JP3096902B2 - Liquid crystal alignment method, liquid crystal element manufacturing method, liquid crystal element and display device by the manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal element used for a light valve used in a flat panel display, a projection display, a printer, and the like, a display device using the liquid crystal element, and a method of manufacturing the same.
Further, the present invention relates to a method for aligning liquid crystal in the liquid crystal element.

[0002]

2. Description of the Related Art Conventionally, widely used liquid crystal elements are, for example, Applied Physics Letters by M. Schadt and W. Helfrich.
Physics Letters, Vol. 18, No. 4 (published Feb. 15, 1971), pp. 127-128, Twisted.
(Nematic) A liquid crystal using a liquid crystal is known.

[0003] A simple matrix type liquid crystal element is known as a typical liquid crystal element configuration. This type is easy to fabricate the element and has an advantage in cost. However, when performing time-division driving using a matrix electrode structure with a high pixel density, there is a problem that crosstalk occurs, so that the number of pixels has been limited. Also, since the response speed is as slow as 10 ms or more,
The use as a display was limited.

In recent years, a liquid crystal element called a TFT (thin film transistor) has been developed for the simple matrix type element as described above. In this type, since a transistor is attached to each pixel, the problems of crosstalk and response speed can be solved.However, the larger the area, the more difficult it is to manufacture a liquid crystal element without defective pixels. Even so, it costs a lot of money.

As a solution to the problems of the conventional liquid crystal device, devices using a liquid crystal exhibiting bistability have been proposed by Clark and Lagerwol.
all) (JP-A-56-1072).
No. 16, US Pat. No. 4,367,924). As a liquid crystal exhibiting this bistability, one of chiral smectic liquid crystals, chiral smectic C (S
A ferroelectric liquid crystal having an (mC ^* ) phase is used. Since the ferroelectric liquid crystal performs inversion switching by spontaneous polarization, a very fast response speed can be obtained and a bistable state having memory properties can be developed. Furthermore, since the viewing angle characteristics are excellent, it is considered that the display element is suitable as a high-speed, high-definition, large-area display element or a light valve.

On the other hand, in a liquid crystal element using a chiral smectic liquid crystal, for example, as described in “Structure and Physical Properties of Ferroelectric Liquid Crystal (Corona Co., Atsuo Fukuda, Hideo Takezoe, 1990), There is a problem that the alignment defect of the ferroelectric liquid crystal is generated and two types of chevron structures are formed by the layer structure of the ferroelectric liquid crystal carried between the upper and lower substrates. This is due to the fact that the bending angle of the structure (the inclination angle δ of the layer) is quite large.Recently, the chevron structure having such a problem has been solved and a layered structure called a bookshelf or a structure similar thereto has been developed. There is a movement to realize a good liquid crystal element with high contrast.
For example, a liquid crystalline compound having a perfluoroether side chain (US Pat. No. 5,262,082, International Patent Application WO 93/22396, the 1993 4th International Conference on Ferroelectric Liquid Crystals) , P-46, Mark Di Radcliffe (M
arc D. Radcliffe)). This liquid crystal can exhibit a structure with a small layer tilt angle close to a bookshelf without using an external field such as an electric field.

It is considered that the reason why the liquid crystal compound having a perfluoroether side chain has a bookshelf structure is that the liquid crystal compound has a property that the liquid crystal molecule interval increases as the temperature becomes lower. That is, in general, in a chiral smectic liquid crystal device, when liquid crystal molecules are oriented from a liquid state (isotropic phase state) at a high temperature through a cooling process, a layer structure is formed in a smectic A (SmA) phase, and an SmC ^* phase [ Or a chiral smectic C _A (SmC _A ) phase], whereby the liquid crystal molecules are tilted from the layer normal direction. At this time, the layer interval is shortened by the amount of the liquid crystal molecules inclined from the layer normal direction, so that a chevron structure has to be adopted to compensate for volume shrinkage. On the other hand, a liquid crystal compound having a perfluoroether side chain has a property that the liquid crystal molecular interval increases as the temperature becomes lower, so that the liquid crystal compound undergoes a phase transition to an SmC ^* phase (or SmC _A phase). Even if the molecules are tilted from the layer normal direction, the SmC ^*
Layer spacing in the phase (or SmC _A phase) can take a value close to the layer spacing in the SmA phase. for that reason,
Even without using an external field such as an electric field, a bookshelf or a structure with a small layer tilt angle close to the bookshelf can be spontaneously produced.

[0008]

However, according to observations made by the present inventors, it has been found that, in the liquid crystal material in which the molecular interval is longer on the low temperature side, the SmC ^* phase (or SmC _A
Phase), it was found that regions having different device characteristics such as an apparent tilt angle and fluctuation of molecules due to an information signal voltage exhibited an orientation state in which the regions were randomly distributed. Here, for the sake of convenience, a region where the apparent tilt angle is relatively large and the amount of fluctuation of molecules due to the information signal voltage is small is defined as a P1 region,
A region where the apparent tilt angle is relatively small and the amount of fluctuation of the molecule due to the information signal voltage is large is referred to as a P2 region.

As a result of detailed studies, the following is considered to be the reason that the areas having different characteristics appear as described above.

[0010] That is, in the liquid crystal material molecules interval becomes longer as the low temperature side, usually SmC ^* phase (or SmC _A phase) as well as intermolecular spacing has a characteristic that it becomes longer as the low-temperature side of the SmA phase . That is, the phase transition from the high temperature side phase (isotropic phase, nematic phase, or cholesteric phase) to the SmA phase forms a bookshelf or a structure having a small layer tilt angle close to the bookshelf. After that, when cooling is further performed, a force for extending the molecular interval acts. However, since the length in the layer normal direction of the liquid crystal element, that is, (layer pitch) × (number of layers) is constant, the molecular interval is increased by cooling. However, the whole system receives the compressive force.

On the other hand, this compression should be applied uniformly to all the layers, but causes uneven compression of a part which is strongly compressed and a part which is not so strongly compressed due to unevenness of cells, temperature and the like. That is, the layer compression unevenness in SmA phase will be appear as unevenness in the element characteristics in the SmC ^* phase (or SmC _A phase).

P1 and P1 having different element characteristics as described above
When the two regions change continuously, this does not pose a problem in practical use. However, when the two regions change discontinuously (rapidly), the boundary between these regions becomes a defect. This causes a reduction in contrast and the generation of an abnormal inversion domain, and a reduction in drive margin.

An object of the present invention is to provide a liquid crystal device using a chiral smectic liquid crystal, in which an Sm ^* phase (or SmC _A) caused by uneven layer compression at high temperature in the SmA phase.
An object of the present invention is to provide a good display device by suppressing the occurrence of unevenness in the element characteristics in the phase), realizing a wide driving margin.

[0014]

The first of the present invention According to an aspect of the Ri liquid crystal exhibiting a chiral smectic phase greens and sandwiched between a pair of electrode substrates, said liquid crystal is a chiral smectic phase temperature range
In circumference, the widest smectic liquid crystal layer spacing d _max
The relationship of the narrowest liquid crystal layer spacing d _min is such that d _min / d _max ≧
A liquid crystal element satisfying 0.990, wherein the liquid crystal is subjected to at least one cycle of a temperature increase and a temperature decrease within a chiral smectic phase temperature range for at least one cycle.

