JPH09222606A - Liquid crystal device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate the effect of an electric field and to improve switching characteristics by forming an orientation controlling film consisting of an amide polymer and a polypyridine polymer on a face of one of a pair of substrates brought into contact with a liq. crystal compsn. SOLUTION: Reduced resistance and uniform orienting property are imparted to an orientation controlling film without passing through a doping process by forming the film with a mixture of an electrically conductive n-type polymer with an insulating p-type polymer. The p-type polymer is preferably an electron donative polymer, a polymer having no π-conjugated system is used and an amide polymer such as polyamide or polyimide is preferably used in consideration of liq. crystal orienting property. The n-type polymer is preferably an electron accepting polymer and a polymer having a π-conjugated system such as polypyridine or its deriv. is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal element used for a light valve used for a flat panel display, a projection display, a printer and the like.

[0002]

2. Description of the Related Art A CRT is known as the most widely used display. CRT
Is widely used as a moving picture output for televisions and VTRs, or as a monitor for personal computers. However, C
Due to the characteristics of RT, when a still image is displayed, flicker or scanning line stripes due to insufficient resolution lowers the visibility, or the phosphor deteriorates due to burn-in. Further, it has recently been revealed that the electromagnetic waves generated by the CRT have a bad influence on the human body, and there is a concern that the health of the VDT worker may be impaired. And the CRT is structurally
Since it has a large volume behind the screen, it may hinder space saving in offices and homes, and may not be able to fulfill its responsibility as a display in a highly information-oriented society.

As a solution to such a drawback of the CRT, there is a liquid crystal element. For example, M. Shut (MS
chadt) and W. Helfrich
Frich), "Applied Physics Letters"
s) A liquid crystal device using a twisted nematic liquid crystal disclosed in Vol. 18, No. 4 (issued on Feb. 15, 1971), pp. 127 to 128 is known. When such liquid crystal elements are classified according to the driving method, one of them is a simple matrix type liquid crystal element which is superior in cost. This liquid crystal element has a problem that crosstalk occurs in time-division driving using a matrix electrode structure with a high pixel density, and thus the number of pixels is limited. In addition, since the response speed is as slow as several tens of milliseconds, the use as a display has been limited. In recent years, an active matrix type liquid crystal element using a TFT (thin film transistor) or the like has been developed to improve the disadvantages of such a simple matrix type liquid crystal element. This type of liquid crystal element
Since switching elements such as transistors are created for each pixel, the problems of crosstalk and response speed are solved.However, the larger the area, the more industrially it is extremely difficult to create a liquid crystal element without defective pixels. And costly if possible.

As a solution to the drawbacks of the conventional liquid crystal device, a liquid crystal device using a bistable liquid crystal device is known as Clark or Lagawell.
gerwall) (Japanese Patent Laid-Open No. 56-
107216, U.S. Pat. No. 4,367,924, etc.). As the liquid crystal having the bistability, a ferroelectric liquid crystal which is a chiral smectic liquid crystal exhibiting a chiral smectic C phase or a chiral smectic H phase is generally used. Since the ferroelectric liquid crystal performs inversion switching by spontaneous polarization, it has a very fast response speed and can exhibit a bistable state with memory properties. Furthermore, since it has excellent viewing angle characteristics when used for a display element, it is considered to be suitably used for a high-speed, high-definition, large-area display element or light valve. Recently, by Chan Dani and Takezoe,
Chiral smectic antiferroelectric liquid crystal devices that exhibit three stable states have also been proposed (Japanese Journal of Applied Physics).
e Journal of Applied Physs
ics) 27, 1988 L729).

In such a chiral smectic liquid crystal device, for example, when liquid crystal molecules are aligned by using a general rubbing-treated polyimide alignment film, an apparent tilt angle (a liquid crystal molecule in two stable states) is obtained. 1/2 of the angle formed by the axis is generally at most 3 ° to 8 °
Therefore, the transmittance of the liquid crystal element was 3 to 5%, and the contrast was around 10 which was a considerably low value. Further, as described in “Structure and Physical Properties of Ferroelectric Liquid Crystal” (Corona Publishing Co., Ltd., Atsuo Fukuzawa, Hideo Takezoe, 1990), generation of zigzag alignment defects and occurrence of liquid crystal molecules between upper and lower substrates. There is also a problem that the contrast is significantly reduced due to the twist (called splay orientation). This alignment defect (zigzag defect) is caused by the fact that the layered structure (smectic layer structure) of the liquid crystal sandwiched between the pair of substrates has a chevron-like structure (chevron structure) in two directions. ing. Hanyu et al. Made the chevron structure uniform in one direction by increasing the pretilt angle of liquid crystal molecules at the interface of the alignment film, and made the splay alignment elastically more unstable than the uniform state (uniform alignment). As a result, a liquid crystal element having a large contrast is obtained by eliminating the zigzag defect and increasing the apparent tilt angle (JP-A-3-252624). However, even if the method of Hanyu et al. Is used, in order to obtain a good driving state, for example, the tilt angle must be 16 ° or less, and the tilt angle (22.5 °) at which the ideal transmittance can be obtained. ), There is room for further improvement. In addition, the inclination of the smectic layer peculiar to the chevron structure also lowers the transmittance, and causes a reduction in contrast.

On the other hand, recently, a chevron structure which is a cause of low contrast has been eliminated, and a layered structure called a bookshelf (hereinafter, this structure is referred to as a bookshelf structure),
Alternatively, there has been a movement to realize a structure close to that and realize high contrast (for example, "Next Generation Liquid Crystal Display and Liquid Crystal Materials", edited by CMC, Atsuo Fukuda, 1992). As a means for realizing such a structure, there is a method of using a naphthalene-based liquid crystal material, but in this case, the tilt angle is about 10 °, and compared with 22.5 ° at which the ideal maximum transmittance is obtained. Very small,
There is a problem of low transmittance. Moreover,
There is also a problem that the bookshelf structure cannot be exposed reversibly with temperature. Another typical method is to induce a bookshelf structure by applying a high electric field from the outside to a liquid crystal device having a chevron structure, but this method also has a problem of instability with respect to external stimuli such as temperature. Has become. A liquid crystal having a bookshelf structure has only recently been discovered in recent years, and there are various other problems for practical use.

