JP3029124B2 - Novel compound, liquid crystal composition containing the same, liquid crystal element and display device using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel compound, a liquid crystal composition containing the same, a liquid crystal element and a display device using the same,
More specifically, the present invention relates to a novel liquid crystal composition having improved response characteristics to an electric field, a liquid crystal element using the same, a liquid crystal element used for a liquid crystal-light shutter, and a display device using the liquid crystal element for display. It is.

[Conventional technology]

Conventionally, liquid crystals have been applied in various fields as electro-optical elements. Most liquid crystal elements currently in practical use are, for example, M. Schadt and
"Applied Physics Letters" by W. Helfrich V
o.18, No.4 (1971.2.15) P.127-128 “Voltage Depen
dent Optical Activity of a Twisted Nematic
TN (Twisted Nematic) shown in "liquid Crystal"
It uses a liquid crystal of a type.

These are based on the dielectric alignment effect of liquid crystal, and utilize the effect that the average molecular axis direction is directed to a specific direction by an applied electric field due to the dielectric anisotropy of liquid crystal molecules.
The limit on the optical response speed of these devices is said to be milliseconds, which is too slow for many applications. On the other hand, in application to a large flat display, driving by the simple matrix method is the most influential in consideration of price, productivity, and the like. In the simple matrix system, an electrode configuration in which a scanning electrode group and a signal electrode group are configured in a matrix is employed. To drive the scanning electrode group, an address signal is sequentially and selectively applied to the scanning electrode group, and the signal electrode group is applied. Adopts a time-division driving method in which a predetermined information signal is selectively applied in parallel in synchronization with an address signal.

However, if the above-described TN type liquid crystal is adopted as an element of such a driving method, a scanning electrode is selected and an area where a signal electrode is not selected or an area where a scanning electrode is not selected and a signal electrode is selected (a so-called “ A finite electric field is also applied to the half-selected point “)”.

If the difference between the voltage applied to the selected point and the voltage applied to the half-selected point is sufficiently large and the voltage threshold required for aligning the liquid crystal molecules perpendicular to the electric field is set to an intermediate voltage value, the display element is Normal operation, but if the number of scanning lines (N) is increased, the whole screen (one frame)
During scanning, the time during which an effective electric field is applied to one selected point (duty ratio) decreases at a rate of 1 / N.

For this reason, the voltage difference as an effective value between the selected point and the non-selected point when the repetitive scanning is performed becomes smaller as the number of scanning lines increases, and as a result, a decrease in image contrast and crosstalk are reduced. It is an inevitable drawback.

Such a phenomenon is caused by a liquid crystal having no bistability (a stable state where liquid crystal molecules are oriented horizontally with respect to the electrode surface, and are vertically oriented only while an electric field is effectively applied. ) Is essentially unavoidable when driving (ie, repeatedly scanning) using the time accumulation effect.

In order to improve this point, a voltage averaging method, a two-frequency driving method, a multiplex matrix method, and the like have already been proposed. At present, the number of scanning lines has reached a plateau due to a failure to sufficiently increase the number of scanning lines.

In order to improve the disadvantages of the conventional liquid crystal device, the use of a bistable liquid crystal device has been proposed by Clarke.
k) and Lagerwell (JP-A-56-107216, U.S. Pat. No. 4,337,924).

In general, a ferroelectric liquid crystal having a chiral smectic C phase (SmC ^* phase) or an H phase (SmH ^* phase) is used as the bistable liquid crystal.

The ferroelectric liquid crystal has a bistable state including a first optically stable state and a second optically stable state with respect to an electric field,
Therefore, unlike the optical modulation element used in the above-mentioned TN type liquid crystal, for example, the liquid crystal is oriented in a first optically stable state with respect to one electric field vector, and the second liquid crystal is aligned with the other electric field vector. The liquid crystal is oriented in an optically stable state. In addition, this type of liquid crystal has a property (bistability) that 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.

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 the transition of the alignment state, and are three to four orders of magnitude faster than the response speed due to the dielectric anisotropy and the action of the electric field.

As described above, ferroelectric liquid crystals have potentially excellent properties, and by utilizing such properties,
Significant improvements are obtained over many of the problems of the conventional TN devices described above. In particular, applications to high-speed optical shutters and high-density, large-screen displays are expected. For this reason, ferroelectric liquid crystal materials have been extensively studied, but the ferroelectric liquid crystal materials developed to date have sufficient characteristics to be used in liquid crystal devices, including low-temperature operation characteristics and high-speed response. It is hard to say that it has.

Between the response time τ and the magnitude Ps of the spontaneous polarization and the viscosity η, the following equation [II] (Where E is the applied electric field). Therefore, in order to increase the response speed, there are (a) increasing the magnitude Ps of spontaneous polarization, (a) decreasing the viscosity η, and (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 is preferably as low as possible. Therefore, it is actually necessary to reduce the viscosity η or increase the value of the magnitude Ps of the spontaneous polarization.

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 large, and there is a tendency that restrictions on an element configuration which can take a bistable state are increased. Further, even if the spontaneous polarization is increased unnecessarily, the viscosity tends to increase with the spontaneous polarization, and as a result, the response speed may not be so high.

In addition, when the operating temperature range of the actual display is, for example, about 5 to 40 ° C., the response speed generally varies.
At present, it is about 20 times, exceeding the limit of adjustment by drive voltage and frequency.

As described above, in order to put a ferroelectric liquid crystal device into practical use, a ferroelectric chiral smectic liquid crystal composition having a low viscosity and a high-speed response and a small temperature dependence of a response speed is required. Is done.