[0015] The second present invention, Ri greens and sandwiched between a liquid crystal exhibiting a chiral smectic phase a pair of electrode substrates, the upper
The liquid crystal has a chiral smectic phase temperature range,
Widest smectic liquid crystal layer spacing d _max and narrowest liquid crystal
The relation of the layer distance d _min satisfies d _min / d _max ≧ 0.990.
Plus A method of manufacturing a liquid crystal device, and descending temperature after injecting liquid crystal isotropic phase in the cell, in the chiral smectic phase temperature range, at least the temperature increase and temperature decrease process to the liquid crystal
A method for manufacturing a liquid crystal element, wherein the method is performed for at least one cycle.

A third aspect of the present invention is a liquid crystal device characterized by being manufactured by the above-described manufacturing method, and a fourth aspect is a display device having the liquid crystal element and its driving means. is there.

The present invention eliminates or alleviates the alignment unevenness due to the layer compression unevenness in the SmA phase, which is peculiar to the liquid crystal material exhibiting a structure having a small book tilt angle close to or near the bookshelf. It is characterized by having improved. That is, in the present invention, the layer compression unevenness caused by the increase in the layer interval due to the cooling of the liquid crystal is made uniform by re-heating in the chiral smectic phase. In a liquid crystal element with reduced compression unevenness, unevenness in element characteristics is suppressed, and a wide drive margin can be obtained.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to one embodiment of the liquid crystal device of the present invention shown in FIG. still,
FIG. 1 is a schematic cross-sectional view.
a and 2b are electrodes, 3 and 4 are alignment control layers, and 5 is a liquid crystal.

In the liquid crystal device of the present invention, a pair of substrates 1a and 1b made of glass, plastic, or the like are arranged to face each other, and electrodes 2a and 2b having a predetermined pattern are formed on each substrate. ing. These electrodes are made of, for example, In ₂ O, SnO ₂ or ITO (Indi).
A transparent conductive film such as um Tin Oxide is used. In the present embodiment, the electrodes 2a and 2b are each formed in a stripe shape, are arranged so as to be substantially orthogonal to each other, and constitute a matrix electrode. In the present invention, one electrode 2 may be formed of metal or the like to form a reflective liquid crystal element. Further, in the present invention, the electrode structure is not limited to the simple matrix structure.

On the electrodes 2a and 2b, alignment control layers 3 and 4 are formed as needed. Either one of the alignment control layers 3 and 4 may be used, or the same film or a combination of different films may be used. In the present embodiment, a preferred embodiment in which the alignment control layers 3 and 4 are formed of different films, which is preferable when a liquid crystal having no cholesteric phase, which will be described later, is used will be described.

The orientation control layer 3 is preferably a layer having a volume resistivity in the range of 1.0 × 10 ^{4 to} 1.0 × 10 ¹⁰ Ωcm. Examples of such a layer include a film made of a polycrystalline or amorphous metal oxide, a film made of a polycrystalline or amorphous semiconductor, and a film in which fine particles (conductive fine particles) are dispersed in a binder, if necessary. Is used. The film made of polycrystalline or amorphous metal oxide, the film made of polycrystalline or amorphous semiconductor, and the fine particles may be added with a conductivity controlling impurity as necessary, and the conductivity is adjusted.

As the film made of the polycrystalline or amorphous metal oxide, for example, a film made of an oxide of a Group IIB element such as ZnO, CdO, ZnCdO _x , GeO ₂ , SnO 2
₂ , GeSnO _x , TiO ₂ , ZrO ₂ , TiZrO _x
And the like, a film made of an oxide of a group IVA element or a group IVB element.

Examples of the film made of the polycrystalline or amorphous semiconductor include a film of a group IVB semiconductor such as Si and SiC.

As the fine particles, for example, the above-mentioned II
Fine particles of an oxide of a group B element, an oxide of a group IVA element, an oxide of a group IVB element, or a semiconductor of a group IVB are used.

The following may be mentioned as the conductivity controlling impurities to be added to the above-mentioned polycrystalline or amorphous metal oxide, polycrystalline or amorphous semiconductor or fine particles as required. Examples of the conductivity control impurity doped into the oxide of the group IIB element include B, Al, which is a group IIIB element, as an n-type impurity (an impurity that enhances donor / electron conductivity).
Ga, In, and the like are p-type impurities (impurities that increase acceptor / hole conductivity), such as C, which is an IA group or IB group element.
u, Ag, Au, Li and the like are used. Examples of the conductivity control impurity doped into the oxide or semiconductor of the IVB group element include P, A, which is a VB group element, as an n-type impurity.
B, Al, Ga, In and the like, which are IIIB elements, are used as s, Sb, and Bi as p-type impurities.

Regarding such conductivity controlling impurities,
A donor is used when the surface potential of the substrate having the orientation control layer including the material to which the impurity is added is positive, and an acceptor is used when the surface potential is negative. The doping concentration of the impurity is set according to the type of the material (combination of the fine particles and the material of the impurity) and the crystal state (the degree of the crystal defect density). The concentration of free holes is 1.0 × 10 ^{11 to} 1.0 × 10 ¹⁴ atm / cm
It is preferable to set it to about ³ . When a polycrystalline or amorphous material is used as a base material to which an impurity is added, 1.0 × 10 4
^The actual addition amount is ^{17 to} 1.0 × 10 ²⁰ atm / cm ³ (about 0.01 to 1% based on the base material).

Examples of a material serving as a binder for dispersing the fine particles include SiO _x , TiO _x , and ZrO.
_x , other oxide melting base materials, siloxane polymers and the like are used.

The orientation control layer 4 has been subjected to a uniaxial orientation treatment. The film thickness is 100 ° or less, preferably 70 ° or less, particularly preferably 50 °.

The orientation control layer 4 is formed, for example, by forming a film of an organic substance by solution coating or the like, and then velvetly coating the film surface.
It can be obtained by rubbing (rubbing) with a fibrous material such as cloth or paper. As a material used for such an orientation control layer, polyvinyl alcohol, polyimide, polyimide amide, polyester, polyamide, polyester imide, polyparaxylene, polycarbonate, polyvinyl acetal, polyvinyl chloride, polystyrene, polysiloxane, cellulose resin, melamine resin,
Organic materials such as urea resin and acrylic resin are exemplified.
Alternatively, an oxide or a nitride such as SiO may be deposited on the substrate by oblique evaporation to form a film, and the film may be formed by an oblique evaporation method that imparts a uniaxial alignment regulating force.

It is particularly preferable to use a polyimide film having a repeating unit represented by the following general formula P as the orientation control layer subjected to the uniaxial orientation treatment.

[0031]

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Further, specific structures of these polyimides include, for example, the following repeating unit structures.

[0033]

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[0034]

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In the liquid crystal device of this embodiment, the substrate 1
a and 1b are bonded together with a sealing material (not shown) at their peripheral portions, and face each other via spacer beads (not shown) within a region defined by the sealing material to form a cell gap. I have. For example, when a ferroelectric liquid crystal is used, the cell gap is set in a range of about 1 to 5 μm. Adhesive beads may be dispersed between the substrates in addition to the spacers in order to enhance the adhesiveness between the substrates.