Further, a liquid crystal compound having a fluorocarbon terminal portion has been proposed as a component of a liquid crystal composition having a bookshelf structure or a structure close thereto (US Pat. No. 5,262,082, International Application Publication WO93 /).
22396, 1993 4th International Conference on Ferroelectric Liquid Crystals P
-46, Mark D. et al. Radcliffe et al., Etc.).
By mixing this liquid crystalline compound with an optically active compound, a bookshelf structure or a structure close to it, which has a small layer tilt angle, can be revealed without using an external field such as an electric field, and high speed, high definition, large Suitable for liquid crystal element and liquid crystal device with large area. However, further improvements are required in terms of speed, orientation, contrast, driving stability, etc. of liquid crystal elements.

[0008]

In particular, by optimizing the apparent tilt angle θa in a liquid crystal device using a liquid crystal composition having the above-mentioned bookshelf structure or a structure close thereto, and expanding the tilt angle θa to about 22.5 °. When trying to achieve high brightness, the viscosity of the liquid crystal composition increases,
The slower electric field response became a new problem.

It is known that the molecular response of the chiral smectic liquid crystal is represented by the following equation (1) by the spontaneous polarization Ps of the liquid crystal and the external electric field E.

Τ = η / PsE Equation (1) where τ is the time constant of the response of the liquid crystal to the electric field, and η is the resistance coefficient called switching viscosity. Therefore, in order to overcome the viscosity increased by the tilt angle optimization for high brightness, it is necessary to increase the spontaneous polarization Ps in the molecular design of the liquid crystal (increasing the electric field is effective to some extent. However, the increase of the drive voltage is limited by power consumption, heat generation, etc., so that it is realistic to increase the spontaneous polarization Ps of the liquid crystal).

When the spontaneous polarization of the liquid crystal is increased, hysteresis occurs in the inversion threshold between the two states, and the temperature dependence of the spontaneous polarization causes a problem that the liquid crystal driving margin decreases as the temperature decreases. I will end up. This means that impurity ions and the like in the liquid crystal accumulate at the interface between the liquid crystal and the alignment control film / electrode, and as a result, the following formula (2),
It is considered that the cause is that the counter electric field component shown in (3) is induced and the electric field response of the liquid crystal molecules is obstructed.

V _reverse = [− 2Ps / (C _i + C _lc )] exp (t / τ) Formula (2) where Ps is the spontaneous polarization of the liquid crystal, and C _i and C _lc are the alignment control film and the liquid crystal layer, respectively. , Τ is a time constant determined from the combined capacitance of the liquid crystal layer and the orientation control film, that is, the relaxation time of the anti-electric field component. The orientation control film and the resistance of the liquid crystal layer are R _i ,
When represented by R _lc , τ = CR = (C _i + C _lc ) / [(1 / R _i ) + (1 / R _lc )] Formula (3) Therefore, the attenuation process of the anti-electric field of the liquid crystal depends on the resistance of the liquid crystal electrode interface as represented by the above formula (2), and the resistance of the alignment control film is reduced to reduce the influence of the anti-electric field. Is possible.

Generally, in order to align a chiral smectic liquid crystal, a polymer film of polyimide (PI), polyamide (PA) or the like having a horizontal orientation or a tilt orientation is formed on the surface of a substrate, and a rubbing treatment is performed in substantially the same direction. A pair of substrates is used. These electrical characteristics are 1 × 10 ¹⁰ Ωc at room temperature.
This is an insulating film having a resistance value of m or more, and the anti-electric field induced in the electric field response of liquid crystal having high spontaneous polarization causes a problem in terms of switching characteristics.

As a method for solving the above-mentioned problems, it is expected that a conductive polymer is used for an orientation control film. In addition to the above-mentioned purpose, the resistance of the orientation control film can be prevented from being electrostatically charged in the orientation control film during the rubbing process to prevent the adsorption of charged foreign matter, and further, it has bistability. In the chiral smectic liquid crystal, the delocalization of the local bias of the charge on the film surface has a great merit that the memory property can be improved and the uniform alignment can be realized.

As an example of lowering the resistance of the orientation control film, a π-conjugated conductive polymer film using polyaniline (Japanese Patent Laid-Open No. Hei 5 (1999) -53977).
No. 19264), one containing conductive fine particles dispersed in a polymer matrix (JP-A-3-92824), one containing a charge transfer complex (US Pat. No. 5,231,523). ) Etc. have been proposed,
Both of them have the following problems as the alignment control film of the liquid crystal element.

In the undoped state, the π-conjugated polymer film as described above is also an insulating film like polyimide or the like, and requires acid, alkali or electrochemical doping treatment to reduce the resistance. These post-treatments not only complicate the manufacturing process, but also pose a problem that there is a risk of contamination and corrosion of the liquid crystal layer and the transparent electrode wiring due to the dopant.

Further, in the case where the conductive fine particles are dispersed as described above, the fine particles and the surrounding binder film are liable to peel off during rubbing, which may cause an alignment defect.

On the other hand, in the case where the charge transfer complex is dispersed as described above, there is a problem that thermal instability of the complex and a rapid increase in resistance when the complex is mixed in the alignment control film.

The present invention has been made in view of the above problems, and its object is to prevent the adsorption of charged foreign matter to the alignment control film by lowering the resistance of the alignment control film. It is to provide a highly reliable liquid crystal element.

Another object of the present invention is to provide a liquid crystal device exhibiting good switching characteristics by suppressing the influence of a counter electric field in a liquid crystal device using a liquid crystal exhibiting a chiral smectic phase.

In addition, an object of the present invention is to provide a chiral smectic liquid crystal device having high contrast and high brightness, which has a bookshelf structure in which a counter electric field has a great influence on switching characteristics or a structure having a small layer tilt angle close to the bookshelf structure. It is intended to realize difficult high-speed switching, and to provide a liquid crystal device with high-speed drawing, high brightness, and high contrast, in particular, a liquid crystal display device by using the element.

Furthermore, in the present invention, the influence of the anti-electric field, which has been a serious problem in the liquid crystal device using the liquid crystal composition containing the liquid crystal compound having the fluorocarbon terminal portion as described above, is reduced by the composition of the alignment control film. It is intended to realize a liquid crystal element exhibiting excellent switching characteristics by solving the above prescription.

[0023]

The present invention is a liquid crystal device in which a liquid crystal composition is sandwiched between a pair of substrates, and the liquid crystal element is aligned on the surface of at least one of the pair of substrates in contact with the liquid crystal composition. A liquid crystal element, in which a control film is formed, and the alignment control film is composed of an amide polymer and a polypyridine polymer.

