[0044]

[Outside 49] (However, u is 0 or 1, and v is an integer of 1 to 14.
* Indicates that it is optically active. ) In the above formula, the common X ₃ is a single bond,

[0045]

[Outside 50] Next, general synthetic examples of the optically active compound represented by the general formula (I) will be shown.

[0046]

[Outside 51] (Note that R ₁ , A ₁ , A ₂ , A ₃ , X ₁ , X ₂ and m are as defined above)

Next, particularly preferred specific examples of the optically active compound represented by the general formula (I) are shown below by structural formulas.

[0048]

[Outside 52]

[0049]

[Outside 53]

[0050]

[Outside 54]

[0051]

[Outside 55]

[0052]

[Outside 56]

[0053]

[Outside 57]

[0054]

[Outside 58]

[0055]

[Outside 59]

[0056]

[Outside 60]

[0057]

[Outside 61]

[0058]

[Outside 62]

[0059]

[Outside 63]

[0060]

[Outside 64]

[0061]

[Outside 65]

[0062]

[Outside 66]

[0063]

[Outside 67]

[0064]

[Outside 68]

[0065]

[Outside 69]

[0066]

[Outside 70]

[0067]

[Outside 71]

[0068]

[Outside 72]

[0069]

[Outside 73]

[0070]

[Outside 74]

[0071]

[Outside 75]

[0072]

[Outer 76]

The liquid crystal composition of the present invention can be obtained by mixing at least one kind of the optically active compound represented by the general formula (I) and one or more kinds of other liquid crystal compounds in an appropriate ratio. The liquid crystal composition according to the present invention is preferably a ferroelectric liquid crystal composition, particularly a ferroelectric chiral smectic liquid crystal composition.

Other liquid crystal compounds used in the present invention are represented by the following general formulas (III) to (XIII).

[0075]

[Outside 77]

Preferred compounds of the formula (III) are (I
IIa) to (IIIe).

[0077]

[Outside 78]

[0078]

[Outside 79]

Preferred compounds of the formula (IV) are (IV
a) to (IVc).

[0080]

[Outside 80]

[0081]

[Outside 81]

As a preferred compound of the formula (V), (V
a) and (Vb) are mentioned.

[0083]

[Outside 82]

[0084]

[Outside 83]

[0085]

[Outside 84]

[0086]

[Outside 85]

[0087]

[Outside 86]

[0088]

[Outside 87]

[0089]

[Outside 88]

[0090]

[Outside 89]

[0091]

[Outside 90]

[0092]

[Outside 91]

[0093]

[Outside 92]

[0094]

[Outside 93]

[0095]

[Outside 94]

[0096]

[Outside 95]

[0097]

[Outside 96]

[0098]

[Outside 97]

[0099]

[Outside 98]

[0100]

[Outside 99]

[0101]

[Outside 100]

[0102]

[Outer 101]

When the optically active compound of the present invention is mixed with one or more of the above liquid crystalline compounds or the liquid crystal composition, the amount of the optically active compound of the present invention in the liquid crystal composition obtained by mixing is The proportion is from 1% to 80% by weight, preferably from 1% to 60% by weight, more preferably from 1% by weight to
It is preferably 40% by weight.

When two or more optically active compounds of the present invention are used, the proportion of the mixture of two or more optically active compounds of the present invention in the liquid crystal composition obtained by mixing is 1% by weight to 80%. It is desirable to set the content by weight, preferably 1% by weight to 60% by weight.

Next, the liquid crystal element of the present invention comprises the above-mentioned liquid crystal composition disposed between a pair of electrode substrates. Particularly, the ferroelectric liquid crystal layer in the ferroelectric liquid crystal element is as described above. The ferroelectric liquid crystal composition thus prepared is preferably heated in vacuum to an isotropic liquid temperature, enclosed in an element cell, and gradually cooled to form a liquid crystal layer and then returned to normal pressure.