[Problems to be solved by the invention]

An object of the present invention is to provide a compound having a high response speed and an effective compound for reducing the temperature dependence of the response speed in order to make a ferroelectric liquid crystal device practical, a liquid crystal composition containing the compound, In particular, it is an object of the present invention to provide a ferroelectric chiral smectic liquid crystal composition, a liquid crystal element and a liquid crystal device using the liquid crystal composition.

[Means for solving the problem]

The present invention relates to the following general formula (I): R ₁ -A ₁ -BA ₂ -R ₂ (I) (wherein R ₁ and R ₂ are linear or branched alkyl groups having 3 to 18 carbon atoms) Wherein one or two or more non-adjacent methylene groups in the alkyl group are May be replaced by Where Z is -O-
Is shown. B is Or A ₁ is a single bond, Or Is shown. A ₂ is a single bond, -A ₃ - shows the - or -A ₃ -A _4.
A ₃ and A ₄ are each independently A ₁ or Is shown. Y ₁ and Y ₂ are each a hydrogen atom, F, Cl, Br, CH ₃ , C
N or CF ₃ ), a liquid crystal composition containing at least one of the compounds, a liquid crystal element in which the liquid crystal composition is disposed between a pair of electrode substrates, and a liquid crystal element having the liquid crystal element. A liquid crystal device is provided.

Preferred examples of R ₁ and R ₂ in the compound represented by the general formula (I) include (i) to (vi).

(I) R ₁ is n−C _m H _{2m + 1} −X ₁ − R ₂ is n−C _l H _{2l + 1} −X ₂ − Where m and l are integers of 3 to 17, p, r, and s are integers of 0 to 7, q
Represents 0 or 1. R ₄ , R ₅ and R ₆ each represent a linear or branched alkyl group. X ₁ and X ₂ are single bonds, Is shown.

X ₁ is preferably a single bond, —O—, and more preferably a single bond. X ₂ is preferably a single bond, —O—.

A ₁ is preferably a single bond or And more preferably a single bond. A ₂ is preferably And more preferably It is. Note that one of A ₁ and A ₂ are may a single bond. B is preferably It is.

To date, liquid crystal compounds using a benzothiazole ring have been described by AIPavluchenko et al., Mol.Cryst.Liq.Cryst.,
37 , 35 (1976).

In that document, the benzothiazole ring is represented by --COO
Most of the compounds are bonded by a bond such as-, -CH = CH-, -N = CH-, -N = N-, and the compound in which the benzene ring is directly bonded to the 2-position of the benzothiazole ring. Although only two types were described, the side chain at the 6-position of the benzothiazole ring was only a methoxy group, and had only a slight nematic phase.

The present inventors have found that a benzothiazole derivative represented by the general formula (I) in which an alkyl group having 3 or more carbon atoms is introduced into a benzothiazole ring alone or a benzothiazole ring directly bonded to an aromatic ring or a cyclohexane ring has low viscosity. In addition, a compound in which a ring is directly bonded becomes a liquid crystalline compound having a liquid crystal phase in a wide temperature range, a ferroelectric chiral smectic liquid crystal composition containing at least one kind of the compound, and a liquid crystal using the same. By using the element, various characteristics such as high-speed response and reduction of the temperature dependency of the response speed have been improved, and it has been found that good display characteristics can be obtained.

[Specific description of the invention]

An example of a method for synthesizing the liquid crystalline compound represented by the general formula (I) is shown below.

(R ₁ , R ₂ , A ₁ , A ₂ , and B are as defined above.) For synthesis of aminobenzenethiol derivatives, Th.
ahrt, J. prakt. Chem., 66 , 511 (1902)., MTBogert et.
al, J. Am. Chem. Soc., 46 , 1308 (1924).

R ₁ and R ₂ are A ₁ , A ₂ and −Z−, In when attached protected with removable protecting groups hydroxyl or carboxyl groups present in A ₁ or A _2, taken away the ring-closed after a protective group _{deprotection, R 1 -A 1 -, R} 2 −A ₂ − is also possible.

The specific structural formula of the compound represented by the general formula [I] is shown below.

The liquid crystal composition of the present invention can be obtained by mixing at least one of the compounds represented by the general formula (I) and one or more other liquid crystal materials in an appropriate ratio.

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

Other liquid crystal materials used in the present invention are represented by formulas (III) to (X
I) shows below.

e: 0 or 1 f: 0 or 1 where e + f = 0 or 1 Y ': H, halogen, CH ₃ , CF ₃ Preferred compounds of the formula (III) are (IIIa) to (III
d) is raised.

g, h: 0 or 1 where g + h = 1 i: 0 or 1 Preferred compounds of the formula (IV) include (IVa) to (IVc).

j: 0 or 1 Y ₁ ′, Y ₂ ′, Y ₃ ′: H, halogen, CH ₃ , CF ₃ Preferred compounds of the formula (V) include (Va) and (Vb).

k, l, m: 0 or 1 However, k + l + m = 0, 1, 2 Preferred compounds of the formula (VI) include (VIa) to (VIf).

Here, 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. May be replaced by -CH halogen-. Further X _1, X ₂ directly bonded to -CH ₂ - one except group or not adjacent two or more -CH ₂ - groups May be replaced by

However, R ₁ 'or R _2' is one of the CH ₂ group -CH halogen - If halogenated alkyl substituted with, R ₁ '
Or, R ₂ ′ is not a single bond to the ring.