Further, the present invention is a liquid crystal device in which a liquid crystal composition is sandwiched between a pair of substrates, and an alignment control film is formed on a surface of at least one of the pair of substrates which is in contact with the liquid crystal composition. The orientation control film is a film made of a conductive polymer and an insulating polymer, and the conductivity of the orientation control film is higher than the conductivity of a film made of the conductive polymer alone. A characteristic liquid crystal element.

In the present invention, the conductive polymer is a polymer having a π-conjugated system, and the insulating polymer is a polymer having no π-conjugated system. It is preferable that the optical absorption based on the π-π ^* transition per 1 π bond of the polymer having is increased by adding the polymer not having the π bond.

With this configuration, the resistance of the orientation control film can be reduced without performing any of chemical doping, electrochemical doping, addition of charge transfer complex, and addition of conductive fine particles to the orientation control film. Can be achieved.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is directed to an alignment control film (alignment film).
In order to solve the above-mentioned problems that hinder the reduction of the resistance of the polymer, a conductive polymer (hereinafter abbreviated as type N polymer) and an insulating polymer (hereinafter type P) are used. The polymer is abbreviated as “polymer”) to form the orientation control film, and thereby the resistance of the orientation control film and the uniform orientation can be realized without a doping process.

As the type P polymer, various insulating polymers can be used, but an electron donating polymer is preferable, and a polymer having no π-conjugated system, and further considering the orientation of liquid crystals. Amide polymers such as polyamide, polyamide, and polyimide are preferably used.

As the type N polymer, various conductive polymers can be used, but electron-accepting polymers are preferable, and polymers having a π-conjugated system such as polypyridine and its derivatives are preferable. Used for.

In the present invention, the conductivity of the orientation control film composed of the type N polymer and the type P polymer is higher than the conductivity of the film composed of the type N polymer alone. In a combination in which the type N polymer has a π-conjugated system and the type P polymer does not have a π-conjugated system, the alignment control film is
The optical absorption based on the π-π ^* transition per 1 π bond of the polymer having the π conjugated system is increased by adding the polymer not having the π bond.

Above all, from the viewpoint of easy mixing,
It is preferable to use a combination of polyamide and polypyridine or a derivative thereof.

Although the details of the mechanism for reducing resistance in the present invention have not been clarified, it is presumed that the reduction in resistance has been achieved due to the following factors. In addition, below, type P
The alignment control film using polyamide as the above polymer and polypyridine or its derivative as the type N polymer will be described as an example, but the same mechanism can be applied to the alignment control films using other polymers according to the present invention. It is considered that low resistance is achieved.

Factor 1 (Efficient Generation of Conductive Carriers Due to Charge Transfer between Both Resins) Since polypyridine has a high oxidation potential due to the strong electronegativity of the lone pair of electrons in the nitrogen of the pyridine ring, it is a cation such as Pd. I can only dope. That is, since it is hard to be oxidized and easily reduced, it is considered that when it is mixed with polyamide such as nylon, it is in an electron rich state by attracting electrons from the polyamide side, while the polyamide is in a proton rich state.

In Table 1, the absorbance around 490 nm based on the π-π ^* transition of the dispersion mixed film of nylon 66 and polythiophene pyridine is shown by the thiophene pyridine ring (-C ₄ H ₂ S-C ₅
H ₃ N-) shows the value normalized by the concentration with respect to the blend weight ratio. Since this absorbance corresponds to the carrier concentration (electron concentration) distributed on the main chain of polythiophene pyridine, the polythiophene pyridine is polarized by the inclusion of nylon in this blend system, and the carrier concentration is higher than that of the polythiophene pyridine single film. It was observed that the concentration was increasing.

[0035]

[Table 1]

Factor 2 (developed carrier conduction path) As is well known, polypyridine and its derivative polymers are π-conjugated polymers, and have a developed conduction electron path on their main chains. There is. On the other hand, polyamide resins such as nylon 66 are generally known as insulators, but are known to be proton (H ⁺ ) conductive under an electric field of about 300 V / cm ( S. Saito, Reports on Progr
ess in Polymer Physics in
Japan, XII, 411 (1969), D.I. A.
Seanor, J .; Polymer. Sci. A-2,
6, 463 (1968)). Therefore, it is considered that even if both resins are mixed, the conduction paths of the generated carriers are mutually guaranteed without being divided.

As described above, it is considered that the two polymers function as a polymer charge transfer complex, so that the resistance of each polymer is lower than that of each of them by mixing.

Also, in the uniform orientation of the chiral smectic liquid crystal, the polypyridine-based polymer and the polyamide-based polymer have excellent orientation. Among them, a nylon-based polyamide-based polymer having a methylene chain in its main chain is used. The polymer is excellent in aligning the liquid crystal composition containing the above-mentioned liquid crystal compound having a fluorocarbon terminal. Further, both have an advantage that they can be easily mixed in terms of process because m-cresol, formic acid and the like are used as a common solvent.

The present invention has a particularly remarkable effect in improving the switching characteristics of a highly spontaneous polarization type chiral smectic liquid crystal having a bookshelf structure or a layer structure close to it, but a chiral smectic structure having a chevron structure is obtained. Also for liquid crystals, it is particularly effective in improving the switching characteristics on the low temperature side. Further, the present invention can be effectively used in liquid crystal elements other than chiral smectic liquid crystals to reduce the resistance of the alignment film.

An example of the liquid crystal element according to the present invention will be described below.

A structural example of the liquid crystal element of the present invention is shown in FIG.
In the liquid crystal element of the present invention, the glass substrates 11a, 11
b on the transparent electrodes 12a and 12b and the alignment control film 14a,
14b is formed, and at least one of the orientation control films 14a and 14b is a mixed film of the above-described type N and type P polymers. Preferably, the type P is the following general formula P
-1 is a polyamide-based polymer having a repeating unit having a structure represented by -1, and Type N is a polypyridine-based polymer having a repeating unit having a structure represented by the following general formula P-2.