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

Referring to FIG. 1, in the liquid crystal element, a liquid crystal layer 1 exhibiting a chiral smectic phase is arranged between a pair of glass substrates 2 provided with a transparent electrode 3 and an insulating alignment control layer 4, respectively, and The layer thickness is set by the spacer 5, and the lead wire 6 is interposed between the pair of transparent electrodes 3.
The power supply 7 is connected so that a voltage can be applied. In addition, the pair of substrates 2 is sandwiched between the pair of crossed Nicols polarizing plates 8,
The light source 9 is arranged on the outer side of one side.

That is, In ₂ O ₃ , SnO ₂ or ITO (indium) is provided on each of the two glass substrates 2.
Indium Tin Oxid
The transparent electrode 3 made of a thin film such as e) is covered. An insulating alignment control layer 4 for arranging the liquid crystal in the rubbing direction is formed by rubbing a polymer thin film such as polyimide with gauze or acetate flocking cloth or the like.

As the insulating orientation control layer 4, for example, silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen. Substance, cerium oxide, aluminum oxide, zirconium oxide, inorganic oxide such as titanium oxide or magnesium fluoride, insulating layer is formed, and polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyparaxylene, polyester , Polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate,
It may have a two-layer structure in which a layer of an organic insulating material such as polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin or photoresist resin is formed, or an inorganic material insulating orientation control layer or an organic material insulating property. The orientation control layer may be a single layer.

If this insulating orientation control layer is an inorganic type, it can be formed by a vapor deposition method or the like, and if it is an organic type, a solution in which an organic insulating substance is dissolved or its precursor solution (0.1 to 20 in a solvent)
% By weight, preferably 0.2 to 10% by weight) and applied by a spinner coating method, a dip coating method, a screen printing method, a spray coating method, a roll coating method, etc. under predetermined curing conditions (for example, under heating). ) And can be formed by curing.

The layer thickness of the insulating orientation control layer 4 is usually 10Å to
1 μm, preferably 10 Å to 3000 Å, more preferably 10 Å to 1000 Å are suitable.

The two glass substrates 2 are held by the spacer 5 at arbitrary intervals. For example, there is a method in which silica beads and alumina beads having a predetermined diameter are used as spacers and sandwiched between two glass substrates, and the periphery is sealed with a sealing material, for example, an epoxy adhesive material. Alternatively, a polymer film or glass fiber may be used as a spacer. A liquid crystal exhibiting a chiral smectic phase is enclosed between the two glass substrates. The liquid crystal layer 1 is
Generally, the thickness is set to 0.5 to 20 μm, preferably 1 to 5 μm.

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

Further, on the outside of the glass substrate 2, a pair of polarizing plates 8 having their polarization axes in the crossed crossed Nicols state, for example, are attached. The example of FIG. 1 is a transmissive type, and includes a light source 9.

FIG. 2 is a schematic drawing of an example of a cell for explaining the operation of a liquid crystal element utilizing ferroelectricity.
21a and 21b are In ₂ O ₃ , SnO _{2 and} ITO (indium tin oxide; Indium), respectively.
It is a substrate (glass plate) covered with a transparent electrode made of a thin film such as Tin Oxide), in which liquid crystal of SmC ^* phase or SmH ^* phase in which the liquid crystal molecular layer 22 is oriented perpendicular to the glass surface is enclosed. Has been done. A thick line 23 represents a liquid crystal molecule, and the liquid crystal molecule 23 has a dipole moment (P⊥) 2 in a direction orthogonal to the molecule.
Have four. When a voltage of a certain threshold value or more is applied between the electrodes on the substrates 21a and 21b, the helical structure of the liquid crystal molecules 23 is unraveled, and the dipole moment (P⊥) 24 is entirely oriented in the electric field direction. Can be changed. The liquid crystal molecule 23 has an elongated shape and exhibits refractive index anisotropy in the major axis direction and the minor axis direction thereof. Therefore, for example, if crossed Nicols polarizers are placed above and below the glass surface, the voltage application polarity It will be easily understood that the liquid crystal optical modulator has optical characteristics that change.

The liquid crystal cell preferably used in the optical modulator of the present invention has a sufficiently thin thickness (for example, 1
0 μ or less). As the liquid crystal layer becomes thinner in this way, as shown in FIG. 3, the helical structure of the liquid crystal molecules is unwound even when no electric field is applied, and the dipole moment Pa or Pb thereof is directed upward (34a) or downward (34b). Take either state. When an electric field Ea or Eb having different polarities equal to or higher than a certain threshold is applied to such a cell by the voltage applying means 31a and 31b, 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 the liquid crystal molecules are changed to the first stable state 33 accordingly.
a or the second stable state 33b.