R ₁ ′ and R ₂ ′ are preferably i) a linear alkyl group having 1 to 15 carbon atoms ii) p: 0-5 q: 1-11 integer Integer may be used iii) r: 0-6 s: 0,1 t: 1-14 Integer Optically active iv) u: 0,1 v: 1 to 16 integer v) w: 1 to 15 integers Optical activity may be used vi) A: 0-2 B: 1-15 Integer Optically active may be used vii) C: 0 to 2 D: 1 to 15 integers Optically active compounds (IIIa) to (IIIdc) are more preferable compounds of (IIIa) to (IIId).

Further preferred compounds of (IVa) to (IVc) include (IVaa) to (IVcb).

As a more preferred compound of (Va) to (Vd), (V
aa) to (Vdf).

More preferred compounds of (VIa) to (VIf) include (VIaa) to (VIfa).

E: 0 or 1 F, G: 0 or 1 As more preferred compounds of (VII), (VIIa), (VII
b) is raised.

Preferred compounds of the formula (VIII) are (VIIIa) and (VIII
b) is raised.

More preferred compounds of (VIIIa) and (VIIIb) include (VIIIaa) to (VIIIbb).

Here, 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. May be replaced by -CH halogen-. Further X _1, X ₂ directly bonded to -CH ₂ - one except group or not adjacent two or more -CH ₂ - groups May be replaced by

However, R ₃ 'or R _4' is one of the CH ₂ group -CH halogen - If halogenated alkyl is replaced by, R ₃ '
Or, R ₄ ′ is not a single bond to the ring.

Further, R ₃ ′ and R ₄ ′ are preferably: i) a linear alkyl group having 1 to 15 carbon atoms; ii) p: 0-5 q: 1-11 integer Integer may be used iii) r: 0-6 s: 0,1 t: 1-14 Integer Optically active iv) u: 0-5 v: 1-16 integer v) w: 1 to 15 integers Optical activity may be used vi) A: 0-2 B: 1-15 Integer Optically active may be used vii) C: 0-2 D: 1-15 Integer Optically active H, J: 0 or 1 where H + J = 0 or 1 Preferred compounds of the formula (IX) include (IXa) to (IXc).

Preferred compounds of the formula (X) include (Xa) and (Xb).

As a more preferred compound of (IXa) to (IXc), (IX
aa) to (IX cc).

As more preferred compounds of (Xa) and (Xb), (Xa
a) to (X bb) are raised.

(XIa) to (XIg) as more preferred compounds of (XI)
Is raised.

Here, R ₅ ′ and R ₆ ′ are linear or branched alkyl groups having 1 to 18 carbon atoms, and X ₁ , X ₂
When direct binding to -CH ₂ - not one or adjacent excluding group two or more -CH ₂ - groups May be replaced by

Further, R ₅ ′ and R ₆ ′ are preferably: i) a linear alkyl group having 1 to 15 carbon atoms ii) p: 0-5 q: 1-11 integer Integer may be used iii) r: 0-6 s: 0,1 t: 1-14 Integer Optically active iv) w: 1 to 15 integers may be optically active v) A: 0-2 B: 1-15 Integer Optically active may be used vi) C: 0 to 2 D: 1 to 15 Integer Optically active may be used The compound represented by the general formula (I) of the present invention and another liquid crystal material or a liquid crystal composition (hereinafter abbreviated as liquid crystal material).
In the formula (I) per 100 parts by weight of the liquid crystal material.
It is desired that the liquid crystal compound represented by the formula is 1 to 300 parts by weight, preferably 2 to 200 parts by weight. When two or more compounds represented by the general formula (I) of the present invention are used, the compounding ratio of the compound represented by the general formula (I) with respect to 100 parts by weight of the liquid crystal material may be two or more. Mix 1 to
It is desired to use 500 parts by weight, preferably 2 to 200 parts by weight.

FIG. 1 is a schematic cross-sectional view in the thickness direction of an example of a liquid crystal display device having a ferroelectric liquid crystal layer, for explaining a configuration of a ferroelectric liquid crystal device.

Referring to FIG. 1, the liquid crystal display element has a ferroelectric liquid crystal layer 1 disposed between a pair of glass substrates 2 provided with a transparent electrode 3 and an alignment control layer 4, respectively, and has a layer thickness of a spacer 5
The power supply 7 is connected between the pair of transparent electrodes 3 via a lead wire 6 so that a voltage can be applied.
The pair of substrates 2 is sandwiched between a pair of crossed Nicol polarizers 8, and a light source 9 is disposed outside one of them.

That is, In ₂ O ₃ ,
Transparent electrodes 3 made of thin film such as SnO ₂ or ITO (Indium-TinOxide) is coated. An alignment control layer 4 for arranging liquid crystals in the rubbing direction is formed thereon by rubbing a thin film of a polymer such as polyimide with a gauze or an acetate flocking cloth. Examples of the orientation control layer 4 include silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen, and cerium oxide. Product, aluminum oxide, zirconium oxide, inorganic oxide layer such as titanium oxide and magnesium fluoride, and polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyparaxylene, polyester, polycarbonate, polyvinyl It may have a two-layer structure in which an organic material such as acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin, or photoresist resin is formed, and the inorganic material is oriented. Control layer or Yes It may be a material orientation control layer single layer. If the orientation control film 4 is inorganic, it can be formed by vapor deposition or the like.
To 20% 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, or the like, and under predetermined curing conditions (for example, under heating) ) Can be formed by curing.

The thickness of the insulating orientation control layer is usually 30 to 1 μm, preferably 30 to 3000, and more preferably 50 to 1000.

