JPH11101993A - Liquid crystal element, method for controlling orientation of liquid crystal and manufacture of liquid crystal element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal element of which both orientation uniformity and driving characteristics are compatibly improved. SOLUTION: Liquid crystal 11 is held between a pair of substrates 12a, 12b and an orientation controlling layer 15a having an uniaxial orientation regulating force to the liquid crystal 11 is selectively provided on at least one substrate. When temp. drops, in the liquid crystal 11 transition generates to the liquid crystal phase from a region being in contact with a plane R1 parallel to the substrate of the orientation controlling layer 15a in a phase transition process of liquid phase-liquid crystal phase and, then, a liquid crystal phase transition region is continuously enlarged along an axial direction of the uniaxial orientation regulating force of the orientation controlling layer 15a to form an orientation state.

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 in a flat panel display, a projection display, a printer, and the like, a method for controlling the alignment of liquid crystal in the element, and a method for manufacturing the element.

[0002]

2. Description of the Related Art Conventionally, in a nematic liquid crystal display device, an active matrix (for example, a TF) in which an active element such as a transistor is disposed in each pixel.
A liquid crystal element called T) is being developed. As a mode of a nematic liquid crystal currently used for a liquid crystal display device using this TFT, for example, M.S.
chadt) and W. Helfrich
frich) Applied Physics Le
Twistered Nematic mode shown on pages 127 to 128 of ters Vol. 18, No. 4 (published on Feb. 15, 1971) is widely used. Recently, in-plane switching (In-Plai switching) using a lateral electric field has been proposed.
n Switching) mode has been announced, and the viewing angle characteristic which has been a defect of the twisted nematic mode liquid crystal display has been improved. In addition, as a typical example of a nematic liquid crystal display element that does not use an active element such as the above-described TFT, a super twisted nematic (Super Twisted Nematic) is used.
There is a mode. As described above, there are various modes in such a liquid crystal display device using a nematic liquid crystal, but in any of these modes, there is a problem that the response speed of the liquid crystal takes several tens of milliseconds or more. did.

In order to improve the disadvantages of such a conventional nematic liquid crystal device, a device using a liquid crystal exhibiting bistability has been proposed by Clark and Lagerwall (Japanese Patent Application Laid-Open No. Sho 56). -107216, U.S. Pat.
Specification). As the liquid crystal exhibiting the bistability, a ferroelectric liquid crystal exhibiting a chiral smectic C phase is generally 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 a memory property can be developed. Furthermore, because the viewing angle characteristics are excellent, high speed,
It is considered to be suitable as a high-definition, large-area display element or light valve.

On the other hand, recently, antiferroelectric liquid crystals exhibiting three stability have attracted attention. This antiferroelectric liquid crystal performs reversal switching by spontaneous polarization similarly to the ferroelectric liquid crystal, so that a very fast response speed can be obtained. This liquid crystal material
When an electric field is not applied, the liquid crystal molecules have a molecular alignment structure that cancels out each other's spontaneous polarization. Therefore, it is characterized in that there is no spontaneous polarization when no electric field is applied. More recently, a thresholdless antiferroelectric liquid crystal developed to drive this antiferroelectric liquid crystal by an active matrix element has been reported.

[0005] Ferroelectric liquid crystals and antiferroelectric liquid crystals that perform inversion switching by such spontaneous polarization are liquid crystals exhibiting a smectic liquid crystal phase. That is, the realization of a liquid crystal display device using a smectic liquid crystal is expected in the sense that the problem relating to the response speed of the conventional nematic liquid crystal can be solved.

[0006]

In a smectic liquid crystal display device having such excellent features, particularly in the case of a device using a ferroelectric liquid crystal which performs inversion switching by spontaneous polarization, it controls the alignment of the liquid crystal in the device. In particular, the electric field generated by the anti-electric field, i.e., the spontaneous polarization of the liquid crystal in the device, is generated by reducing the thickness of the alignment control layer made of an ordinary insulating material for regulating the uniaxial alignment and increasing the electric capacity of the alignment control layer. The electric field in the reverse direction is reduced, the switching characteristics are improved, and the driving margin is increased. Since the generation of the anti-electric field becomes more conspicuous as the spontaneous polarization increases, it is essential to reduce the thickness of the insulating alignment control film, especially when using a liquid crystal material with a large spontaneous polarization to improve the response speed. Becomes