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

The first is that the response speed is extremely fast, and the second is that the alignment of the liquid crystal molecules has bistability. Explaining the second point further with reference to FIG. 3, for example, when the electric field Ea is applied, the liquid crystal molecules are aligned in the first stable state 33a, but this state is stable even when the electric field is cut off.
When an electric field Eb in the opposite direction is applied, the liquid crystal molecules are oriented in the second stable state 33b and change their orientation.
After all, it remains in this state even when the electric field is turned off. Also, unless the applied electric field Ea or Eb exceeds a certain threshold value,
Each is also maintained in the previous orientation.

By using the liquid crystal device of the present invention in the display panel section and taking the communication information synchronizing means by the data format as the image information having the scanning line address information and the SYNC signal shown in FIGS. 4 and 5, the liquid crystal display device is obtained. To realize.

In the figure, the symbols are as follows. 101 ferroelectric liquid crystal display device 102 graphic controller 103 display panel 104 scanning line driving circuit 105 information line driving circuit 106 decoder 107 scanning signal generating circuit 108 shift register 109 line memory 110 information signal generating circuit 111 driving control circuit 112 GCPU 113 host CPU 114 VRAM

The image information is generated by the graphics controller 102 on the main body side, and transferred to the display panel 103 according to the signal transfer means shown in FIGS. The graphics controller 102 is a CP
U (central processing unit, hereinafter abbreviated as GCPU 112) and VRAM (memory for storing image information) 114 are used as cores for managing image information and communication between the host CPU 113 and the liquid crystal display device 101, and controlling the present invention. The method is mainly implemented on the graphics controller 102.

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

[0123]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Production of Optically Active 5-decyl- [2- (4-tetrahydrofurfuryloxy) phenyl] pyrimidine (Exemplified Compound 1) It was produced according to the following steps.

[0125]

[Outside 102]

(Step 1) Production of Optically Active Tetrahydrofurfuryl Alcohol Under nitrogen conditions, 0.62 g (12 mmol) of lithium aluminum hydride and 1 tetrahydrofuran
0 ml was stirred at 0 ° C., and R-(+)-tetrahydrofuran-2 diluted with 10 ml of tetrahydrofuran was added thereto.
-1.2 g (10.3 mmol) of carboxylic acid was added dropwise. After the completion of dropping, the mixture was heated to 50 ° C. and stirred for 3 hours. Then, a saturated aqueous sodium sulfate solution was added to precipitate crystals, which were then removed by decantation. Then, sodium sulfate was added and dried, and then sodium sulfate was filtered off and removed. The filtrate was concentrated and then purified by atmospheric distillation to obtain 0.64 g (6.27 mmol) of optically active tetrahydrofurfuryl alcohol in a yield of 61% (bp.174-178 ° C).

(Step 2) Production of optically active tetrahydrofurfuryl p-toluenesulfonate R-(+)-tetrahydrofurfuryl alcohol 0.6
4 g (6.27 mmol) and 5 ml of dichloromethane were stirred at room temperature, 1.20 g (6.27 mmol) of p-toluenesulfonic acid chloride and 3 ml of pyridine were added, and the mixture was stirred at room temperature for about 1 hour. Then, this was concentrated and subjected to silica gel column chromatography (ethyl acetate / toluene = 1/1) to give 0.32 g (1.25 mmo) of optically active tetrahydrofurfuryl p-toluenesulfonate.
l) was obtained with a yield of 20%.