The two glass substrates 2 are kept at an arbitrary interval by a spacer 5. For example, there is a method in which silica beads or alumina beads having a predetermined diameter are sandwiched between two glass substrates as spacers, and the periphery is sealed with a sealing material, for example, an epoxy-based adhesive. In addition, a polymer film or a glass fiber may be used as the spacer. A ferroelectric liquid crystal 4 is sealed between the two glass substrates. Generally 0.5 to 20 μm, preferably 1 to 5
The thickness is set to μm.

The transparent electrode 3 is connected to an external power supply 7 by a lead wire. Outside the glass substrate 2, a pair of polarizing plates 8 having their polarization axes in, for example, a crossed Nicols state are bonded together. The example of FIG. 1 is of a transmission type and has a light source 9.

FIG. 2 schematically illustrates an example of a cell for explaining the operation of the ferroelectric liquid crystal element. 21a and 21b are respectively
A substrate (glass plate) coated 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 was oriented so as to be perpendicular to the glass surface Liquid crystal of SmC ^* phase or SmH ^* phase is sealed.
A bold line 23 represents a liquid crystal molecule, and the liquid crystal molecule 23 has a dipole moment (P⊥) 14 in a direction perpendicular to the molecule. When a voltage exceeding a certain threshold value is applied between the electrodes on the substrates 21a and 21b, the helical structure of the liquid crystal molecules 23 is released, and the liquid crystal molecules 23 are oriented so that all dipole moments (P⊥) 24 are directed in the direction of the electric field. You can change direction. The liquid crystal molecules 23 have an elongated shape and exhibit refractive index anisotropy in the major axis direction and the minor axis direction. It can be easily understood that the liquid crystal optical modulator has a changed optical characteristic.

The thickness of the liquid crystal cell preferably used in the optical modulation element of the present invention can be made sufficiently thin (for example, 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 its dipole moment Pa or Pb is directed upward (34a) or downward (34b). ). As shown in FIG. 3, an electric field Ea or Eb having a different polarity or more than a certain threshold value is applied to such a cell as shown in FIG.
And 31b, the dipole moment is upward 34a or downward 34b corresponding to the electric field vector of the electric field Ea or Eb.
In response, the liquid crystal molecules are aligned in one of the first stable state 33a and the second stable state 33b.

As described above, there are two advantages of using such ferroelectricity as the optical modulation element.

The first is that the response speed is extremely fast.
Means that the orientation of liquid crystal molecules has bistability. Second
If the electric field Ea is applied, the liquid crystal molecules are oriented to the 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 brought into the second stable state 33b.
Although the orientation of the molecule is changed, the orientation of the molecule is changed, but the state remains even when the electric field is cut off. And the applied electric field Ea or
As long as Eb does not exceed a certain threshold, each is still maintained in the previous alignment state.

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”.

Example 1 2- (P-octylphenyl) -6 according to the following steps
Hexylbenzothiazole (Exemplified Compound I-126) was produced.

(1) Synthesis of 2-amino-6-hexylbenzothiazole 50.0 g of P-hexylaniline (0.28 mol
l), potassium thiocyanate 54.8g (0.56mol), acetic acid 400
ml was charged and cooled to 10 ° C. or less. Under strong stirring,
A solution of 45.0 g of bromine in 135 ml of acetic acid was added dropwise at 40 ° C. or lower over 40 minutes. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 1.5 hours. Next, 500 ml of water was added, and the precipitate was dissolved by heating, followed by hot filtration. The filtrate was made basic by adding aqueous ammonia and cooled with ice. The precipitated crystals were filtered, washed with water and dried to obtain crude crystals. This was recrystallized from n-hexane / benzene (1/1) to give 33.0 g of 2-amino-6-hexylbenzothiazole.
I got Yield 49.9%.

(2) Synthesis of 5-hexyl-2-aminothiol zinc salt A reaction vessel was charged with 30.0 g (0.128 mol) of 2-amino-6-hexylbenzothiazole, 136 ml of water, and 136.4 g of KOH.
The mixture was refluxed for 6.5 hours. After cooling, ethanol was added to dissolve the crystals, and a 5N aqueous acetic acid solution was added dropwise to adjust the pH to 9. The precipitate was removed by filtration, and 8.9 g of ZnCl ₂ was added to the filtrate.
A solution dissolved in 40 ml of a 40% aqueous acetic acid solution was added dropwise. After completion of the dropwise addition, the mixture was heated at 70 ° C. for 30 minutes and filtered. The crystals were washed with hot water, ethanol and water, dried and dried to give 5-hexyl-2-
27.0 g of zinc aminobenzenethiol salt was obtained. Yield 73.4
%.

(3) Synthesis of 2- (P-octylphenyl) -6-hexylbenzothiazole To 3.74 g (16.0 mmol) of P-octylbenzoic acid, 20 ml of thionyl chloride was added, and the mixture was refluxed for 1 hour. After the reflux, excess thionyl chloride was distilled off under reduced pressure. Benzene was added and further distilled off. 3.84 g (8.0 mmol) of 5-hexyl-2-aminobenzenethiol zinc salt was added to this acid chloride, followed by stirring at 200 ° C. for 30 minutes. The reaction solution was allowed to cool, diluted sodium hydroxide aqueous solution (40 ml) was added, and the mixture was extracted with ethyl acetate. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by a silica gel column (developing solvent: hexane / benzene = 10/1). Then, after activated carbon treatment, recrystallization from ethanol
3.45 g of-(P-octylphenyl) -6-hexylbenzothiazole were obtained. Yield 52.9%.