General Formula P-1 —CONH— (CH ₂ ) _n —NHCO— (CH ₂ ) _m — General Formula P-2-AB— (wherein, m and n are the same or different 1 to 1)
Any integer of 2. A is a pyridine ring and the bonding position with B is the 2 or 5 position, and B is any of a pyridine ring, a thiophene ring, a pyrrole ring, a fluorenone ring, an isothianaphthenepyridine ring, a furan ring and a thiophenepyridine ring. In the thiophene ring and the pyrrole ring, the proton at the 3- or 4-position is an alkyl group, an alkoxy group, a carboxylic acid ester group, a phenyl group, a naphthyl group, an anthracene
It may be substituted with an yl group. )

Here, the degree of polymerization of the polyamide polymer having a repeating unit of the structure represented by P-1 is 1,000 or more and 100,000 in consideration of the orientation control ability and the solubility.
The following is preferred. Further, the polymerization degree of the polypyridine-based polymer having a repeating unit represented by P-2 is 100 or more and 10000 in view of the orientation control ability and the solubility.
0 or less is preferable, and 1000 or more and 50,000 or less is more preferable.

In the present invention, the weight ratio of the amide polymer and the polypyridine polymer is preferably 5:95 to 45:55 from the viewpoint of lowering the resistance, and is 15: 8.
It is more preferable that the ratio is 5 to 35:65.

In the present invention, the orientation control film 14 is used.
Insulating films 13a and 13b formed by sputtering or vapor deposition of silicon oxide, tantalum oxide, or the like may be provided between a and 14b and the transparent electrodes 12a and 12b.

The above substrate is used as a spacer 16 such as silica beads.
A sealing material is used to bond them together to form a cell. The liquid crystal composition 15 is injected into this cell by using a capillary phenomenon or the like to manufacture the liquid crystal element of the present invention.

As the liquid crystal composition 15, a nematic liquid crystal composition, a chiral smectic liquid crystal composition, or the like is used. Particularly, by using the chiral smectic liquid crystal composition, a great effect can be obtained in terms of suppressing the counter electric field.

The liquid crystal composition used in the present invention preferably has a fluorocarbon terminal portion and a hydrocarbon terminal portion, and both terminal portions are bound by a central nucleus to have a smectic mesophase or a latent smectic mesophase. Those containing a fluorine-containing liquid crystal compound are desirable.

Generally, the fluorine-containing liquid crystal compound used in the present invention has a central nucleus, and the central nucleus has at least two aromatic rings, heteroaromatic rings, aliphatic rings, or substituted aromatic rings. A ring or a substituted aliphatic ring, and these rings are --COO--, --COS--, --HC = N--,-
It may be bound by a functional group selected from COSe-. These rings may be fused or unfused. The heteroatoms in the heteroaromatic ring contain at least one atom selected from N, O or S. Non-adjacent methylene groups in the aliphatic ring may be replaced by O.

In the fluorine-containing liquid crystal compound, the fluorocarbon terminal portion is a group represented by -D ¹ -C _xa F _2xa -X (provided that xa is 1 to 20, X
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 single bonds, 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.

[0052]

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 --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- , <sub>--O
- (CH 2) ra -,</sub> - (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 --O--C _qa H _2qa --O--C _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).

[0059]

Embedded image Represents

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

L ³ and L ⁴ are 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 -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;

[0063] 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.

[0064] 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, -O-}} C qc H 2qc -R 6, -CO-O-C
_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)
JP-A-2-142755, U.S. Pat.
2,587.
Specific examples of such compounds are listed below.

[0067]

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[0068]

[Chemical 6]

[0069]

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[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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[0075]

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[0076]

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[0077]

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[0078]

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The compounds represented by the above general formula (II) are described in International Publication WO93 / 22396, Japanese Patent Publication No. 7-506.
368 can be obtained.
Specific examples of such compounds are listed below.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

[Chemical 21]

The chiral smectic liquid crystal composition used in the present invention contains, for example, a compound having a chiral moiety as shown below.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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These compounds are used alone or in the form of a mixture of plural compounds as a base material of the chiral smectic liquid crystal composition.

For the chiral smectic liquid crystal composition used in the present invention, various other liquid crystal compounds including a chiral compound and an achiral compound other than those described above are appropriately selected depending on the compatibility of the compounds, the control of the layer spacing and the like. To use. In particular, the compound having a fluorocarbon terminal portion as described above is used as an essential component, and the compounding ratio of the chiral compound is appropriately set according to the type. For example, the chiral compound is blended in a range of about 0.5 to 50% by weight.
When a chiral compound having no fluorine-based end portion is used, the compounding ratio of the chiral compound is 0.1 to 10% by weight in consideration of compatibility with a compound having a base fluorocarbon end portion. It is preferable that In addition, antioxidants, UV absorbers, dyes,
Additives such as pigments may be contained.

Next, an example of the structural formula of the repeating unit of the polyamide polymer represented by the general formula P-1 will be shown.

[0099]

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Next, an example of the structural formula of the repeating unit of the polypyridine polymer represented by the general formula P-2 is shown.

[0101]

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[0102]

EXAMPLES Specific examples and comparative examples will be shown below. First, each evaluation method in the present example and comparative example will be described.

[Evaluation of Uniform Orientation] Orientation (Layer normal direction)
The homogeneity of T is measured by measuring the transmittance in the darkest state in the SmA phase with crossed Nicols between the polarization axes of the analyzer and the polarizer, and normalized by the amount of transmitted light when the polarization axes of the analyzer and the polarizer are set to Paranicol. _It was evaluated using the parameter _d . This is 100%
It is desirable that the absolute value is small, with the upper limit being.

T _d = I _c / I _p I _c = Amount of transmitted light at the darkest position when the polarizer-analyzer is set to crossed Nicols I _p = Positioner-at the darkest position when the analyzer is set to para-Nicol Amount of transmitted light [Evaluation of film resistivity] Corning # 7059 substrate was ultrasonically cleaned with trichlorethylene, acetone, ethanol and pure water, and finally purified water was cleaned and dried in a dry nitrogen atmosphere. Prepare and coat the substrate with the orientation control film material solution by spin coating etc. to a film thickness of 100Å and bake it, and then evaporate 300Å the gold electrode of the comb-teeth type opposing shape by resistance heating to obtain the resistance in the sheet direction. The volume resistance was measured and measured (temperature 25 ° C., humidity 55%). For volume resistance, a ring-shaped gold film was prepared by coating and baking an alignment control film to a film thickness of 1000 Å by the same method as above using a substrate having 700 Å vapor-deposited ITO on a # 7059 substrate also manufactured by Corning. 300 by resistance heating evaporation of electrodes
It can also be obtained by forming with Å and measuring the resistance in the film thickness direction.