(Step 3) Optically active 5-decyl- [2-
Preparation of (4-tetrahydrofurfuryloxy) phenyl] pyrimidine 5-decyl-2- (p-hydroxyphenyl) pyrimidine 0.32 g (1.02 mmol), dimethylformamide (DMF) 5 ml, sodium hydride 0.0
45 g was stirred at room temperature, and 0.26 g (1.02 g) of optically active tetrahydrofurfuryl p-toluenesulfonate was added thereto.
mmol) and 3 ml of DMF were added, and the mixture was stirred at 100 ° C. for about 2 hours. After that, water was added thereto, an organic layer was extracted with ethyl acetate, washed with a saturated saline solution, added with sodium sulfate, and dried. Then, sodium sulfate was filtered off and concentrated, and then, by silica gel column chromatography (ethyl acetate / toluene = 1/10), optically active 5-decyl- [2- (4-tetrahydrofurfuryloxy) phenyl] pyrimidine. 21 g (0.46 mmol) was obtained with a yield of 45%.

[0129]

[Outside 103]

Example 2 Preparation of Optically Active Tetrahydrofurfuryl 4- (5-decylpyrimidin-2-yl) benzoate (Exemplified Compound 32) It was prepared according to the following steps.

[0131]

[Outside 104]

4- (5-decylpyrimidin-2-yl)
Benzoic acid 0.60 g (1.76 mmol), R-(+)
-Tetrahydrofurfuryl alcohol 0.18 g (1.
76 mmol) and 10 ml of dichloromethane were stirred at room temperature, 0.36 g (1.75 mmol) of N, N'-dicyclohexylcarbodiimide and 0.02 g of 4-pyrrolidinopyridine were added thereto, and the mixture was stirred at room temperature for about 6 hours. The precipitated crystals were separated by filtration and removed, and the filtrate was concentrated, and then subjected to silica gel column chromatography (toluene / ethyl acetate =
10/1), recrystallized (toluene / ethanol) to give optically active tetrahydrofurfuryl 4- (5-decylpyrimidin-2-yl) benzoate 0.30 g (0.71 mmo)
l) was obtained with a yield of 41%. mp. 54 ° C.

Example 3 A liquid crystal composition A was prepared by mixing the following compounds including the exemplified compound 1 produced in Example 1 in the following parts by weight.

[0134]

[Outside 105]

[0135]

[Outside 106] This composition A exhibits the following phase transition temperatures.

[0136]

[Outside 107]

Example 4 Two 0.7 mm thick glass plates were prepared, an ITO film was formed on each glass plate, and voltage application electrodes were prepared.
Further, SiO ₂ was vapor-deposited on this to form an insulating layer. Silane coupling agent on glass plate [KB manufactured by Shin-Etsu Chemical Co., Ltd.
M-602] 0.2% isopropyl alcohol solution was rotated at a rotation speed of 2000 r. p. Apply for 15 seconds at m speed,
A surface treatment was applied. After that, a heat drying treatment was performed at 120 ° C. for 20 minutes.

A polyimide resin precursor [Toray Industries, Inc. SP-
510] 1.5% dimethylacetamide solution was rotated at a rotation speed of 2000 r.p.m. p. m spinner for 15 seconds.
After the film formation, the film was heat-condensed and baked at 300 ° C. for 60 minutes. At this time, the film thickness of the coating film was about 250Å.

The film after firing was rubbed with an acetate flocked cloth, then washed with an isopropyl alcohol solution and sprayed with alumina beads having an average particle size of 2 μm on one glass plate, and then each rubbed treatment. The axes were made parallel to each other, the glass plates were bonded together using an adhesive sealant [Rixon Bond (Chisso Corporation)], and dried by heating at 100 ° C. for 60 minutes to prepare a cell.

The liquid crystal composition A mixed in Example 3 was poured into this cell in an isotropic liquid state and gradually cooled from the isotropic phase to 25 ° C. at 20 ° C./h to obtain a ferroelectric liquid crystal element. Created. When the cell thickness of this cell was measured with a Beret phase plate, it was about 2 μm.

Using this ferroelectric liquid crystal element, the magnitude Ps of spontaneous polarization and the peak-to-peak voltage Vpp = 20.
The response speed (hereinafter referred to as optical response speed) was measured by detecting the optical response (change in transmitted light amount 0 to 90%) under the crossed Nicols by applying the voltage V.

The results are shown below.

[0143]

[Outer 108]

Example 5 A liquid crystal composition B was prepared by mixing the following compounds, including the exemplified compound 32 produced in Example 2, in the following parts by weight.

[0145]

[Outside 109]

[0146]

[Outside 110] This composition B has the following phase transition temperatures.