The liquid crystal 5 used in the present invention is a chiral smectic liquid crystal, and in the SmA phase, a liquid crystal whose layer interval increases when the temperature is lowered is used. Therefore, the effects of the present invention can be obtained not only with ferroelectric liquid crystals but also with antiferroelectric liquid crystals having similar characteristics. In particular, the present invention is preferably applied to a liquid crystal in which the layer spacing increases by 1% or more in the SmA phase.

In the present invention, the relationship between the widest smectic liquid crystal layer distance d _max and the narrowest liquid crystal layer distance d _{min in} the chiral smectic phase temperature range is represented by d:
LCD to meet the _min / d _max ≧ 0.990 is needed use.

Particularly, the liquid crystal used in the present invention includes a liquid crystal having no cholesteric phase.
In addition, when a liquid crystal having no cholesteric phase is used, the alignment state is formed while the tone is gradually generated by the isotropic-smectic phase transition, but the cell is formed by combining different alignment control films as described above. With this configuration, a state in which the battone starts to be generated from one substrate and grows toward the other substrate appears, and it is easy to realize good uniform orientation.

Further, the liquid crystal used in the present invention preferably has a fluorocarbon terminal portion and a hydrocarbon terminal portion, both terminal portions of which are linked by a central nucleus, and which has a smectic intermediate phase or a latent smectic intermediate phase. A liquid crystal composition containing a liquid crystal compound is desirable.

In the fluorine-containing liquid crystal compound, the terminal portion of the fluorocarbon is a group represented by -D ¹ -C _xa F _2xa -X (provided that xa is 1 to 20;
It represents -H or -F, D ¹ is, -CO-O- (C
_{H 2) ra -, - O-} (CH 2) ra -, - (CH 2) ra -,
_{-O-SO 2 -, - SO} 2 -, - SO 2 - (CH 2) ra -,
_{-O- (CH 2) ra -O- (} CH 2) rb -, - (CH 2)
_{ra -N (C pa H 2pa +} 1) -SO 2 -, or - (CH _{2) ra
-N (C pa H 2pa + 1} ) represents the -CO-. ra and rb
Is independently 1 to 20, and pa is 0 to 4. ),
Alternatively, a group represented by -D ^2- (C _xb F _2xb -O) _za -C _ya F _{2ya + 1} (where xb is each of (C
_xb F _2xb -O) is independently 1 to 10, and ya is 1 to
10, za is 1 to 10, and D ² is -CO-
_{O-C rc H 2rc, -O} -C rc H 2rc -, - C rc H 2rc -,
_{-O- (C sa H 2sa -O)} ta -C rd H 2rd -, - O-SO
_{2 -, - SO 2 -,} - SO 2 -C rc H 2rc -, - C rc H 2rc
_{-N (C pb H 2pb + 1} ) -SO 2 -, - C rc H 2rc -N (C
_pb H _2pb + 1) -CO-, selected from a single bond, rc and r
d is independently 1 to 20, sa is independently 1 to 10 for each (C _sa H _2sa -O), and ta is 1
And pb is 0-4. ) Can be used.

Particularly preferably, a fluorine-containing liquid crystal compound represented by the following general formula (I) or (II) can be used.

[0042]

Embedded image Represents

Ga, ha and ia each independently represent an integer of 0 to 3 (provided that ga + ha + ia is at least 2).

Each of L ¹ and L ² is independently a single bond, -CO
-O-, -O-CO-, -COS-, -S-CO-,-
CO-Se-, -Se-CO-, -CO-Te-, -T
_{e-CO -, - CH 2} CH 2 -, - CH = CH -, - C≡
C -, - CH = N - , - N = CH -, - CH 2 -O-,
-O-CH ₂ -, - CO- or represent -O-.

Each of X ¹ , Y ¹ , and Z ¹ is a substituent of A ¹ , A ² , and A ³ and independently represents —H, —Cl, —F, —Br, —
_{I, -OH, -OCH 3, -CH} 3, -CN, or -NO
₂ and each of ja, ma and na independently represents an integer of 0-4.

J ¹ is —CO—O— (CH ₂ ) _ra —, —O
_{- (CH 2) ra -,} - (CH 2) ra -, - O-SO 2 -,
_{-SO 2 -, - SO 2 -} (CH 2) ra -, - O- (CH 2)
_{ra -O- (CH 2) rb -} , - (CH 2) ra -N (C pa H
_2pa + 1) -SO ₂ -, or _{- (CH 2) ra -N (} C pa H
_{2pa + 1} ) represents -CO-. ra and rb are independently 1
-20 and pa is 0-4.

R ¹ is _{-OC qa} H _{2qa -OC qb} H
_{2qb + 1, -C qa H 2qa} -O-C qb H 2qb + 1, -C qa H 2qa -
_{^{R 3, -O-C qa H}} 2qa -R 3, -CO-O-C qa H 2qa -
R ³ or —O—CO—C _qa H _2qa —R ³ , which may be linear or branched (where R ³ _{is-
O-CO-C qb H 2qb} + 1, -CO-O-C qb H 2qb + 1, -
_{H, -Cl, -F, -CF 3} , -NO 2, represents a -CN, qa and qb are 20 independently).

R ² represents C _xa F _2xa -X (X represents -H or -F, and xa is an integer of 1 to 20).

[0049]

Embedded image Represents

Gb, hb and ib are each independently 0 to 3
(Where gb + hb + ib is at least 2).

Each of L ³ and L ⁴ is independently a single bond, —CO
-O-, -O-CO-, -CO-S-, -S-CO-,
-CO-Se-, -Se-CO-, -CO-Te-,-
Te-CO -, - (CH 2 CH 2) ka - (ka is 1
4), -CH = CH-, -C≡C-, -CH = N-,-
_{N = CH -, - CH 2} -O -, - O-CH 2 -, - CO-
Or -O-.

Each of X ² , Y ² and Z ² is a substituent of A ⁴ , A ⁵ and A ⁶ and independently represents —H, —Cl, —F, —Br,
_{I, -OH, -OCH 3, -CH} 3, -CF 3, -O-C
F ₃ , —CN, or —NO ₂ , and each jb, m
b and nb each independently represent an integer of 0 to 4;

J ² is —CO—O—C _rc H _2rc —, —O—
_{C rc H 2rc -, - C} rc H 2rc -, - O- (C sa H 2sa -
O) _ta -C _rd H _2rd- , _-O -SO _2- , -SO ₂ -,-
_{SO 2 -C rc H 2rc -,} - C rc H 2rc -N (C pb H 2pb + 1)
_{-SO 2 -, - C rc H} 2rc -N (C pb H 2pb + 1) -CO-
_Where rc and rd are independently 1-20, sa is independently 1-10 for each (C _sa H _2sa -O), ta is 1-6, pb is 0-4. is there.

R ⁴ is -O- (C _qc H _2qc -O) _wa- C _{qd
H 2qd + 1, - (C} qc H 2qc -O) wa -C qd H 2qd + 1, -C
_qc H _2qc -R ⁶ , _{-OC qc} H _2qc -R ⁶ , -CO- _OC
qc H _2qc -R ^6, or represents _{-O-CO-C qc H 2qc} -R 6, linear, may be either branched (Here, R
⁶ is _{-O-CO-C qd H 2qd} + 1, -CO-O-C qd H
_{2qd + 1, -Cl, -F,} -CF 3, -NO 2, represents -CN, or -H, qc and qd are independently an integer of 1 to 20, the wa is an integer of 1 to 10).