Phase transition temperature (℃) Examples 2 to 4 2- (P-butylphenyl) -6-hexylenzothiazole (Example 2, Exemplified Compound I-122), 2- (P-hexylphenyl) -6 by a method similar to that of the synthesis method of Example 1. -Hexylbenzothiazole (Example 3, Exemplified Compound 1-124), 2- (P-octyloxyphenyl)
-6-Hexylbenzothiazole (Example 4, Exemplified Compound I-174) was produced.

-2- (P-butylphenyl) -6-hexylbenzothiazole (Example 2) Phase transition temperature (° C) -2- (P-hexylphenyl) -6-hexylbenzothiazole (Example 3) Phase transition temperature (° C) -2- (P-octyloxyphenyl) -6-hexylbenzothiazole (Example 4) Phase transition temperature (° C) Example 5 According to the following steps, 2- [2- (5-butylpyridyl)]-6-benzothiazole (Exemplified compound I-334)
Was manufactured.

(1) Synthesis of fusaric acid chloride 10 ml of thionyl chloride was added to 0.72 g (4.0 mmol) of fusaric acid, and the mixture was refluxed for 1 hour. After the reflux, excess thionyl chloride was distilled off under reduced pressure. Benzene was added and further distilled off to obtain an acid chloride.

(2) Synthesis of 2- [2- (5-butylpyridyl)]-6-hexylbenzothiazole 0.96 g (2.0 mmol) of 5-hexyl-2-aminobenzenethiol zinc salt was added to fusaric acid chloride, and the mixture was heated at 230 ° C. At 30
Stirred for minutes. The reaction solution was allowed to cool, 10 ml of a dilute aqueous sodium hydroxide solution was added, and the mixture was extracted with ethyl acetate. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by a silica gel column (developing solvent: benzene / hexane = 7/10).
Then, after activated carbon treatment, recrystallized from ethanol,
0.36 g of 2- [2- (5-butylpyridyl)]-6-hexylbenzothiazole was obtained. Yield 51.0%.

Phase transition temperature (℃) Example 6 2- [P- (trans-4-pentylcyclohexyl) phenyl] -6-hexylbenzothiazole (exemplified compound I-293) was produced according to the following steps.

(1) Synthesis of P- (trans-4-pentylcyclohexyl) benzoic acid chloride 2.0 g (7.3 mmol) of P- (trans-4-pentylcyclohexyl) benzoic acid and 10 ml of benzene were charged into a 30 ml reaction vessel, and the mixture was stirred at room temperature. 1.55 g (7.4 mmol) of PCl ₅ were added over 25 minutes. Thereafter, the mixture was heated under reflux for 4 hours, and the solvent was distilled off.
(Trans-4-pentylcyclohexyl) benzoic acid chloride was obtained.

(2) Synthesis of 2- [P- (trans-4-pentylcyclohexyl) phenyl] -6-hexylbenzothiazole 1.76 g (3.7 mmol) of 5-hexyl-2-aminobenzenethiol zinc salt in a 20 ml reaction vessel, (Trans-4-pentylcyclohexyl) benzoic acid chloride was charged, and 200
Stirred at 30 ° C. for 30 minutes. After the reaction, 10 ml of a diluted NaOH aqueous solution was added, and the mixture was extracted with chloroform. After washing with water and drying MgSO ₄
The solvent was distilled off to obtain 3.1 g of crude crystals. This was purified on a silica gel column with n-hexane / ethyl acetate = 50/1, and 2.4 g
Column purified product was obtained. Then recrystallize with ethanol 2
1.7 g of-[P- (trans-4-pentylcyclohexyl) phenyl] -6-hexylbenzothiazole were obtained. Yield 52.1%.

Phase transition temperature (℃) Example 7 By a method similar to the synthesis method of Example 7, 2- [2- (7
-Hexyl) fluorenyl] -6-hexylbenzothiazole (Exemplified Compound I-390) was produced.

Phase transition temperature (℃) Example 8 2- (trans-4-pentylcyclohexyl) -6
Preparation of hexylbenzothiazole (exemplified compound I-279) trns-4-pentylcyclohexanecarbonyl chloride 0.867 g (4.0 mmol) 5-hexyl-2-aminobenzenethiol zinc salt 0.964 g (2.0 mmol) was added, and the mixture was added at 200 ° C for 30 minutes.
Stirred for minutes. The reaction solution was allowed to cool, 10 ml of a diluted aqueous sodium hydroxide solution was added, and the mixture was extracted with ethyl acetate. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by a silica gel column (developing solvent benzene / hexane = 1/30). Then, it was treated with activated carbon to give 2- (trans-4-pentylcyclohexyl) -6-hexylbenzothiazole 0.35.
7 g were obtained. Yield 48.0%.

Phase transition temperature (℃) Example 9 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition A.

Further, with respect to this liquid crystal composition A, the exemplary compound I-12
4 were mixed in the following parts by weight to prepare a liquid crystal composition B.

Example 10 Two glass plates having a thickness of 0.7 mm were prepared, an ITO film was formed on each of the glass plates, a voltage application electrode was formed, and SiO ₂ was deposited thereon to form an insulating layer. Silane coupling agent [KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.] on glass plate
A 2% isopropyl alcohol solution was applied by a spinner having a rotation speed of 2000 rpm for 15 seconds to perform a surface treatment. After this,
A heat drying treatment was performed at 120 ° C. for 20 minutes.

Further, a 1.5% dimethylacetamide solution of a polyimide resin precursor [Toray Co., Ltd. SP-510] was applied onto a glass plate with an ITO film having been subjected to a surface treatment for 15 seconds by a spinner having a rotation speed of 2000 rpm. After the film formation, a heat condensation calcination treatment was performed at 300 ° C. for 60 minutes. At this time, the thickness of the coating film was about 250 °.