[0147]

[Outside 111]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used.
The optical response speed and the magnitude Ps of the spontaneous polarization were measured by the same method as in.

The measurement results are shown below.

[0150]

[Outside 112]

Example 6 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition C.

[0152]

[Outside 113]

[0153]

[Outside 114]

Further, with respect to this liquid crystal composition C, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition D.

[0155]

[Outside 115]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that the liquid crystal composition D was injected into the cell.
The optical response speed was measured.

The results are shown below.

[0158]

[Outside 116]

Comparative Example 1 A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that the liquid crystal composition C mixed in Example 6 was injected into the cell, and the optical response speed was measured.

The results are shown below.

[0161]

[Outside 117]

Example 7 A liquid crystal composition E was prepared by mixing the exemplified compounds shown below in place of the exemplified compounds 2 and 4 used in Example 6 in the weight parts shown below.

[0163]

[Outside 118]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used.
The optical response speed was measured by the same method.

The measurement results are shown below.

[0166]

[Outer 119]

Example 8 A liquid crystal composition F was prepared by mixing the following Exemplified Compounds in place of Exemplified Compounds 2 and 4 used in Example 6 in the following parts by weight.

[0168]

[Outside 120]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 4.

The measurement results are shown below.

[0171]

[Outside 121]

Example 9 Liquid crystal composition G was prepared by mixing the following compounds in the following parts by weight.

[0173]

[Outside 122]

[0174]

[Outside 123]

Furthermore, the liquid crystal composition H was prepared by mixing the following exemplary compounds with the liquid crystal composition G in the following parts by weight.

[0176]

[Outside 124]

Except for injecting the liquid crystal composition H into the cell,
A ferroelectric liquid crystal device was prepared by exactly the same method as in Example 4, the optical response speed was measured, and the switching state and the like were observed.

The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.

The measurement results are shown below.

[0180]

[Outside 125]

Further, a clear switching operation was observed during driving, and the bistability when the voltage application was stopped was good.

Comparative Example 2 A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that the liquid crystal composition G mixed in Example 9 was injected into the cell, and the optical response speed was measured.

The results are shown below.

[0184]

[Outside 126]

Example 10 Instead of the Exemplified Compounds 54 and 90 used in Example 9, the Exemplified Compounds shown below were mixed in the respective parts by weight shown below,
A liquid crystal composition I was prepared.

[0186]

[Outer 127]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used, and the optical response speed was measured to observe the switching state and the like.

The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.

The measurement results are shown below.

[0190]

[Outside 128]

Example 11 Instead of the Exemplified Compounds 54 and 90 used in Example 9, the Exemplified compounds shown below were mixed in the respective parts by weight shown below,
A liquid crystal composition J was prepared.

[0192]

[Outside 129]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used, and the optical response speed was measured to observe the switching state and the like.

The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.

The measurement results are shown below.

[0196]

[Outside 130]

Example 12 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition K.

[0198]

[Outer 131]

[0199]

[Outside 132]

Further, with respect to this liquid crystal composition K, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition L.

[0201]

[Outside 133]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used, the optical response speed was measured, and the switching state and the like were observed.

The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.

The measurement results are shown below.

[0205]

[Outside 134]

Comparative Example 3 A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that the liquid crystal composition K mixed in Example 12 was injected into the cell, and the optical response speed was measured.

The results are shown below.

[0208]

[Outside 135]

Example 13 A liquid crystal composition M was prepared by mixing the exemplary compounds shown below in place of the exemplary compounds 144 and 146 used in Example 12 in the following parts by weight.

[0210]

[Outer 136]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used.
The optical response speed was measured by the same method.

The measurement results are shown below.

[0213]

[Outer 137]

Example 14 A liquid crystal composition N was prepared by mixing the exemplified compounds shown below instead of the exemplified compounds 144 and 146 used in Example 12 in the weight parts shown below.

[0215]

[Outer 138]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 4 except that this liquid crystal composition was used.
The optical response speed was measured by the same method.

The measurement results are shown below.