R ⁵ is (C _xb F _2xb -O) _za -C _ya F
_{2ya + 1} is represented by (wherein, the formula xb is 1 to 10 independently of each _{(C xb F 2xb -O),} ya is 1
And za is 1-10).

The compound represented by the above general formula (I) is
JP-A-2-142755, U.S. Pat.
2,587.
Specific examples of such compounds are listed below.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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The compound represented by the above general formula (II) is described in WO 93/22396, JP-T-Hei 7-506.
368 can be obtained.
Specific examples of such compounds are listed below.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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The chiral smectic liquid crystal used in the present invention may contain other compounds, for example, additives such as dyes, pigments, antioxidants and ultraviolet absorbers.

The configuration of the liquid crystal element of the present invention is not limited to the configuration of the above-described embodiment, but may be appropriately applied to a conventional liquid crystal element, particularly a configuration applied to a chiral smectic liquid crystal element.

In the present invention, for example, a liquid crystal heated to an isotropic phase is injected into the cell having the structure of the above embodiment, and the SmC
^* In the phase (or SmC _A phase), heating, cooling step to one or more cycles, preferably for 2 or more cycles.

In the present invention, the temperature range for raising and lowering the temperature is a temperature range showing a chiral smectic phase, and the lower limit is-.
The upper limit is set to 20 ° C. or more, and the upper limit is set to a temperature lower by 0.5 ° C. than a phase transition temperature from a higher-order phase (for example, a smectic A phase) to a chiral smectic phase. Further, the temperature range of the temperature rise and the temperature fall is preferably about 10 to 50 ° C.

In the present invention, the structure of the smectic layer was analyzed by the following X-ray diffraction method.

Basically, the method performed by Clark and Lagerwal [Japan Display (Japan)
n Display) '86, Sep. 30 to Oct.
2, 1986.456 to 458] to determine the layer spacing d and the inclination angle δ of the smectic layer. As the measuring device, an X-ray diffractometer (manufactured by MAC Science) equipped with a rotating cathode type X-ray generating unit equipped with an automatic temperature controller is used. The liquid crystal cell has a small heat capacity and absorbs X-rays on a glass substrate. In order to reduce the size, a microsheet (80 μm thick) manufactured by Corning was used for the substrate.

First, the layer interval d was determined by using a sample obtained by applying a bulk liquid crystal (a liquid crystal composition to be injected into a cell) to a glass substrate so as to have a surface of 5 mm square and having a smooth surface. The resulting peak is referred to as Bragg (Br
agg) was obtained by applying the diffraction condition equation.

The measurement temperature is set to a temperature at which each liquid crystal composition becomes an isotropic liquid state in order to increase the smoothness of the diffraction surface, and then the temperature is decreased by 3 ° C., and at a temperature near the transition point, by 1 ° C. The measurement was performed up to a temperature at which no diffraction peak could be obtained. The automatic temperature controller used in the experiment showed a control accuracy of about ± 0.3 ° C at each temperature.

Next, the smectic layer structure formed in the cell is scanned with the X-ray detector at the diffraction angle 2θ corresponding to the layer spacing determined previously, and the cell is θ-scanned. Determined by

The setting conditions of the X-ray diffractometer were as follows: κα ray of copper was used as the analysis line, and X-ray output = 45 KV × 30 mA
= 13.5 KW, divergence slit: 0.5 °, scanning slit: 0.5 °, light receiving slit: 0.15 mm, scanning speed: 8 ° / min, the irradiation area is determined by the cell jig and the slit. 0 × 1.8 mm ² and cell thickness of 2.0
μm. In addition, Sone is used for background removal.
The veld method was used.

The liquid crystal element of the present invention can be used for a liquid crystal device having various functions.
A liquid crystal display device is realized by using the element in a display panel unit and employing a data synchronization format using image data having scanning line address information shown in FIGS. In the figure, reference numeral 101 denotes a liquid crystal display device, 102 denotes a graphic controller, 1
03 is a display panel, 104 is a scanning line driving circuit, 105 is an information line driving circuit, 106 is a decoder, 107 is a scanning line signal generation circuit, 108 is a shift register, 109 is a line memory, 110 is an information signal generation circuit, and 111 is Drive control circuit, 112 is a GCPU, 113 is a host CPU, 11
4 is a VRAM.

The image information is generated by the graphic controller 102 of the main unit, and is transferred to the display panel 103 according to the signal transmission means shown in FIGS. The graphic controller 102 has a host CPU 113 and a liquid crystal display device 1 with a GCPU (central processing unit) 112 and a VRAM (image information storage memory) 114 as cores.
It is responsible for management and communication of image information during 01. Note that a light source is disposed on the back surface of the display panel.

The display device according to the present invention exhibits excellent drive characteristics because the alignment unevenness of the liquid crystal element as a display medium is suppressed and the drive margin described later is wide, so that a display image of high definition, high speed and large area can be displayed. Obtainable.

The driving method of the liquid crystal element of the present invention is described in, for example, JP-A-59-193426 and JP-A-59-193.
Nos. 427 and 60-156046 and 60-156.
The driving method described in Japanese Patent No. 156047 can be used.

Hereinafter, with reference to the drawings, the matrix driving in the liquid crystal element of the present invention and the driving characteristics which are important at that time will be described.

FIG. 4 is a plan view of an example of a liquid crystal panel on which matrix electrodes are arranged. In the figure, the liquid crystal panel 61, the scanning line of the scanning electrode group 62 (S ₁ ~S _m) and information electrodes 63 of the data line and (I ₁ ~I _n) are wired to cross each other, the scanning line A liquid crystal is arranged between the data line and the data line. Then, each intersection of the scanning line and the data line becomes a pixel which is one display unit, and a voltage is applied from the scanning line and the data line to drive the liquid crystal.

FIGS. 5 and 6 show examples of waveforms of the driving method (multiplex driving) employed in the matrix electrode structure shown in FIG.

The drive waveform shown in FIG. 5 is a reset write type waveform in which black display is set with a positive polarity with respect to the scanning line side and the reset direction is set on the black display side. In the figure, S ₀ represents a scanning signal waveform applied to the scanning line,
I ₁ the information signal waveform applied to the data line (white display waveform)
And I ₂ represents an information signal waveform (black display waveform) applied to the data line. In the figure, (S ₀ -I
₁ ) and (S ₀ -I ₂ ) are voltage waveforms applied to the selected pixel, and the pixel to which the voltage (S ₀ -I ₁ ) is applied becomes a white display state, and the voltage (S ₀ -I ₂ ) Are applied to the black display state (the reset is set to the black display side as described above).

In FIG. 6, (S ₂ -I ₀ ) and (S ₃ -I
₀ ) is a driving waveform shown in FIG. 5, which is applied to the second pixel and the third pixel when "white, white, black, black" is displayed on, for example, four consecutive pixels on the same data line. FIG.

In the driving waveforms shown in FIGS. 5 and 6, the reset pulse for clearing one line is (5/2) Δ with respect to the writing pulse width Δt applied to the pixel on the selected scanning line.
t, and a pulse (1/2) Δt which assists the reset pulse side after the write pulse exists.
Therefore, in the driving waveforms shown in FIGS. 5 and 6, one line scanning period (1H) is 4Δt. However, as shown in FIG. 6, in addition to scanning without providing a scan waveform overlapping time for each line, in addition to providing a scanning waveform of two or more scanning lines (for example, adjacent scanning lines) overlapping an output (for example, It is also possible to shorten the practical one-line scanning time (1H) (for example, to 2Δt).