[Driving Characteristic Evaluation] The effect of the anti-electric field on the electric field response of the liquid crystal was evaluated at 10 ° C. by operating the operation pulse including the reset pulse and the bipolar pulse as shown in FIG.
A voltage of ₁ and V ₄ is applied to the 1-second intervals while changing the 0V → 40V → 0V at 4V / min, V ₄ is applied after the end of 800
The transmittance in msec was determined, and the inversion threshold voltage was determined from the 50% transmission condition of the resulting voltage-transmittance curve.
At this time, the inversion threshold voltage in the process of 0V → 40V is V ₁₂ , and the inversion threshold voltage in the process of 40V → 0V is V _21.
In this case, the hysteresis voltage is defined as the difference in inversion threshold value V _H = V ₁₂ −V ₂₁ .

Example 1 The liquid crystal element of this example was manufactured as follows.

A Corning # 7059 substrate was ultrasonically cleaned with trichloroethylene, acetone, ethanol, and pure water, and finally with pure water, dried in a dry nitrogen atmosphere, and then nylon 66 having a degree of polymerization of 5000. And a mixed formic acid solution of polythiophene pyridine (PTpy) having a polymerization degree of 2000 was spin-coated. As the coating solution, a 0.5 wt% formic acid solution was prepared in which the solid content ratio of nylon 66 and PTpy was adjusted to 25:75. Spin conditions were 2000 rpm and 20 seconds. This substrate, 8
After solvent drying in an oven at 0 ° C for 5 minutes,
It was heated and baked in an oven at 0 ° C. for 1 hour. The thickness of the obtained mixed film was about 100Å.

Next, a tooth-shaped gold electrode was provided on the obtained film by an evaporation method of resistance heating to about 300 Å, and then the resistance value was measured by a micro ammeter. At this time, the volume resistance is 5 × 10 ⁷ Ω
cm.

Next, a transparent electrode 15 is formed by sputtering.
A pair of glass substrates on which ITO (indium tin oxide) having a thickness of 00Å was formed was prepared, and one of the substrates was spin-coated with the mixed formic acid solution. This substrate, 80 ℃
After solvent-drying in the oven for 5 minutes, it was heated and baked in the oven at 180 ° C. for 1 hour. The mixed film obtained is about 1
With a thickness of 00Å, push roller into this film 0.4m
m, roller rotation speed 1000 rpm, substrate feed speed 5 m
The rubbing treatment was performed 3 times at m / sec. The roller was a roller having a diameter of 8 cm wrapped with a nylon cloth.

Then, an IPA (isopropyl alcohol) solution in which 0.01% by weight of silica beads having an average particle size of 2.0 μm are dispersed on the surface of one of the substrates is 1500.
Spin coating under conditions of rpm, 10 seconds, distribution density 300
The number of beads spacers per unit / mm ² was scattered.

On the opposite substrate, a 0.5 wt% ethanol solution of a silane coupling agent (ODS-E) was added.
It was applied with a spinner under the conditions of 00 rpm and 20 seconds and subjected to vertical alignment treatment. Then, it was dried in an oven at 180 ° C. for 1 hour. A thermosetting liquid adhesive was applied to this substrate by a printing method.

The two substrates thus obtained were laminated facing each other and thermoset in an oven at 150 ° C. for 90 minutes to form a cell.

The liquid crystal composition described below was injected into this cell under reduced pressure (10 Pa) at an isotropic phase temperature (100 ° C.),
A liquid crystal element was obtained by gradually cooling to the SmC ^* phase.

The mixed liquid crystal composition used in this example is shown below.

Weight ratio: Compound A / B / C / D / E = 4
6.4 / 15.5 / 30.9 / 5.2 / 2.0

[0116]

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[0117]

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The physical property parameters of this composition are shown below.

[0119]

[Equation 1]

The methods for measuring the tilt angle and the spontaneous polarization are as follows.

[Measurement of tilt angle] ± 30 to ± 50 V,
While applying an AC (alternating current) of 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 crossed Nicols, and at the same time, the photomultiplier ( The first extinction position (the position where the transmittance is lowest) and the second extinction position are determined while detecting the optical response with Hamamatsu Photonics Co., Ltd. The angle of the angle from the first extinction position to the second extinction position at this time is 1
/ 2 is the tilt angle.

[Measurement Method of Spontaneous Polarization]
Miyasato et al. "Direct measurement method of spontaneous polarization of ferroelectric liquid crystal using triangular wave" (Journal of the Japan Society of Applied Physics 22, 10 (66)
1) 1983, "Direct Method wit
h Triangular Waves for Me
asuring Spontaneous Polar
Ization in Ferroelectric L
liquid Crystal ", as descri
bed by K.M. Miyasato et al (J
ap. J. Appl. Phys. 22. No. 10, L
661 (1983))).

The above chiral smectic liquid crystal cell was placed on the FP82 hot stage controlled by the Mettler FP80HT temperature controller, and the temperature decreasing rate from the isotropic phase (90 ° C.) to the SmA phase (50 ° C.) was -1 ° C./min. And the transmittance was measured by obtaining the darkest state in the SmA phase under crossed Nicols, and the transmittance was 100% under Paranicols, and T _d was 0.50%. Further, when the inversion threshold was measured at 10 ° C. with the voltage variable with a pulse width of 20 μsec, the inversion threshold V ₁₂ and the inversion threshold V
The difference (V _H ) of ₂₁ was 0.3V.

[Comparative Example 1] # 7059 manufactured by Corning Incorporated
Prepare a substrate washed in the same manner as in Example 1,
A 1.0 wt% formic acid solution of nylon 66 having a degree of polymerization of 5000 was spin-coated on the substrate. Spin condition is 300
It was carried out at 0 rpm for 20 seconds. This substrate was solvent-dried in an oven at 80 ° C. for 5 minutes, and then heated and baked in an oven at 180 ° C. for 1 hour. The thickness of the obtained mixed film was about 100Å.

Next, a comb-teeth-shaped gold electrode was provided on the obtained film by a resistance heating vapor deposition method at about 300 Å, and then the resistance value was measured by a minute ammeter. At this time, the volume resistance is 2 × 10 ^10.
Ωcm.

Next, as in Example 1, a pair of glass substrates having transparent electrodes formed thereon were prepared, and the nylon 66 film was formed on one of the substrates under the above-mentioned conditions, and the same rubbing as in Example 1 was performed. Then, the other substrate was subjected to the same vertical alignment treatment as in Example 1 to fabricate a cell.