[0218]

[Outside 139]

As is clear from Examples 3 to 14, the ferroelectric liquid crystal device containing the liquid crystal compositions D, E, F, H, I, J, L, M and N according to the present invention operates at a low temperature. The characteristics and high-speed response are improved, and the temperature dependence of response speed is also reduced.

Example 15 Except that the polyimide resin precursor 1.5% dimethylacetamide solution used in Example 6 was replaced with a 2% aqueous solution of polyvinyl alcohol resin [PUA-117 manufactured by Kuraray Co., Ltd.]. Create a ferroelectric liquid crystal element by the method of
The optical response speed was measured in the same manner as in Example 6.

The results are shown below.

[0222]

[Outside 140]

Example 16 A ferroelectric liquid crystal device was prepared and carried out in the same manner as in Example 6 except that the alignment control layer was prepared only with a polyimide resin without using SiO ₂ used in Example 6. The optical response speed was measured in the same manner as in Example 6.

The results are shown below.

[0225]

[Outer 141]

As is apparent from Examples 15 and 16, even when the element structure was changed, the element containing the ferroelectric liquid crystal composition according to the present invention had much improved low-temperature operating characteristics as in Example 6. In addition, the temperature dependence of the response speed is reduced.

[0227]

The element containing the ferroelectric liquid crystal composition of the present invention is a liquid crystal element having good switching characteristics and improved low temperature operation characteristics, and a liquid crystal element having reduced temperature dependence of response speed. can do.

A display device in which the liquid crystal device of the present invention is used as a display device in combination with a light source, a drive circuit, etc. is a good device.

[Brief description of 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 block diagram showing a liquid crystal display device having a liquid crystal element utilizing ferroelectricity and a graphics controller.

FIG. 5 is a timing chart of image information communication between the liquid crystal display device and the graphics controller.

[Explanation of symbols]

 1 Liquid crystal layer having a chiral smectic phase 2 Glass substrate 3 Transparent electrode 4 Insulating orientation control layer 5 Spacer 6 Lead wire 7 Power source 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 molecule 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 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 11 Drive control circuit 112 GCPU 113 host CPU 114 VRAM

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical indication location C07D 417/12 9051-4C C09K 19/34 9279-4H G02F 1/13 500 9225-2K (72) Inventor Iwashiro Takashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Goji Kadano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yoko Yamada Tokyo 3-30-2 Shimomaruko, Ota-ku Canon Inc.

Claims (28)