On the other hand, a liquid crystal element using a chiral smectic liquid crystal such as a ferroelectric liquid crystal or an antiferroelectric liquid crystal is
Since both use the principle of switching by the response of the liquid crystal by applying a pulsed electric field, the magnitude of the voltage effectively applied to the liquid crystal layer depends on the layers constituting the liquid crystal element (liquid crystal layer, alignment control layer, etc.). Is determined by the capacity ratio (reverse ratio). Therefore, in order to effectively increase the voltage applied to the liquid crystal layer and obtain higher-speed switching characteristics, the capacitance of the alignment control layer is designed to be sufficiently larger than the capacitance of the liquid crystal layer. Should be designed to be sufficiently smaller than the thickness of the liquid crystal layer.

However, as the thickness of the orientation control layer is reduced, it becomes more difficult for the orientation control layer to function to perform desired orientation control on liquid crystal molecules. As a result, according to the above-described design concept of the chiral smectic liquid crystal element, it is extremely difficult to achieve both the improvement of the switching characteristics (suppression of the anti-electric field and the expansion of the driving margin), the improvement of the response speed, and the uniform alignment. Further, with respect to a manufacturing process for forming an alignment film uniformly, it becomes more difficult to strictly control the thinner the film thickness.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to realize a liquid crystal element having a wide driving margin while realizing uniform liquid crystal molecular alignment and having higher switching characteristics. In particular, it is an object of the present invention to provide a liquid crystal device using a chiral smectic liquid crystal, for example, a liquid crystal having ferroelectricity or antiferroelectricity.

[0010]

A liquid crystal element according to the present invention has a liquid crystal between a pair of substrates, is in contact with the liquid crystal on at least one of the substrates, and has at least a selectively provided liquid crystal with uniaxial alignment control. A first region having a force, and a second region having a weak uniaxial orientation regulating force or substantially no uniaxial orientation regulating force compared to the first region outside the first region. ,
The liquid crystal undergoes a transition from a portion in contact with the first region to a liquid crystal phase in a liquid phase-liquid crystal phase transition process at the time of temperature decrease between the substrates, and the liquid crystal moves along a uniaxial alignment axis in the first region. A phase transition region is grown, and the liquid crystal phase transition region is continuously enlarged in the second region to form an alignment state.

Further, according to the present invention, a liquid crystal is provided between a pair of substrates and is in contact with the liquid crystal on at least one substrate side. In a liquid crystal device having a region and a second region having a weak uniaxial alignment regulating force or substantially no uniaxial alignment regulating force compared to the first region outside the first region, the substrate By gradually cooling the liquid crystal between the liquid phase and the liquid crystal phase, a transition from a portion in contact with the first region to a liquid crystal phase occurs during a phase transition process between the liquid phase and the liquid crystal phase when the temperature is lowered between the substrates. Forming a liquid crystal phase transition region along a uniaxial alignment axis in the region and continuously expanding the liquid crystal phase transition region in the second region to form an alignment state. , And a liquid crystal having a liquid crystal between a pair of substrates A method for manufacturing a child, wherein at least one of a first region having a uniaxial alignment regulating force with respect to at least a selectively provided liquid crystal and the first region outside the first region is compared. Forming a cell by opposing a pair of substrates having a second region having a weak uniaxial alignment regulating force or having substantially no uniaxial alignment regulating force, and injecting a liquid crystal into the cell; By gradually cooling the liquid crystal between the substrates injected into the cell from the liquid phase, a transition from the portion in contact with the first region to the liquid crystal phase during the liquid phase-liquid crystal phase transition process between the substrates when the temperature is lowered. Causing the liquid crystal phase transition region to grow along the uniaxial alignment axis in the first region and continuously expanding the liquid crystal phase transition region in the second region to form an alignment state. Liquid crystal alignment control method and liquid crystal element Production method is provided.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the liquid crystal device of the present invention will be described below in detail with reference to the drawings.

A first embodiment of the liquid crystal device of the present invention will be described with reference to FIGS. FIG. 1 is a plan view of one embodiment of one substrate 12a (a substrate on which an alignment control film having a uniaxial alignment regulating force is selectively provided) constituting the liquid crystal element of the present invention, as viewed from the upper surface side. Is a cross-sectional view showing the structure of the element 1 using the substrate 12a shown in FIG. 1 as one substrate (FIG.
2 shows a cross section of the substrate shown in FIG.