Each parameter of the driving waveforms shown in FIGS. 5 and 6, the scanning signal voltage V _S , the information signal voltage V _I , and the driving voltage V
_op = V _S + V _I, bias ratio _{= V I / (V S +} V I),
The value of Δt is determined by the switching characteristics of the liquid crystal material used.

FIG. 7 shows the driving waveform shown in FIG.
When the above-mentioned bias ratio is fixed to 1 / 3.4, the driving voltage V _op is fixed at 20 V, and the pulse width Δt is changed, the final after applying the driving waveform (after selecting application) to the corresponding pixel. 5 shows a change in the transmittance T.

In the figure, a solid line indicates a white display waveform (S _0-
I ₁ ) (black erasure (reset), white writing), and dashed lines indicate transmittance when a black display waveform (S ₀ −I ₂ ) (black erasure (reset), black maintenance) is applied.

When a solid white waveform (S ₀ -I ₁ ) is applied, the state before the waveform of the pixel is applied is a black display state, and completely white with a pulse width of Δt ₁ or more. Writing to the display state can be performed.
_At Δt greater than ₂ , writing to the white display state cannot be performed again (the white display waveform (S ₀ −
( _{1 1} ) The black display state occurs again by the application of the reverse polarity auxiliary pulse following the W pulse of I).

In the black display waveform (S ₀ -I ₂ ) of the wavy line, the state before application of the waveform of the corresponding pixel is the opposite white display state, and completely black with a pulse width of Δt ₃ or more. Reset to the display state and holding are realized, and Δt ₄
At a larger Δt, the black display state cannot be maintained (the white display state is achieved by the application of the reverse polarity holding pulse following the B pulse of the black display waveform (S ₀ -I ₂ ) shown in FIG. 5). Become).

Normally, since Δt ₃ <Δt ₁ , Δt ₁ is called the threshold pulse width, and the smaller of Δt _{2 and} Δt ₄ (Δt ₄ in FIG. 7) is called the crosstalk pulse width (Δt ₃ )
₂ is also called a white crosstalk pulse width, and Δt ₄ is also called a black crosstalk pulse width).

Matrix driving is performed by a driving waveform having a pulse width between the threshold pulse width and the crosstalk pulse width, and a white display waveform (white display waveform (S ₀ -I ₁ ) in FIG. 5).
And a reliable black display by a black display waveform (black display waveform (S ₀ -I ₂ ) in FIG. 5) can be realized.
Good white and black images can be displayed only by the difference between the polarities of the information signals.

By increasing the bias ratio described above, it is possible to increase the value of the crosstalk pulse width of Δt ₂ or Δt _4. However, increasing the bias ratio requires increasing the width of the information signal. This means that image quality is not preferable because it causes an increase in flicker and a decrease in contrast.
According to the study of the present inventors, the bias ratio is 1/3 to 1/1.
About 5 was appropriate.

Regarding such drive characteristics, a characteristic of how much margin is provided for setting drive conditions is called a drive margin. As an index for quantitatively evaluating the drive margin, the above-described threshold pulse width Δt is used. _A parameter [M2] representing the width of the value of ₁ and the value of the crosstalk pulse width Δt ₄ (or Δt _{2 in} some cases) from the center value can be used.

M2 = (Δt ₄ −Δt ₁ ) / (Δt ₄ + Δt ₁ )

At a certain temperature, two states of black and white can be written to the selected pixel according to the two directions of the information signal as described above, and the non-selected pixels maintain the black or white state. The drive margin that can be performed differs depending on the liquid crystal material and the element configuration, and is unique. In addition, since the drive margins are different depending on the change in the environmental temperature, in an actual liquid crystal display device,
It is necessary to set optimal driving conditions for the liquid crystal material, element configuration, and environmental temperature. The larger the drive margin parameter M2 is, of course, the more advantageous the display element is.

The driving characteristics (driving margin) shown in FIG.
Is evaluated, the drive voltage V _op is fixed and the pulse width Δ
Although t was changed, conversely, the pulse width Δt may be fixed and the drive voltage V _op may be changed, or both parameters may be changed.

[0107]

EXAMPLE A glass substrate was used as a substrate, and an ITO target was used with a general DC sputtering apparatus.
Power: 1 W / cm ² , Ar: 90S as sputtering gas
CCM, O ₂ : 10 SCCM was flowed, and an ITO film having a thickness of 700 ° was deposited by discharging for 2.5 minutes. The ITO film was patterned into a square of 1 cm × 1 cm by ordinary wet etching to form an electrode.

On one electrode substrate, a solution in which ultrafine particles of antimony-doped SnO _x oxide were dispersed in a silicon oxide base material made of a SiO _x polymer was applied.
rpm, spin for 10 sec, thickness 150
A 0 ° film was formed. Thereafter, baking was performed at 200 ° C. for 60 minutes to form an orientation control layer A.

On the other electrode substrate, a polyimide having the following repeating unit diluted (0.5% by weight) with a mixed solution (2: 1) of NMP (N-methylpyrrolidone) and nBC (n-butylcellosolve) was 500 rpm. , 15 sec
Then, spin coating was performed under the conditions of 1500 rpm and 30 sec, and this was baked at 200 ° C. for 60 minutes to form a polyimide film having a thickness of 50 °. After that, 1000 rpm, pushing amount 0.4 mm, feed speed 50 mm / sec,
The orientation control layer B was formed by performing a rubbing treatment twice in one direction on the polyimide film.

[0110]

Embedded image

Subsequently, 2.4 μm was formed on the orientation control layer B.
A solution containing SiO ₂ fine particles having a diameter of m was spin-coated and then dispersed and fixed by heating. Subsequently, a solution of adhesive particles (particle size: about 5 μm) manufactured by Toray Co., Ltd. was spin-coated, heated and dispersed and fixed.

On the other hand, a sealing material was applied to a desired position on the orientation control layer A using a printing machine, and this was prebaked at 90 ° C. for 5 minutes.

[0113] bonded to the above-mentioned two substrates, and pressed at a pressure of 50gf / cm ² using a press machine. Further, with the same pressure applied by an air cushion, at 150 ° C,
Heating was performed for 90 minutes to cure the sealing material. The cell was arranged between a pair of polarizing plates whose polarization values were orthogonal to each other.

Then, the empty cell produced by the above operation is
Put in a normal load lock type vacuum chamber, 1.0 × 10
After evacuation to about ⁻³ Pa, the liquid crystal element was immersed in a liquid crystal storage tank heated to 85 ° C. in a vacuum of about 1.0 Pa so as to have an injection port, and liquid crystal was injected into the element to produce a liquid crystal element.
In this example, a liquid crystal composition FLC-1 was prepared using the following liquid crystal compounds (a) to (d) and used. This cell was arranged between a pair of polarization axes whose polarization axes were orthogonal to each other.