The baked film is subjected to a rubbing treatment with an acetate flocking cloth, then washed with an isopropyl alcohol solution, and alumina beads having an average particle size of 2 μm are sprayed on one glass plate. The glass plates are glued together using an adhesive sealant [Rixon Bond (Chitsuso Co., Ltd.)].
The cells were dried by heating at 100 ° C for minutes.

The liquid crystal composition B mixed in Example 9 was injected into this cell in an isotropic liquid state, and the cell was gradually cooled from the isotropic phase to 25 ° C. at 20 ° C./h, thereby producing a ferroelectric liquid crystal element. The cell thickness of this cell was about 2
μm.

Using this ferroelectric liquid crystal element, the optical response under crossed Nicols by applying a voltage of Ps of spontaneous polarization and a peak-to-peak voltage Vpp = 20V (transmission light change 0-90%)
And the response speed (hereinafter referred to as the optical response speed) was measured. The results are shown below.

10 ° C 30 ° C 45 ° C Response speed 528 μsec 240 μsec 136 μsec Ps 3.4 nC / Cm ² 2.2 nC / Cm ² 1.2 nC / Cm ² Example 11 To the liquid crystal composition A used in Example 9, Exemplified Compound I-174 was used. The liquid crystal composition C was prepared by mixing the following parts by weight.

This indicates the following phase transition temperature:

Example 12 A ferroelectric liquid crystal device was prepared in the same manner as in Example 10 except that the liquid crystal composition C was used, and the magnitude Ps of spontaneous polarization and the optical response speed were measured in the same manner as in Example 10. did.

10 ° C. 30 ° C. 45 ° C. Response speed 518 μsec 226 μsec 140 μsec Ps 4.1 nC / Cm ² 2.9 nC / Cm ² 1.9 nC / Cm ² Example 13 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition D.

Further, to the liquid crystal composition D, the following exemplary compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition E.

Example 10 was repeated except that the liquid crystal composition E was injected into the cell.
A ferroelectric liquid crystal device was prepared in the same manner as described above, and the optical response speed was measured.

 The results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 730 μsec 355 μsec 191 μsec Comparative Example 13 A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10, except that the liquid crystal composition D mixed in Example 13 was injected into the cell. The optical response speed was measured.

 The results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 784 μsec 373 μsec 197 μsec The thing F was created.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 663 μsec 324 μsec 180 μsec The thing G was created.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 631 μsec 310 μsec 177 μsec Example 16 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition H.

Further, to the liquid crystal composition H, the following exemplary compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition I.

Example 10 was repeated except that the liquid crystal composition I was injected into the cell.
A ferroelectric liquid crystal device was prepared in the same manner as described above, and the optical response speed was measured.

 The results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 576 μsec 274 μsec 150 μsec Comparative Example 16 A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that the liquid crystal composition H mixed in Example 16 was injected into the cell. The optical response speed was measured.

 The results are shown below.

10 ° C 25 ° C 40 ° C Response speed 653 μsec 317 μsec 159 μsec Example 17 Exemplified compounds I-122, I-264, I-29 used in Example 16
3, Instead of I-319, the following exemplary compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition J.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C 25 ° C 40 ° C Response speed 596 μsec 288 μsec 149 μsec Example 18 Exemplified compounds I-122, I-264, I-29 used in Example 16
3, Instead of I-319, the following exemplified compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition K.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 560 μsec 272 μsec 141 μsec Example 19 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition L.

Further, the liquid crystal composition L was mixed with the exemplified compounds shown below in parts by weight shown below to prepare a liquid crystal composition M.

Example 10 was repeated except that the liquid crystal composition M was injected into the cell.
A ferroelectric liquid crystal device was prepared in the same manner as described above, and the optical response speed was measured.

 The results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 559 μsec 298 μsec 169 μsec Comparative Example 19 A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that the liquid crystal composition L mixed in Example 19 was injected into the cell. The optical response speed was measured.

 The results are shown below.

10 ° C 25 ° C 40 ° C Response speed 668 μsec 340 μsec 182 μsec Example 20 Exemplified Compounds I-124, I-259, I-41 Used in Example 19
2, Instead of I-416, the following exemplified compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition N.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C 25 ° C 40 ° C Response speed 536 μsec 285 μsec 161 μsec Example 21 Exemplified Compounds I-124, I-259, I-41 Used in Example 19
2, Instead of I-416, the following exemplary compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition O.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 499 μsec 269 μsec 154 μsec Example 22 Instead of the polyimide resin precursor 1.5% dimethylacetamide solution used in Example 13, a polyvinyl alcohol resin [PU-A-117 manufactured by Kuraray Co., Ltd.] 2% A ferroelectric liquid crystal device was prepared in exactly the same manner except that an aqueous solution was used, and the optical response speed was measured in the same manner as in Example 13. The results are shown below.

Without using the 10 ℃ 25 ℃ 40 ℃ 725μsec 348μsec 189μsec Example 23 Example 13 SiO ₂ used in the ferroelectric liquid crystal in exactly the same manner as in Example 13 except that created an orientation control layer only a polyimide resin An element was prepared, and the optical response speed was measured in the same manner as in Example 13. The results are shown below.

10 ° C. 25 ° C. 40 ° C. 722 μsec 343 μsec 185 μsec As is clear from Examples 22 and 23, the device containing the ferroelectric liquid crystal composition according to the present invention operates at a low temperature similarly to Example 13 even when the device configuration is changed. Very improved in properties,
In addition, the temperature dependence of the response speed is reduced.