As shown in FIG. 2, the basic structure of the element 1 is as follows.
A liquid crystal 11 composed of a liquid crystal composition is used as a pair of substrates 12a, 12
b.

On the substrate 12a, an electrode 13a for applying an electric field to the liquid crystal 11 is provided, and on the electrode 13a, an orientation control layer 15a is interposed via a layer 14a serving as a base.
It is selectively provided in a planar shape such as a stripe pattern shape shown in FIG. The alignment control layer 15a is made of a material which is made of an insulating material or the like and which exerts a uniaxial alignment regulating force on the liquid crystal by performing an appropriate treatment.
The surface (R1) in contact with the liquid crystal substantially parallel to 2a is subjected to uniaxial alignment treatment, and has a uniaxial alignment regulating force on the liquid crystal.

That is, in the substrate 12a, a first region (a region constituting the surface R1) having a uniaxial alignment regulating force with respect to the liquid crystal corresponding to at least the selectively provided alignment control layer 15a, and a layer serving as an underlayer. A second region (a region constituting the surface R2) that is in contact with the liquid crystal 11 is formed in other portions corresponding to 14a. Here, the uniaxial orientation regulating force on the surface R1 is larger than the uniaxial orientation regulating force of the second region, or the orientation regulating force of the second region R2 is substantially zero.

On the other hand, the liquid crystal 11
An electrode 13b for applying an electric field is provided, and an alignment control layer 15b that is in contact with the liquid crystal 11 and can contribute to the alignment control of the liquid crystal is formed on the electrode 13b.

In such an electrode, substrates 11a and 11b provided with an orientation control layer are opposed to each other at a fixed distance via a spacer 16.

A polarizing plate is provided on the outer surfaces of the substrates 11a and 11b as required. Further, a light source is provided as necessary behind the element 1 when viewed from the observer side (not shown).

In the above structural element 1, the electrodes 12a and 1a are turned on in response to a switching signal from a signal power supply (not shown).
An electric field is applied to the liquid crystal layer 11 by 2b to perform switching, and external light is modulated by the liquid crystal 11.

In the liquid crystal element 1 having the above structure, it is in contact with the liquid crystal 11. By appropriately setting the pattern-shaped alignment control layers 15a, 14a, and the alignment control layer 15b, and further appropriately setting the material, processing method, and conditions of the liquid crystal 11, the liquid crystal 11 has a liquid crystal phase-liquid crystal phase when the temperature is lowered. In the transfer process, a surface R1 of the orientation control layer 15a selectively provided in the direction parallel to the substrate is provided.
The transition from the region in contact with to the liquid crystal phase occurs, and the liquid crystal phase transition region grows continuously along the axial direction of the uniaxial alignment regulating force (axial direction of the uniaxial alignment treatment) of the alignment control layer 15a. This is characterized in that the liquid crystal phase transition region is expanded and an alignment state is formed.

Hereinafter, the formation of this alignment state will be described with reference to FIGS.

FIGS. 3A to 3C show the substrate 1 shown in FIG.
Regarding the formation of the alignment state from the liquid crystal region in contact with the selectively formed alignment control layer 15a in 2a, the direction of the uniaxial alignment control (the direction of the uniaxial alignment treatment performed on the alignment control layer 15a) U is set to the alignment control layer 15a. Is set substantially perpendicular to the longitudinal direction, and a smectic liquid crystal is used as the liquid crystal. When the temperature is lowered, the state of the phase transition process to the smectic liquid crystal phase changes ((A), (B), (C)). FIG. 5 is an explanatory diagram schematically showing what the optical microscope proceeds with a polarization microscope.

First, as shown in FIG. 3A, when the temperature is lowered (cooled) from a phase having a higher order than the liquid crystal smectic liquid crystal phase, the surface R1 of the alignment control film 15a having a strong uniaxial alignment regulating force on the substrate 12a. From the liquid crystal, a region N called a butene, which is a smectic nucleus that appears in the smectic liquid crystal phase transition, is generated.