[Claims] 1. An optically active compound represented by the following general formula (I). [Outer 1] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. m and n are 0 or 1 each independently. A ₁ ,
A ₂ and A ₃ are [external 3] Each is independently selected. However, P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. X _{1 and} X ₂ are single bonds, [External 4] * Indicates that it is optically active. ) 2. The optically active compound according to claim 1, wherein the optically active compound represented by the formula (I) is any one of (Ia) to (Ij). [Outside 5] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. A ₁ , A ₂ , and A ₃ are [external 7] Each is independently selected. However, P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. * Indicates that it is optically active. ) 3. The compound represented by the general formula (I) is represented by any one of (Iaa) to (Ija).
The optically active compound described. [Outside 8] [Outside 9] [Outside 10] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. ) 4. In the general formula (I), R ₁ is the following (1).
The optically active compound according to claim 1, which is any one of (4) to (4). _{(1) -X 3 -C 1 H} 2l + 1 -n ( where, l is an integer of 3-12.) (2) [outer 12] (However, m is an integer of 0 to 6, and n is an integer of 1 to 8.
It may also be optically active. ) (3) [Outside 13] (However, r is an integer of 0 to 6, s is 0 or 1, and t is 1 to
Indicates an integer of 12. It may also be optically active. ) (4) [Outside 14] (However, u is 0 or 1, and v is an integer of 1 to 14.
* Indicates that it is optically active. ) In the above formula, the common X ₃ is a single bond, and 5. A liquid crystal composition comprising at least one kind of the optically active compound according to claim 1. 6. The liquid crystal composition according to claim 5, wherein the optically active compound represented by formula (I) is contained in an amount of 1 to 80% by weight based on the liquid crystal composition. 7. The liquid crystal composition according to claim 5, which contains the optically active compound represented by the general formula (I) in an amount of 1 to 60% by weight based on the liquid crystal composition. 8. The liquid crystal composition according to claim 5, wherein the optically active compound represented by the general formula (I) is contained in an amount of 1 to 40% by weight based on the liquid crystal composition. 9. The liquid crystal composition according to claim 5, wherein the liquid crystal composition has a chiral smectic phase. 10. A liquid crystal device comprising the liquid crystal composition according to claim 5 disposed between a pair of electrode substrates. 11. The liquid crystal device according to claim 10, further comprising an alignment control layer provided on the electrode substrate. 12. The liquid crystal device according to claim 11, wherein the alignment control layer is a layer subjected to a rubbing treatment. 13. The liquid crystal device according to claim 10, wherein the pair of electrode substrates are arranged with a film thickness in which the helical structure of the liquid crystal is released. 14. A display device comprising the liquid crystal element according to claim 10. 15. The display device according to claim 14, wherein liquid crystal molecules are switched by utilizing the ferroelectricity of the liquid crystal composition for display. 16. The display device according to claim 14, further comprising a light source. 17. A display method using a liquid crystal composition containing an optically active compound represented by the following general formula (I) for display. [Outside 16] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are —Y—, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. m and n are 0 or 1 each independently. A ₁ ,
A ₂ and A ₃ are [outer 18] Each is independently selected. However, P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. X _{1 and} X ₂ are single bonds, and * Indicates that it is optically active. ) 18. The display method according to claim 17, wherein the optically active compound represented by the formula (I) is (Ia) to (Ij). [Outside 20] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. A ₁ , A ₂ , and A ₃ are [external 22] Each is independently selected. However, P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. * Indicates that it is optically active. ) 19. The compound represented by the general formula (I) is represented by any one of (Iaa) to (Ija).
7. The display method described in 7. [Outside 23] [Outside 24] [Outside 25] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are -Y-, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. ) 20. The display method according to claim 17, wherein in the general formula (I), R ₁ is any of the following (1) to (4). _{(1) -X 3 -C 1 H} 2l + 1 -n ( where, l is an integer of 3-12.) (2) [outer 27] (However, m is an integer of 0 to 6, and n is an integer of 1 to 8.
It may also be optically active. ) (3) [Outside 28] (However, r is an integer of 0 to 6, s is 0 or 1, and t is 1 to
Indicates an integer of 12. It may also be optically active. ) (4) [Outside 29] (However, u is 0 or 1, and v is an integer of 1 to 14.
* Indicates that it is optically active. ) In the above formula, X _{3 in} common is a single bond, 21. The display method according to claim 17, wherein the optically active compound represented by the general formula (I) is contained in an amount of 1 to 80% by weight based on the liquid crystal composition. 22. The display method according to claim 17, wherein the optically active compound represented by the general formula (I) is contained in an amount of 1 to 60% by weight based on the liquid crystal composition. 23. The display method according to claim 17, wherein the optically active compound represented by the general formula (I) is contained in an amount of 1 to 40% by weight based on the liquid crystal composition. 24. The display method according to claim 17, wherein the liquid crystal composition has a chiral smectic phase. 25. A display method in which a liquid crystal device comprising a liquid crystal composition containing an optically active compound represented by the following general formula (I) is disposed between a pair of electrode substrates for display. [Outside 31] (R ₁ is H, halogen, CN or a carbon number of 1 to 18
Up to a linear or branched alkyl group, wherein one or two or more non-adjacent methylene groups in the alkyl group are —Y—, May be replaced by However, Y represents a -O- or -S-, W represents a halogen, CF _3, CN. m and n are 0 or 1 each independently. A ₁ ,
A ₂ and A ₃ are [external 33] Each is independently selected. P ₁ and P ₂ represent H, halogen, CH ₃ , CF ₃ and CN. X _{1 and} X ₂ are single bonds, and * Indicates that it is optically active. ) 26. The display method according to claim 25, further comprising an alignment control layer provided on the electrode substrate. 27. The display method according to claim 26, wherein the orientation control layer is a layer subjected to a rubbing treatment. 28. The display method according to claim 25, wherein the pair of electrode substrates are arranged with a film thickness in which the helical structure of liquid crystal is released.