Examples 24 to 26 2- (P-hexyloxyphenyl) -6-butylbenzothiazole (Example 24, Exemplified Compound I-163), 2- (P-hexyl) in the same manner as in the synthesis method of Example 1. (Oxyphenyl) -6-hexylbenzothiazole (Example 25, Exemplified Compound I-173) and 2- (P-hexylphenyl) -6-hexyloxybenzothiazole (Example 26, I-207) were produced.

-2- (P-hexyloxyphenyl) -6-butylbenzothiazole (Example 24) Phase transition temperature (° C) -2- (P-hexyloxyphenyl) -6-hexylbenzothiazole (Example 25) Phase transition temperature (° C) -2- (P-hexylphenyl) -6-hexyloxybenzothiazole (Example 26) Phase transition temperature (° C) Example 27 According to the following steps, 2- (P-octyloxycarbonylphenyl) -6-octylbenzothiazole (Exemplified Compound I-461) was produced.

(1) 2- (P-methoxycarbonylphenyl) -6
Synthesis of octylbenzothiazole terephthalic acid monomethyl ester chloride 2.26g (11.4m
mol), and 3.00 g (5.57 mmol) of zinc salt of 5-octyl-2-aminobenzenethiol was added thereto, followed by stirring at 210 to 216 ° C for 30 minutes. After allowing the reaction solution to cool, ethyl acetate was added and dissolved by heating. Water was added under cooling with ice water, and the precipitated crystals were collected by filtration. The ethyl acetate layer of the filtrate was separated, washed with brine, dried over anhydrous sodium sulfate, and filtered to remove sodium sulfate.
The filtrate was concentrated and cooled, and the precipitated crystals were collected by filtration. Combined with the above crystals, 2.64 g of 2- (P-methoxycarbonylphenyl) -6-octylbenzothiazole was obtained.
Yield 62.1%.

(2) Synthesis of 2- (P-carboxyphenyl) -6-octylbenzothiazole 85% potassium hydroxide 0.76 g (11.5 mmol) and ethanol 5
After stirring and dissolving at about 65 ° C., 2- (P-methoxycarbonylphenyl) -6-octylbenzothiazole was added.
1.80 g (4.72 mmol) was added, the mixture was stirred at this temperature for 20 minutes, poured into water, and 1.5 ml of concentrated hydrochloric acid was added. After washing with water, drying was performed to obtain 1.66 g of 2- (P-carboxyphenyl) -6-octylbenzothiazole. 95.7% yield.

(3) 2- (P-octyloxycarbonylphenyl)
Synthesis of -6-octylbenzothiazole 2- (P-carboxyphenyl) -6-octylbenzothiazole 0.30 g (0.82 mmol), octanol 0.12 g
(0.92 mmol) and 10 ml of methylene chloride, and N,
N'-dicyclohexylcarbodiimide 0.17 g (0.82mmo
l), 0.02 g of 4-dimethylaminopyridine was added, and the mixture was stirred at room temperature for 6 hours. The resulting dicyclohexylurea was filtered off, washed with methylene chloride and combined with the filtrate. The methylene chloride solution was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: toluene) and recrystallized from toluene / methanol to give 2- (P-octyloxycarbonylphenyl) -6-. 0.20 g of octylbenzothiazole was obtained. Yield 51.1%.

Phase transition temperature (℃) Examples 28 to 30 By a method similar to the synthesis method of Example 27, 2- (P-butyloxycarbonylphenyl) -6-octylbenzothiazole (Example 28, Exemplified Compound I-459), 2-
(P-hexyloxycarbonylphenyl) -6-octylbenzothiazole (Example 29, Exemplified Compound I-46
0), 2- (P-octyloxycarbonylphenyl)
-6-Hexylbenzothiazole (Example 30, Exemplified Compound I-458) was produced.

-2- (P-butyloxycarbonylphenyl) -6
Octylbenzothiazole (Example 28) Phase transition temperature (° C) .2- (P-hexyloxycarbonylphenyl) -6
-Octylbenzothiazole (Example 29) Phase transition temperature (° C) .2- (P-octyloxycarbonylphenyl) -6
-Hexylbenzothiazole (Example 30) Phase transition temperature (° C) Example 31 2- [2- (6-decyloxy) naphthyl] -6-butylbenzothiazole (exemplified compound I-
372).

1.00 g (2.8 g of 6-decyloxy-2-naphthoic acid chloride)
0.58 g (1.22 mmol) of 5-butyl-2-aminobenzenethiol zinc salt was added to 8 mmol), and the mixture was stirred at 200 to 205 ° C for 20 minutes. Ethyl acetate was added, and water and toluene were added at room temperature with stirring. The organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered to remove sodium sulfate, concentrated, and purified by silica gel column chromatography (developing solvent: toluene / hexane = 1/1). After recrystallization from ethyl acetate, the mixture was treated with activated carbon in toluene / ethyl acetate to give 2- [2
-(6-decyloxy) naphthyl] -6-butylbenzothiazole (0.62 g) was obtained. Yield 53.6%.

Phase transition temperature (℃) Example 32 2- (P-hexylcarbonyloxyphenyl) -6-hexylbenzothiazole (exemplified compound I-462) was produced according to the following steps.