[0115]

Embedded image

The spontaneous polarization (Ps) of the liquid crystal composition FLC-1 was determined by K. Miyasato et al. "Direct measurement method of spontaneous polarization of ferroelectric liquid crystal by triangular wave" (Journal of the Japan Society of Applied Physics,
22, No. 10 (661) 1983, "Direct M
method with Triangular Wav
es for Measuring Spontane
ous Polarization in Ferro
electric Liquid Crystal ”,
as described by K.S. Miyasat
o et al. (Jap. J. Appl. Phys.
22. No. 10, L661 (1983))).

The tilt angle (Θ) of the liquid crystal composition FLC-1 was determined as follows. That is, ± 30 to ± 5
While applying an AC (alternating current) of 0 V, 1 to 100 Hz between the upper and lower substrates of the liquid crystal element via electrodes, the liquid crystal element disposed therebetween is rotated in parallel with the polarizing plate under orthogonal cross Nicols, Maru (Hamamatsu Photonics)
The first extinction position (the position where the transmittance is lowest) and the second extinction position are determined while detecting the optical response in step (1). At this time, the angle from the first extinction position to the second extinction position is 1 /
Let 2 be the tilt angle Θ.

In this embodiment, the above liquid crystal element was processed under the following two conditions. Example 80 ° C. → 25 ° C. (−1 ° C./min) 25 ° C. → 45 ° C. (1 ° C./min) 45 ° C. → 30 ° C. (−1 ° C./min) Comparative Example 80 ° C. → 30 ° C. (−1 ° C./min) )

The drive margin at 30 ° C. of the liquid crystal element is determined by the method described above using the drive waveforms (V _OP = 20 V, bias ratio = 1 / 3.3, duty ratio = 1/1000) shown in FIGS. (Equivalent, white and black are displayed with a single pixel). The parameter M2 indicating the driving margin is 0.230 for the liquid crystal element of the example and 0.155 for the comparative example.
Thus, according to the present invention, it was found that the driving margin was greatly improved.

[0120]

As described above, according to the present invention,
In a chiral smectic liquid crystal element, alignment unevenness is suppressed, and as a result, a liquid crystal element with a wide driving margin can be obtained, and a high-definition, high-speed, large-area display device with excellent display characteristics can be configured.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of one embodiment of a liquid crystal element of the present invention.

FIG. 2 is a block diagram showing a liquid crystal display device including a liquid crystal element of the present invention and a graphic controller.

FIG. 3 is a diagram showing a timing chart of image information communication between a liquid crystal display device and a graphic controller.

FIG. 4 is a plan view of a liquid crystal panel on which matrix electrodes are arranged.

FIG. 5 is a diagram showing an example of a driving waveform used for driving the liquid crystal element of the present invention.

FIG. 6 is a diagram showing an example of a driving waveform used for driving the liquid crystal element of the present invention.

FIG. 7 is a diagram showing a relationship between a pulse width Δt and a transmittance T when the driving waveform of FIG. 5 is used.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1a, 1b Substrate 2a, 2b Electrode 3, 4 Orientation control layer 61 Display panel 62 Scan electrode group 63 Information electrode group 101 Liquid crystal display device 102 Graphic controller 103 Display panel 104 Scan line drive circuit 105 Information line drive circuit 106 Decoder 107 Scan line Signal generation circuit 108 Shift register 109 Line memory 110 Information signal generation circuit 111 Drive control circuit 112 GCPU 113 Host CPU 114 VRAM

──────────────────────────────────────────────────続 き Continued on the front page (72) Takao Takiguchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Koji Noguchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Yasushi Shimizu 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-8-262386 (JP, A) JP-A-62-30222 (JP) JP-A-64-32020 (JP, A) JP-A-2-1422753 (JP, A) JP-A-6-167711 (JP, A) JP-A-4-246623 (JP, A) 6-324340 (JP, A) JP-A-6-51258 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/1337 510 G02F 1/133 560

Claims (28)