Subsequently, by further lowering the temperature of the liquid crystal, as shown in FIG. 3 (B), the tone N becomes a uniaxial alignment processing direction U which is a direction perpendicular to the longitudinal direction of the uniaxial alignment control layer 15a, that is, the smectic layer. Grow in the normal direction. Normally, the smectic liquid crystal phase battone has a growth anisotropy that it is easy to grow in the normal direction of the smectic layer,
According to this characteristic, the orientation control layer 1 is oriented along the normal direction of the smectic layer (corresponding to the uniaxial orientation processing direction U) determined by the nuclei of the bones N generated as shown in FIG.
The liquid crystal region corresponding to the portion between the lines 5a (the liquid crystal region corresponding to R2 in contact with the liquid crystal of the layer 14a between the lines of the adjacent alignment control layer 15a in the cross-sectional view of FIG. 2) grows almost linearly. Expanding. Here, due to the anisotropy of the bone growth of the smectic liquid crystal of the liquid crystal itself, R
Even in the alignment state of the liquid crystal formed in the portion (R2) where the alignment regulating force is small or substantially does not exist as compared with 1, the smectic layer direction is uniformly arranged.

When the temperature is further reduced, FIGS.
As shown in FIG. 7, the bone N starts growing not only in the direction U in which the uniaxial orientation is regulated, but also in a direction perpendicular to that direction (in the longitudinal direction of the orientation control layer 15a). At this time, the batone N not only grows thicker as a whole but also grows so that a branch appears from the side of the batone. The branch gradually grows in the direction of the smectic layer (the longitudinal direction of the orientation control layer 15a). As shown in FIG. Growth progresses.

As described above, cooling is performed until the entire region between the substrates in the device becomes a smectic phase.
In the liquid crystal region corresponding to both the portion where 5a exists and the portion where it does not exist, an alignment state is formed in which the smectic layer is uniformly arranged in the longitudinal direction of the alignment control layer 15a.

On the other hand, FIGS. 4A to 4C show FIGS.
In the formation of the alignment state from the selectively formed alignment control layer 15a on the substrate 12a shown in FIG. 1, the direction of the uniaxial alignment control (the direction of the uniaxial alignment treatment applied to the alignment control layer 15a) U is defined as the alignment control layer. 15a is set substantially in parallel (parallel) to the longitudinal direction, and a smectic liquid crystal is used as the liquid crystal. Changes in the state of the phase transition process to the smectic liquid crystal layer at the time of temperature decrease ((A), (B), ( FIG. 4 is an explanatory diagram schematically showing observation of a temperature falling in the order of C) by a polarizing microscope.

First, as shown in FIG.
As in the case of (A), when the temperature of the liquid crystal is lowered from a higher order phase than the smectic liquid crystal phase, the liquid crystal on the surface R1 of the alignment control film 15a having a strong uniaxial alignment regulating force on the substrate 12a changes the smectic liquid crystal phase transition. A region N called batone, which is a smectic nucleus expressed in the above, is generated.

Subsequently, by further lowering the temperature of the liquid crystal, as shown in FIG. 4 (B), the B-tone N is formed based on the anisotropy characteristic of the B-thone growth of the smectic liquid-crystal phase.
As shown in (A), the uniaxially oriented treatment direction U, which is the normal direction of the smectic layer determined by the generated nuclei of the bone N, ie, the same direction as the longitudinal direction of the uniaxially oriented control layer 15a. Here, since the growth direction of the above-mentioned battone due to the anisotropy of battone growth and the longitudinal direction of the pattern of the orientation control layer 15a having the uniaxial orientation regulating force coincide with each other, as shown in FIG. Is the orientation control layer 1
It grows more quickly on the surface R1 of 5a.

When the temperature is further reduced, FIGS. 4 (B) to 4 (C)
As shown in the figure, the bone N starts to grow not only in the longitudinal direction of the orientation control layer 15a but also in the direction perpendicular to that direction. At this time, the liquid crystal region corresponding to the portion where the uniaxial alignment control force between the lines is small or substantially nonexistent so that the branch N appears to grow from the side of the groove, as well as the bone N gradually grows as a whole. (The liquid crystal region corresponding to the portion R2 where the layer 14a is in contact with the liquid crystal between the lines of the adjacent alignment control layer 15a in the sectional view of FIG. 2). Finally, the B tones N grown from the island line portions of the adjacent orientation control layers 15a are finally joined to form an orientation state in which the smectic layer is substantially uniform.

As described above, the entire region between the substrates in the device is cooled until it becomes a smectic phase.
In the liquid crystal regions corresponding to all of the portion where 5a exists and the portion where it does not exist, an alignment state is formed in which the smectic layers are uniformly arranged perpendicular to the longitudinal direction of the alignment control layer 15a.