The liquid crystal composition used in Example 1 was injected into this cell under reduced pressure (10 Pa) at an isotropic phase temperature (100 ° C.), and the liquid crystal element was obtained by gradually cooling to the SmC ^* phase.

When the transmittance of this liquid crystal cell in the darkest state was measured in the same manner as in Example 1, it was T _d = 0.45%. When the inversion threshold was measured at 10 ° C. with a variable pulse width of 20 μsec, V _H was 1.5 V.
Met.

[Comparative Example 2] # 7059 manufactured by Corning Incorporated
Prepare a substrate washed in the same manner as in Example 1,
A 1.0 wt% formic acid solution of PTpy was applied on the substrate. Spin conditions were 1000 rpm and 20 seconds. The substrate was dried in a 80 ° C. oven for 5 minutes with a solvent, and then heated and baked in a 180 ° C. oven for 1 hour.
The thickness of the obtained mixed film was about 100Å.

Next, a comb-teeth type gold electrode was provided on the obtained film by a resistance heating evaporation method at about 300 Å, and then the resistance value was measured by a micro ammeter. At this time, the volume resistance is 9 × 10 ⁹
Ωcm.

Next, as in Example 1, a pair of glass substrates having transparent electrodes formed thereon was prepared, and the PTpy film was formed on one of the substrates under the above-mentioned conditions, and the same rubbing treatment as in Example 1 was performed. Then, the other substrate was subjected to the same vertical alignment treatment as in Example 1 to fabricate a cell.

The liquid crystal composition used in Example 1 was injected into this cell at a reduced pressure (10 Pa) at an isotropic phase temperature (100 ° C.) and gradually cooled to the SmC ^* phase to obtain a liquid crystal element.

When the transmittance of this liquid crystal cell in the darkest state was measured in the same manner as in Example 1, T _d was 1.85%. When the inversion threshold was measured at 10 ° C. with a variable pulse width of 20 μsec, V _H was 1.0 V.
Met.

[Comparative Example 3] # 7059 manufactured by Corning Incorporated
Prepare a substrate washed in the same manner as in Example 1,
A NMP (N-methylpyrrolidone): nBC (n-butyl cellosolve) mixed solution of a polyimide precursor polyamic acid LP64 (manufactured by Toray Industries, Inc.) was spin-coated on the substrate. As a coating solution, LP64 was adjusted to 1.0% by weight in a mixed solution of NMP: nBC = 2: 1, and spin conditions were 2700 rpm and 20 seconds. This substrate was solvent-dried in an oven at 80 ° C. for 5 minutes, and then heated and baked in an oven at 200 ° C. for 1 hour to imidize. The thickness of the obtained polyimide film is about 1
It was 00 $.

Next, a comb-teeth-shaped gold electrode was provided on the obtained film by a resistance heating vapor deposition method at about 300 Å, and then the resistance value was measured by a micro ammeter. At this time, the volume resistance is 2 × 10 ¹¹
Ωcm.

Next, as in the case of Example 1, a pair of glass substrates having transparent electrodes formed thereon were prepared, and the polyimide film was formed on one of the substrates under the above conditions, and the same rubbing treatment as in Example 1 was performed. Then, the other substrate was subjected to the same vertical alignment treatment as in Example 1 to fabricate a cell.

The liquid crystal composition used in Example 1 was injected into this cell at a reduced pressure (10 Pa) at an isotropic phase temperature (100 ° C.) and gradually cooled to the SmC ^* phase to obtain a liquid crystal element.

When the transmittance of this liquid crystal cell in the darkest state was measured in the same manner as in Example 1, it was T _d = 0.07%. Further, when the inversion threshold was measured at 10 ° C. with a variable pulse width of 20 μsec, V _H was 2.0 V.
Met.

The results of Example 1 and Comparative Examples 1 to 3 are shown in Table 2.

[0140]

[Table 2]

[Example 2] # 7059 manufactured by Corning Incorporated
A substrate washed in the same manner as in Example 1 was prepared, and one substrate was spin-coated with a mixed formic acid solution of nylon 66 and polypyridine (Ppy) having a degree of polymerization of 5000. As the coating solution, a 0.5 wt% formic acid solution was prepared in which the solid content ratio of nylon 66 to Ppy was adjusted to 25:75.
Spin conditions were 2000 rpm and 20 seconds. This substrate was dried in a 80 ° C. oven for 5 minutes with a solvent, and then heated and baked in a 180 ° C. oven for 1 hour. The thickness of the obtained mixed film was about 100Å.

Next, a comb-teeth type gold electrode was provided on the obtained film by an evaporation method of resistance heating to about 300 Å, and then the resistance value was measured by a minute ammeter. At this time, the volume resistance is 9 × 10 ⁷
Ωcm.

Next, as in Example 1, a pair of glass substrates having transparent electrodes formed thereon were prepared, the above mixed film was formed on both substrates under the above conditions, and the same rubbing treatment as in Example 1 was performed. Then, the cells were prepared by laminating them so that the rubbing directions were antiparallel to each other.

The liquid crystal composition used in Example 1 was injected into this cell under reduced pressure (10 Pa) at an isotropic phase temperature (100 ° C.), and only one substrate was rapidly cooled, and then the whole cell was SmC ^*.
A liquid crystal element was obtained by gradually cooling to the phase.

When the transmittance of this liquid crystal cell in the darkest state was measured in the same manner as in Example 1, T _d was 0.50%. Further, when the inversion threshold was measured at 10 ° C. with a variable pulse width of 20 μsec, V _H was 0.5 V.
Met.

[Comparative Example 4] # 7059 manufactured by Corning Incorporated
Prepare a substrate washed in the same manner as in Example 1,
A 1.0 wt% formic acid solution of nylon 6 having a degree of polymerization of 5000 was applied onto the substrate. Spin condition is 2000 rpm,
It took 20 seconds. Place this substrate in an oven at 80 ° C for 5
After solvent drying for 1 minute, it was heated and baked in an oven at 180 ° C. for 1 hour. The thickness of the obtained nylon film is about 100.
Was Å.

Next, a comb-teeth-shaped gold electrode was provided on the obtained film by a resistance heating vapor deposition method at about 300 Å, and then the resistance value was measured by a micro ammeter. At this time, the volume resistance is 1.5 × 1
It was 0 ¹⁰ Ωcm.