(57) [Claims] 1. A Ri name by sandwiching a liquid crystal exhibiting a chiral smectic phase between a pair of electrode substrates, said liquid crystal is a chiral
The broadest smectic temperature in the smectic phase temperature range
Narrowest relationship of the liquid crystal layer spacing d _min and click the liquid crystal layer spacing d _max
A liquid crystal element satisfying d _min / d _max ≧ 0.990, wherein the liquid crystal is subjected to at least one cycle of temperature raising and lowering in a chiral smectic phase temperature range. 2. The method according to claim 1, wherein the liquid crystal falls in a smectic A phase.
2. The method for aligning liquid crystals according to claim 1, wherein the layer spacing increases by 1% or more at a temperature . 3. The method according to claim 1, wherein the liquid crystal is in a chiral smectic phase.
And bookshelf or similar, with a small layer tilt angle
The method for aligning a liquid crystal according to claim 1 , having a structure . 4. The method for aligning a liquid crystal according to claim 1, wherein the liquid crystal has no cholesteric phase . 5. The method according to claim 1, wherein the liquid crystal is a fluorocarbon terminal portion.
And a hydrocarbon terminal portion, wherein both terminal portions are in the central nucleus.
Therefore, they are bound to form a smectic mesophase or potential smectic
Liquid containing fluorine-containing liquid crystal compound having tic mesophase
LCD method of alignment according to claim 4 Symbol mounting a crystal composition. 6. The liquid crystal composition according to claim 1, wherein
The end portion of the orocarbon is represented by -D ¹ -C _xa F _2xa -X
The liquid crystal alignment method according to claim 5, wherein the group is a group to be formed . (However
In the above formula, xa is 1 to 20, and X is -H or -F
And D ¹ represents —CO—O— (CH ₂ ) _ra —, —O—
(CH ₂ ) _ra -,-(CH ₂ ) _ra- , -O -SO ₂ -,-
SO _2- , -SO _2- (CH ₂ ) _ra- , -O- (CH ₂ ) _{ra
-O- (CH 2) rb -,} - (CH 2) ra -N (C pa H
_2pa + 1) -SO ₂ -, or _{- (CH 2) ra -N (} C pa H
_{2pa + 1} ) represents -CO-. ra and rb are independently 1
-20 and pa is 0-4. ) 7.Full in the fluorine-containing liquid crystal compound
Orocarbon terminal portion is -D ^Two − (C _xb F _2xb -O) _za
-C _ya F _{2ya + 1} Is a group represented byThe liquid according to claim 5.
Crystal orientation method.(Where xb in the above formula is (C
_xb F _2xb -O) is independently 1 to 10, and ya is 1 to
10, za is 1 to 10, D _Two Is -CO-
OC _rc H _2rc -, -OC _rc H _2rc -, -C _rc H
_2rc -, -O- (C _sa H _2sa -O) _ta -C _rd H _2rd −, −
O-SO _Two -, -SO _Two -, -SO _Two -C _rc H _2rc -, -C
_rc H _2rc −N (C _pb H _{2pb + 1} ) -SO _Two -, -C _rc H _2rc −
N (C _pb H _{2pb + 1} ) Selected from -CO-, a single bond, and rc
And rd are each independently 1 to 20, and sa is
Each (C _sa H _2sa -O) independently from 1 to 10, t
a is 1 to 6, and pb is 0 to 4. ) 8.The fluorine-containing liquid crystal compound, the following general
Represented by formula (I)Claim5The liquid crystal alignment method described in the above. Embedded image Represents ga, ha, and ia are each independently an integer of 0 to 3 (provided that
And ga + ha + ia is at least 2)
You. Each L ¹ And L ^Two Is independently a single bond, -CO-O-,
-O-CO-, -COS- , -S-CO-, -CO-S
e-, -Se-CO-, -CO-Te-, -Te-CO
-, -CH _Two CH _Two -, -CH = CH-, -C≡C-,-
CH = N-, -N = CH-, -CH _Two -O-, -OC
H _Two Represents-, -CO- or -O-. Each X ¹ ,
Y ¹ , Z ¹ Is A ¹ , A ^Two , A ^Three And independently represents-
H, -Cl, -F, -Br, -I, -OH, -OC
H _Three , -CH _Three , -CN, or -NO _Two Represents each of
ja, ma and na each independently represent an integer of 0-4. J ¹
Is -CO-O- (CH _Two ) _ra -, -O- (CH _Two )
_ra -,-(CH _Two ) _ra -, -O-SO _Two -, -SO _Two −,
-SO _Two − (CH _Two ) _ra -, -O- (CH _Two ) _ra -O-
(CH _Two ) _rb -,-(CH _Two ) _ra −N (C _pa H _{2pa + 1} )-
SO _Two -Or-(CH _Two ) _ra −N (C _pa H _{2pa + 1} ) -C
Represents O-. ra and rb are independently 1-20
Pa is 0-4. R ¹ Is -OC _qa H _2qa -O
-C _qb H _{2qb + 1} , -C _qa H _2qa -OC _qb H _{2qb + 1} , -C
_qa H _2qa -R ^Three , -OC _qa H _qa -R ^Three , -CO-OC
_qa H _2qa -R ^Three Or -O-CO-C _qa H _2qa -R ^Three Represents
And may be either linear or branched (provided that R
^Three Is -O-CO-C _qb H _{2qb + 1} , -CO-OC _qb H
_{2qb + 1} , -H, -Cl, -F, -CF _Three , -NO _Two , -C
N, and qa and qb are independently 1-20).
R ^Two Is C _xa F _2xa Represents -X (X represents -H or -F
And xa is an integer of 1 to 20). ] 9.The fluorine-containing liquid crystal compound, the following general
Represented by the formula (II)Claim5Alignment of liquid crystal described
Law. Embedded image Represents gb, hb and ib are each independently 0 to 3
Integer (however, gb + hb + ib is at least 2)
Represents Each L ^Three , L ^Four Is independently a single bond, -CO-
O-, -O-CO-, -CO-S-, -S-CO-,-
CO-Se-, -Se-CO-, -CO-Te-, -T
e-CO-,-(CH _Two CH _Two ) _ka -(Ka is 1 to 4),
-CH = CH-, -C≡C-, -CH = N-, -N = C
H-, -CH _Two -O-, -O-CH _Two -, -CO- or-
Represents O-. Each X ^Two , Y ^Two , Z ^Two Is A ^Four , A ^Five , A ⁶ of
Substituents, independently -H, -Cl, -F, -Br,-
I, -OH, -OCH _Three , -CH _Three , -CF _Three , -OC
F _Three , -CN, or -NO _Two And jb, m for each
b and nb each independently represent an integer of 0 to 4; J ^Two Is -C
O-OC _rc H _2rc -, -OC _rc H _2rc -, -C _rc H
_2rc -, -O- (C _sa H _2sa -O) _ta -C _rd H _2rd −, −
O-SO _Two -, -SO _Two -, -SO _Two -C _rc H _2rc -, -C
_rc H _2rc −N (C _pb H _{2pb + 1} ) -SO _Two -, -C _rc H _2rc −
N (C _pb H _{2pb + 1} ) -CO-, and rc and rd are German
It is between 1 and 20 and sa is Each (C _sa H _2sa −
O) independently from 1 to 10, ta from 1 to 6, p
b is 0-4. R ^Four Is -O- (C _qc H _2qc -O) _wa
-C _qd H _{2qd + 1} ,-(C _qc H _2qc -O) _wa -C
_qd H _{2qd + 1} , -C _qc H _2qc -R ⁶ , -OC _qc H _2qc −
R ⁶ , -CO-OC _qc H _2qc -R ⁶ Or -O-CO-
C _qc H _2qc -R ⁶ Represents a linear or branched
May be used (however, R ⁶ Is -O-CO-C _qd H _{2qd + 1} , −
CO-OC _qd H _{2qd + 1} , -Cl, -F, -CF _Three , -N
O _Two , -CN or -H, and qc and qd are independent
Is an integer of 1 to 20, and wa is an integer of 1 to 10.) R
^Five Is (C _xb F _2xb -O) _za -C _ya F _{2ya + 1} Represented by
(Where xb in the above formula is (C _xb F _2xb -O)
Is independently 1 to 10, ya is 1 to 10, za
Is 1 to 10.) ] 10. The liquid crystal according to claim 10, wherein said liquid crystal is a ferroelectric liquid crystal.
10. The liquid crystal alignment method according to any one of 1 to 9 . 11. A liquid crystal method orientation according to any one of claims 1-9 said liquid crystal are anti-ferroelectric liquid crystal. 12. A liquid crystal exhibiting a chiral smectic phase.
The liquid crystal is sandwiched between a pair of electrode substrates,
The broadest smectic in the lusmectic phase temperature range
Click relationship of the liquid crystal layer spacing d _max narrowest liquid crystal layer spacing d _min
Of liquid crystal element satisfying d _min / d _max ≧ 0.990
A method comprising: injecting an isotropic phase liquid crystal into a cell, and then lowering the temperature.
In the chiral smectic phase temperature range,
The crystal is subjected to at least one cycle of heating and cooling.
A method for manufacturing a liquid crystal element, comprising: 13. At least one of said pair of electrode substrates