(1) Synthesis of 2- (P-acetoxyphenyl) -6-hexylbenzothiazole To 1.80 g (10.0 mmol) of P-acetoxybenzoic acid, 10 ml of thionyl chloride was added, and the mixture was refluxed for 1 hour. After the reflux, excess thionyl chloride was distilled off under reduced pressure. Benzene was added and further distilled off. To this acid chloride was added 2.40 g (5.0 mmol) of 5-hexyl-2-aminobenzenethiol zinc salt, and the mixture was added at 200 ° C.
For 30 minutes. The reaction solution was allowed to cool, an aqueous sodium carbonate solution was added, and the mixture was extracted with ethyl acetate. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by a silica gel column (developing solvent: ethyl acetate / hexane = 1/10).

Then, recrystallization from ethyl acetate / hexane gave 2- (P
-Acetoxyphenyl) -6-hexylbenzothiazole 0.7 g was obtained. Yield 20.0%.

(2) Synthesis of 2- (P-hydroxyphenyl) -6-hexylbenzothiazole 0.7 g (2.0 mmol) of 2- (P-acetoxyphenyl) -6-hexylbenzothiazole, 0.25 g of sodium hydroxide
(6.ommol) and 50 ml of ethanol were added, and the mixture was stirred at room temperature for 10 hours. The mixture was poured into water, 2 ml of concentrated hydrochloric acid was added, and the precipitated crystals were collected by filtration. After washing well with water, dry and dry 2- (P-
(Hydroxyphenyl) -6-hexylbenzothiazole
0.6 g was obtained. 96.5% yield.

(3) 2- (P-hexylcarbonyloxyphenyl)
Synthesis of -6-hexylbenzothiazole 0.32 g (1.03 mmol) of 2- (P-hydroxyphenyl) -6-hexylbenzothiazole, 0.13 g of heptanoic acid (1.
03 mmol), 15 ml of methylene chloride and tetrahydrofuran
5 ml, N, N'-dicyclohexylcarbodiimide 0.21 g under stirring at room temperature, 0.02 g of 4-pyridinopyrazine was added,
The mixture was stirred at room temperature for 6 hours. The resulting dicyclohexylurea was filtered off, washed with methylene chloride and combined with the filtrate. The methylene chloride solution was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent, toluene), and recrystallized twice from toluene / methanol to give 2- (P
-Hexylcarbonyloxyphenyl) -6-hexylbenzothiazole 0.39 g was obtained. 88.6% yield.

Phase transition temperature (℃) Example 33 2- (2-fluoro-4-hexylcarbonyloxyphenyl) -6 was prepared in the same manner as in Example 32 except that 2-fluoro-4-acetoxybenzoic acid was used instead of P-acetoxybenzoic acid. -Hexylbenzothiazole (Exemplified Compound I-463) was produced.

Phase transition temperature (℃) Example 34 In place of Exemplified Compounds I-13 and I-23 used in Example 13, the following Exemplified Compounds were mixed in the following parts by weight, respectively, to prepare a liquid crystal composition.

A ferroelectric liquid crystal device was prepared in exactly the same manner as in Example 10 except that this liquid crystal composition was used, and the optical response speed was measured in the same manner as in Example 10.

 The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 650 μsec 318 μsec 178 μsec [Effects of the Invention] As described above, according to the present invention, a liquid crystal element having good switching characteristics and improved low-temperature operation characteristics, and the temperature dependence of the response speed Provided are a reduced liquid crystal element, and a liquid crystal compound and a liquid crystal composition useful for constituting such a liquid crystal element.

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

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an example of a liquid crystal display device using a ferroelectric liquid crystal, and FIGS. 2 and 3 are perspective views schematically showing an example of an element cell for explaining the operation of the ferroelectric liquid crystal device. FIG. 1 ...... ferroelectric liquid crystal layer 2 ...... glass substrate 3 ...... transparent electrode 4 ...... orientation control layer 5 ...... spacer 6 ...... lead 7 ...... power 8 ...... polarizer 9 ...... source I ₀ ...... incident Light I Transmitted light 21a Substrate 21b Substrate 22 Ferroelectric 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

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoko Yamada 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shinichi Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (56) References JP-A-54-3064 (JP, A) JP-A-54-163815 (JP, A) JP-A-61-220889 (JP, A) JP-A-63-99383 (JP, A A) JP-A-1-281450 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 277/66 C09K 19/34 C09K 19/42 G02F 1/13 500 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (7)

(57) [Claims] 1. A compound represented by the following general formula (I). R ₁ -A ₁ -BA ₂ -R ₂ (I) (where B is A ₁ is a single bond or And A ₂ is Is shown. R ₁ and R ₂ are selected from any of the following (i) to (vi). (I) R ₁ is n−C _m H _{2m + 1} −X ₁ − R ₂ is n−C _l H _{2l + 1} −X ₂ − Here, m and l are integers of 3 to 17, p, r, and s are integers of 0 to 7, and q is 0 or 1. R ₄ , R ₅ and R ₆ each represent a linear or branched alkyl group. X ₁ and X ₂ are single bonds, Is shown. (2) at least one of the compounds according to (I)
A liquid crystal composition comprising a seed. 3. The compound represented by the general formula (I) of the present invention is mixed with another liquid crystal material in an amount of 1 to 300 per 100 parts by weight of the other liquid crystal material. The liquid crystal composition according to claim 2, which is mixed by weight. 4. When two or more kinds of the compounds represented by the general formula (I) of the present invention are used, 100 parts by weight of another liquid crystal material
A mixture of two or more compounds of the general formula (I)
The liquid crystal composition according to claim 2, wherein the liquid crystal composition is mixed in an amount of 500 parts by weight. 5. A liquid crystal device comprising the liquid crystal composition according to claim 2 disposed between a pair of electrode substrates. 6. An apparatus according to claim 5, further comprising an alignment film.
The liquid crystal element according to the above. 7. A display device having the liquid crystal element according to claim 5.