Next, as in Example 1, a pair of glass substrates having transparent electrodes were prepared, the nylon film was formed on both substrates under the above conditions, and the same rubbing treatment as in Example 1 was performed. Then, the cells were pasted so as to face each other so that the rubbing directions were opposite to each other.

The liquid crystal composition used in Example 1 was injected into this cell under reduced pressure (10 Pa) at an isotropic phase temperature (100 ° C.), and only one substrate was rapidly cooled, and then the whole cell was SmC ^*.
A liquid crystal element was obtained by gradually cooling to the phase.

When the transmittance of this liquid crystal cell in the darkest state was measured in the same manner as in Example 1, T _d was 1.5%. Further, when the inversion threshold value was measured at 10 ° C. with a variable pulse width of 20 μsec, V _H was 2.8 V.

Table 3 shows the results of Example 2 and Comparative Example 4.

[0152]

[Table 3]

Example 3 A liquid crystal device was produced in the same manner as in Example 1 except that polypyridine having a degree of polymerization of 2000 was used instead of polythiophene pyridine. When this liquid crystal element was evaluated in the same manner as in Example 1, the volume resistivity was 8 × 10 ⁷ Ωcm. T _d = 0.20%
Met. In addition, V _H was 0.3V.

[0154]

As described above, according to the present invention,
It is possible to provide a liquid crystal element having an alignment control film that exhibits good conductivity. In particular, high-contrast, high-brightness chiral smectic liquid crystal elements having a structure with a small book tilt or a layer inclination angle close to it without introducing conductive fine particles or doubants into the orientation control film, which has been difficult in the past, cannot achieve high-speed switching. In addition, a liquid crystal device using a liquid crystal compound having a fluorocarbon terminal portion has solved a counter electric field component, which has been a problem in the past, by controlling the composition of an alignment control film, and has a good switching characteristic. The element is realized.

[Brief description of drawings]

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

FIG. 2 is an explanatory diagram of a drive waveform for measuring a hysteresis amount of an inversion threshold which is a drive characteristic of the liquid crystal element of the present invention.

[Explanation of symbols]

 11a, 11b Glass substrate 12a, 12b Transparent electrode 13a, 13b Insulating film 14a, 14b Alignment control film 15 Chiral smectic liquid crystal 16 Bead spacer 17a, 17b Polarizing plate

Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C09K 19/06 C09K 19/06 (72) Inventor Yasuaki Takeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Kiya (72) Inventor Ikuo Nakazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Innovator Masanobu Asaoka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yukio Hanyu 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (37)