13. An alignment control layer is provided on a surface in contact with the liquid crystal of claim 12.
Of manufacturing a liquid crystal element. 14. The method for manufacturing a liquid crystal element according to claim 13, wherein an alignment control layer is provided on a surface of each of the pair of electrode substrates which is in contact with the liquid crystal. 15. The manufacturing method of the liquid crystal element of the pair of claim 14, wherein the liquid crystal in contact with the surface of the electrode substrate and the different orientation control layer provided with each other. 16. A method of manufacturing a liquid crystal element of the pair according to claim 1 4, wherein the liquid crystal in contact with the surface of the electrode substrate provided with the same orientation control layer. 17. The liquid crystal in the smectic A phase
17. The layer interval increases by 1% or more when the temperature is lowered.
A method for manufacturing a liquid crystal element according to any one of the above. 18. The liquid crystal according to claim 1, wherein said liquid crystal has a chiral smectic phase.
In the bookshelf or near it, the inclination angle is small
The method for manufacturing a liquid crystal device according to any one of claims 12 to 17, which has a simple structure . 19. The liquid crystal according to claim 19, wherein the liquid crystal has no cholesteric phase.
A method for manufacturing a liquid crystal device according to any one of claims 12 to 18. 20. The method according to claim 19, wherein the liquid crystal is a fluorocarbon terminal.
And a hydrocarbon terminal portion, wherein both terminal portions are a central nucleus.
By a smectic mesophase or latent smectic
Contains a fluorine-containing liquid crystal compound with a ctic mesophase
The method for producing a liquid crystal device according to claim 19 , which is a liquid crystal composition . 21.In the fluorine-containing liquid crystal compound,
The terminal portion of the fluorocarbon is -D ¹ -C _xa F _2xa Table with -X
GroupClaim20How to manufacture the described liquid crystal element
Law.(Where xa is 1 to 20 and X is -H
Or -F, and D ¹ Is -CO-O- (CH _Two )
_ra -, -O- (CH _Two ) _ra -,-(CH _Two ) _ra -, -O-
SO _Two -, -SO _Two -, -SO _Two − (CH _Two ) _ra -, -O-
(CH _Two ) _ra -O- (CH _Two ) _rb -,-(CH _Two ) _ra -N
(C _pa H _{2pa + 1} ) -SO _Two -Or-(CH _Two ) _ra -N
(C _pa H _{2pa + 1} ) Represents -CO-. ra and rb are
Independently, it is 1 to 20, and pa is 0 to 4. ) 22. The fluorine-containing liquid crystal compound according to claim 20, wherein
Fluorocarbons terminal ^{_{portion, -D 2 - (C xb F}} 2xb -O)
_za -C _ya F _{2ya + 1} The method according to claim 20 liquid crystal device wherein a group represented by. (However, in the above formula, xb is each
(C _xb F _2xb -O) independently represents 1 to 10;
Is 1 to 10, za is 1 to 10, and D ² is
_{-CO-O-C rc H 2rc} -, - O-C rc H 2rc -, - C rc
H _2rc- , -O- (C _sa H _2sa -O) _ta -C _rd H _2rd- ,
_{-O-SO 2 -, - SO} 2 -, - SO 2 -C rc H 2rc -, -
_{C rc H 2rc -N (C pb} H 2pb + 1) -SO 2 -, - C rc H 2rc
—N (C _pb H _{2pb + 1} ) —CO—, a single bond, and r
c and rd are each independently 1 to 20, and sa is
_Each (C _sa H _2sa -O) is independently 1 to 10,
ta is 1 to 6, and pb is 0 to 4. ) 23.The fluorine-containing liquid crystal compound has the following one
Represented by the general formula (I)Claim21Of the described liquid crystal element
Construction method. Embedded image Represents ga, ha, and ia are each independently an integer of 0 to 3 (provided that
And ga + ha + ia is at least 2)
You. Each L ¹ And L ^Two Is independently a single bond, -CO-O-,
-O-CO-, -COS-, -S-CO-, -CO-S
e-, -Se-CO-, -CO-Te-, -Te-CO
-, -CH _Two CH _Two -, -CH = CH-, -C≡C-,-
CH = N-, -N = CH-, -CH _Two -O-, -OC
H _Two Represents-, -CO- or -O-. Each X ¹ ,
Y ¹ , Z ¹ Is A ¹ , A ^Two , A ^Three And independently represents-
H, -Cl, -F, -Br, -I, -OH, -OC
H _Three , -CH _Three , -CN, or -NO _Two Represents each of
ja, ma and na each independently represent an integer of 0-4. J ¹
Is -CO-O- (CH _Two ) _ra -, -O- (CH _Two )
_ra -,-(CH _Two ) _ra -, -O-SO _Two -, -SO _Two −,
-SO _Two − (CH _Two ) _ra -, -O- (CH _Two ) _ra -O-
(CH _Two ) _rb -,-(CH _Two ) _ra −N (C _pa H _{2pa + 1} )-
SO _Two -Or-(CH _Two ) _ra −N (C _pa H _{2pa + 1} ) -C
Represents O-. ra and rb are independently 1-20
Pa is 0-4. R ¹ Is -OC _qa H _2qa -O
-C _qb H _{2qb + 1} , -C _qa H _2qa -OC _qb H _{2qb + 1} , -C
_qa H _2qa -R ^Three , -OC _qa H _2qa -R ^Three , -CO-OC
_qa H _2qa -R ^Three Or -O-CO-C _qa H _2qa -R ^Three Represents
And may be either linear or branched (provided that R
^Three Is -O-CO-C _qb H _{2qb + 1} , -CO-OC _qb H
_{2qb + 1} , -H, -Cl, -F, -CF _Three , -NO _Two , -C
N, and qa and qb are independently 1-20).
R ^Two Is C _xa F _2xa Represents -X (X represents -H or -F
And xa is an integer of 1 to 20). ] 24.The fluorine-containing liquid crystal compound has the following one
Represented by the general formula (II)Claim20Of the described liquid crystal element
Production method. Embedded image Represents gb, hb and ib are each independently 0 to 3
Integer (however, gb + hb + ib is at least 2)
Represents Each L ^Three , L ^Four Is independently a single bond, -CO-
O-, -O-CO-, -CO-S-, -S-CO-,-
CO-Se-, -Se-CO-, -CO-Te-, -T
e-CO-,-(CH _Two CH _Two ) _ka -(Ka is 1 to 4),
-CH = CH-, -C≡C-, -CH = N-, -N = C
H-, -CH _Two -O-, -O-CH _Two -, -CO- or-
Represents O-. Each X ^Two , Y ^Two , Z ^Two Is A ^Four , A ^Five , A ⁶ of
Substituents, independently -H, -Cl, -F, -Br,-
I, -OH, -OCH _Three , -CH _Three , -CF _Three , -OC
F _Three , -CN, or -NO _Two And jb, m for each
b and nb each independently represent an integer of 0 to 4; J ^Two Is -C
O-OC _rc H _2rc -, -OC _rc H _2rc -, -C _rc H
_2rc -, -O- (C _sa H _2sa -O) _ta -C _rd H _2rd −, −
O-SO _Two -, -SO _Two -, -SO _Two -C _rc H _2rc -, -C
_rc H _2rc −N (C _pb H _{2pb + 1} ) -SO _Two -, -C _rc H _2rc −
N (C _pb H _{2pb + 1} ) -CO-, and rc and rd are German
And sa is the respective (C _sa H _2sa −
O) independently from 1 to 10, ta from 1 to 6, p
b is 0-4. R ^Four Is -O- (C _qc H _2qc -O) _wa
-C _qd H _{2qd + 1} ,-(C _qc H _2qc -O) _wa -C
_qd H _{2qd + 1} , -C _qc H _2qc -R ⁶ , -OC _qc H _2qc −
R ⁶ , -CO-OC _qc H _2qc -R ⁶ Or -O-CO-
C _qc H _2qc -R ⁶ Represents a linear or branched
May be used (however, R ⁶ Is -O-CO-C _qd H _{2qd + 1} , −
CO-OC _qd H _{2qd + 1} , -Cl, -F, -CF _Three , -N
O _Two , -CN or -H, and qc and qd are independent
Is an integer of 1 to 20, and wa is an integer of 1 to 10.) R
^Five Is (C _xb F _2xb -O) _za -C _ya F _{2ya + 1} Represented by
(Where xb in the above formula is (C _xb F _2xb -O)
Is independently 1 to 10, ya is 1 to 10, za
Is 1 to 10.) ] 25. The liquid crystal according to claim 25, wherein said liquid crystal is a ferroelectric liquid crystal.
25. The method for manufacturing a liquid crystal element according to any one of 12 to 24 . 26. The method according to claim 12 , wherein the liquid crystal is an antiferroelectric liquid crystal . 27. The product according to claim 12,
A liquid crystal element manufactured by a manufacturing method. 28. A liquid crystal device according to claim 27, and said liquid crystal.
A display device comprising: element driving means.