[Claims] 1. A liquid crystal device having a liquid crystal composition sandwiched between a pair of substrates, wherein an alignment control film is formed on a surface of at least one of the pair of substrates in contact with the liquid crystal composition, A liquid crystal element, wherein the alignment control film is composed of an amide polymer and a polypyridine polymer. 2. The liquid crystal device according to claim 1, wherein the amide polymer is polyimide or polyamide. 3. The amide-based polymer is represented by the following general formula P-1.
The liquid crystal device according to claim 1, which is a polyamide-based polymer having a repeating unit represented by the following formula. Formula _{P-1 -CONH- (CH 2)} n -NHCO- (CH 2) m - ( wherein, m and n are different identical or respectively 1 to 1
Any integer of 2. ) 4. The liquid crystal according to claim 1, wherein the polypyridine polymer is a polypyridine polymer having a repeating unit having a structure represented by the following general formula P-2. element. General formula P-2-AB- (In formula, A is a pyridine ring and the coupling | bonding position with B is 2nd-position or 5th.
And B is any of a pyridine ring, a thiophene ring, a pyrrole ring, a fluorenone ring, an isothianaphthenepyridine ring, a furan ring and a thiophenepyridine ring, and the thiophene ring and the pyrrole ring are protons at the 3rd or 4th positions. May be substituted with an alkyl group, an alkoxy group, a carboxylic acid ester group, a phenyl group, a naphthyl group, or an anthracene-yl group. ) 5. The liquid crystal element according to claim 1, wherein the alignment control film is uniaxially aligned. 6. The liquid crystal device according to claim 1, wherein the liquid crystal composition is a chiral smectic liquid crystal composition. 7. The liquid crystal composition has a bookshelf structure or a structure having a small layer inclination close to the bookshelf structure.
The liquid crystal element according to the above. 8. The liquid crystal device according to claim 1, wherein the liquid crystal composition has ferroelectricity. 9. The liquid crystal element according to claim 1, wherein the alignment control film is provided on both of the pair of substrates. 10. The liquid crystal element according to claim 1, wherein the alignment control film is provided only on one of the pair of substrates. 11. The degree of polymerization of the polyamide-based polymer is 1
The liquid crystal element according to any one of claims 3 to 10, which is 000 or more and 100,000 or less. 12. The liquid crystal device according to claim 4, wherein the polypyridine polymer has a degree of polymerization of 1,000 or more and 50,000 or less. 13. The weight ratio of the amide-based polymer to the polypyridine-based polymer is 5:95 to 45:55.
13. The liquid crystal element according to any one of 1 to 12. 14. The liquid crystal device according to claim 1, wherein the weight ratio of the amide polymer to the polypyridine polymer is 15:85 to 35:65. 15. The orientation control film is chemically doped,
15. The liquid crystal element according to claim 1, wherein neither electrochemical doping, addition of a charge transfer complex, nor addition of conductive fine particles is performed. 16. A liquid crystal element having a liquid crystal composition sandwiched between a pair of substrates, wherein an alignment control film is formed on a surface of at least one of the pair of substrates in contact with the liquid crystal composition. The alignment control film is a film made of a conductive polymer and an insulating polymer, and the conductivity of the alignment control film is higher than the conductivity of a film made of the conductive polymer alone. Liquid crystal element. 17. The conductive polymer is a polymer having a π-conjugated system, the insulating polymer is a polymer having no π-conjugated system, and the alignment control film has the π-conjugated system. The liquid crystal device according to claim 16, wherein the optical absorption based on the π-π ^* transition per 1 π bond of the polymer is increased by adding the polymer not having the π bond. 18. The liquid crystal device according to claim 17, wherein the polymer having the π-conjugated system is a polypyridine-based polymer, and the polymer having no π-conjugated system is an amide-based polymer. 19. The liquid crystal device according to claim 18, wherein the amide polymer is polyimide or polyamide. 20. The amide-based polymer is represented by the following general formula P-
The liquid crystal device according to claim 18, which is a polyamide polymer having a repeating unit represented by the formula 1. Formula _{P-1 -CONH- (CH 2)} n -NHCO- (CH 2) m - ( wherein, m and n are different identical or respectively 1 to 1
Any integer of 2. ) 21. The liquid crystal device according to claim 18, wherein the polypyridine polymer is a polypyridine polymer having a repeating unit having a structure represented by the following general formula P-2. . General formula P-2-AB- (In formula, A is a pyridine ring and the coupling | bonding position with B is 2nd-position or 5th.
And B is any of a pyridine ring, a thiophene ring, a pyrrole ring, a fluorenone ring, an isothianaphthenepyridine ring, a furan ring and a thiophenepyridine ring, and the thiophene ring and the pyrrole ring are protons at the 3rd or 4th positions. May be substituted with an alkyl group, an alkoxy group, a carboxylic acid ester group, a phenyl group, a naphthyl group, or an anthracene-yl group. ) 22. The liquid crystal device according to claim 17, wherein the alignment control film is subjected to a uniaxial alignment treatment. 23. The liquid crystal device according to claim 17, wherein the liquid crystal composition is a chiral smectic liquid crystal composition. 24. The liquid crystal composition has a bookshelf structure or a structure having a small layer inclination close to the bookshelf structure.
3. The liquid crystal device according to item 3. 25. The liquid crystal device according to claim 17, wherein the liquid crystal composition has ferroelectricity. 26. The liquid crystal element according to claim 17, wherein the alignment control film is provided on both of the pair of substrates. 27. The liquid crystal device according to claim 17, wherein the alignment control film is provided only on one of the pair of substrates. 28. The degree of polymerization of the amide polymer is 100.
The liquid crystal element according to any one of claims 20 to 27, which is 0 or more and 100,000 or less. 29. The degree of polymerization of the polypyridine polymer is 1,000 or more and 50,000 or less.
The liquid crystal element according to any one of 1. 30. The weight ratio of the amide polymer and the polypyridine polymer is 5:95 to 45:55.
The liquid crystal device according to any one of 8 to 29. 31. The liquid crystal device according to claim 18, wherein the weight ratio of the amide polymer to the polypyridine polymer is 15:85 to 35:65. 32. Chemical doping is applied to the orientation control film,
32. The liquid crystal element according to claim 17, wherein neither electrochemical doping, addition of a charge transfer complex, nor addition of conductive fine particles is performed. 33. A fluorine-containing liquid crystal compound having a fluorocarbon terminal portion and a hydrocarbon terminal portion, the both terminal portions being bound by a central nucleus, and having a smectic mesophase or a latent smectic mesophase. 33. The liquid crystal element according to claim 1, which contains. 34. The liquid crystal device according to claim 33, wherein the fluorocarbon terminal portion of the fluorine-containing liquid crystal compound is a group represented by —D ¹ —C _xa F _2xa —X. (However,
The formula xa is 1 to 20, X represents -H or -F, D ¹ _{is, -CO-O- (CH 2)} ra -, - O- (C
_{H 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 to 20, and pa is 0 to 4. ) 35. The fluorocarbon terminal portion of the fluorine-containing liquid crystal compound is —D ² — (C _xb F _2xb —O).
_za -C _ya F _{2ya + 1} liquid crystal device according to claim 33, wherein a group represented by. (However, in the above formula, xb is (C _xb
F _2xb —O) is independently 1 to 10, and ya is 1 to 1
0, za is 1 to 10, 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 single bonds, 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. ) 36. The liquid crystal device according to claim 33, wherein the fluorine-containing liquid crystal compound is represented by the following general formula (I). 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 L ¹ and L ² is independently a single bond, —CO—O—,
-O-CO-, -COS-, -S-CO-, -CO-S
e-, -Se-CO-, -CO-Te-, -Te-CO
_{-, - CH 2 CH 2 -} , - CH = CH -, - C≡C -, -
CH = N -, - N = CH -, - CH 2 -O -, - O-C
Represents H ₂ —, —CO— or —O—. Each X ¹ ,
Y ¹ and Z ¹ are substituents of A ¹ , A ² and A ³ , and independently
H, -Cl, -F, -Br, -I, -OH, -OC
Represents H ₃ , —CH ₃ , —CN, or —NO ₂ , and each of ja, ma, and na independently represents an integer of 0 to 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) -C
Represents O-. ra and rb are independently 1 to 20, and pa is 0 to 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 ³ , _{-OC qa} H _2qa -R ³ , -CO- _OC
qa H _2qa -R ^3, or represents _{-O-CO-C qa H 2qa} -R 3, linear, may be either branched (Here, R
_{^3, -O-CO-C qb H} 2qb + 1, -CO-O-C qb H
_{2qb + 1, -H, -Cl,} -F, -CF 3, -NO 2, -C
N, and qa and qb are independently 1-20).
R ² represents a C _xa F _2xa -X (X represents -H or -F, xa is an integer of 1 to 20). ] 37. The liquid crystal device according to claim 33, wherein the fluorine-containing liquid crystal compound is represented by the following general formula (II). Embedded image Represents gb, hb, and ib are each independently an integer of 0 to 3 (however, gb + hb + ib is at least 2)
Represents L ³ and L ⁴ are each independently a single bond, -CO-
O-, -O-CO-, -CO-S-, -S-CO-,-
CO-Se-, -Se-CO-, -CO-Te-, -T
e-CO -, - (CH 2 CH 2) ka - (ka is 1 to 4),
-CH = CH-, -C≡C-, -CH = N-, -N = C
_{H -, - CH 2 -O -} , - O-CH 2 -, - CO- or -
Represents 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, -OC
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, -C
_{O-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—, rc and rd are independently 1 to 20, 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 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 -O-CO-
_{C qc} H 2qc -R ⁶ represents a linear, it may be either branched (wherein, R ⁶ is _{-O-CO-C qd H 2qd} + 1, -
_{CO-O-C qd H 2qd} + 1, -Cl, -F, -CF 3, -N
Represents O ₂ , —CN, or —H, qc and qd are each independently an integer of 1 to 20, and wa is an integer of 1 to 10). R
^5, (C _xb F _2xb -O) represented by _za -C _ya F _{2ya + 1} (where the above formula xb is each (C _xb F _2xb -O)
Is independently 1 to 10, ya is 1 to 10, za
Is 1 to 10.) ]