In such a liquid crystal element, an alignment control layer (1) having a uniaxial alignment regulating force, usually having an insulating property, in the element.
5a) is a nucleus (Battone) serving as a starting portion for forming an alignment state
Is provided in a pattern shape necessary for supplying the liquid crystal, and a uniform alignment state is reliably formed on the entire surface of the element by the process of forming the alignment state as described above. In addition, the amount of the orientation control layer (15a) made of an insulating material that electrically obstructs the driving of the liquid crystal and has a uniaxial orientation regulation force is reduced as much as possible. As a result, the effective voltage applied to the liquid crystal during driving by the pulse voltage can be increased. In this way, it is possible to make the alignment state uniform and to speed up the liquid crystal driving (switching).

With respect to the members constituting the liquid crystal element 1,
This will be described in more detail.

The substrates 12a and 12b are preferably made of a highly transparent material such as glass or plastic. In addition, a transparent electrode such as ITO is used for the electrodes 13a and 13b, and a metal electrode may be provided in contact with the transparent electrode if necessary to reduce the resistance of the whole electrode (not shown).

As a liquid crystal material constituting the liquid crystal 11, a chiral smectic liquid crystal having ferroelectric or antiferroelectric properties is preferably used. In this case, the cell gap (distance between substrates) is set to 0.5 to 5 μm in order to realize bistability based on the Clark and Ragawell models described above.
m is preferable. Nematic liquid crystal can also be used as a liquid crystal material.

In particular, in the present invention, the above-mentioned chiral smectic liquid crystal, which does not have a cholesteric phase at a reduced temperature, is suitably used as the liquid crystal material. For example, in the case of a liquid crystal exhibiting antiferroelectricity, most of the synthesized liquid crystal materials do not have a cholesteric phase. Alternatively, in the case of a liquid crystal exhibiting ferroelectricity, a chevron structure is eliminated, and a layered structure called a bookshelf, that is, a structure in which the smectic layer is substantially perpendicular to the substrate, or a structure close thereto is developed, and a high contrast is obtained. In order to realize a good liquid crystal element, as an example, a liquid crystal compound having a perfluoroether side chain (Marc D. Radcliffe, 4th International Conference on Ferroelectric Liquid Crystals, P-46, 1993)
e) is preferably used, but such a liquid crystal material is
A material capable of exhibiting a structure of a smectic layer with a small layer tilt angle close to the bookshelf due to the characteristics of the material itself, and having no cholesteric phase and exhibiting an isotropic phase-smectic liquid crystal phase transition. .

As the liquid crystal material exhibiting the bookshelf layer structure, specifically, a structure in which a terminal portion of a fluorocarbon and a hydrocarbon portion are bonded by a central nucleus,
A chiral smectic liquid crystal composition containing at least one fluorine-containing liquid crystal compound having a smectic intermediate phase or a latent smectic intermediate phase can be used. The compound having a latent smectic mesophase referred to herein, even if it does not show a smectic mesophase by itself, in a mixture with a compound having a smectic mesophase or a compound having another potential smectic mesophase,
Refers to a compound that exhibits a smectic mesophase under appropriate conditions. In the structure of the fluorine-containing liquid crystal compound, the central nucleus refers to at least two aromatic rings, aliphatic rings,
Or a substituted aromatic ring or a substituted heteroaromatic, and these rings are mutually represented by -COO-, -COS-, -HC = N
—, —COSe— may be bonded by a group selected from the group consisting of —COSe—. Even if these rings are fused,
You don't have to. Heteroatoms in the heteroaromatic ring are N,
It contains at least one atom selected from O and S. Non-adjacent methylene groups in the aliphatic ring may be replaced by O.

Specific examples of the formulation of the above-mentioned fluorine-containing liquid crystal compound or a chiral smectic liquid crystal composition containing the same are described in JP-A-63-27451 and JP-A-2-17-1.
No. 42753, U.S. Pat. No. 5,262,082, WO 93/22396, U.S. Pat. No. 5,417,813 and the like.

The cholesteric phase does not show the above-mentioned cholesteric phase,
A liquid crystal material exhibiting an isotropic phase-smectic liquid crystal phase transition has a remarkable anisotropy of the above-mentioned Battone growth with respect to alignment formation, and after a fine nucleus of the smectic liquid crystal phase is generated, a normal direction of the smectic layer is formed. Rapidly grows, and furthermore, the area of the bone is rapidly expanded to the smectic layer. Therefore, in the element using the liquid crystal material, a distribution is provided in the uniaxial alignment regulating force or the wettability with the liquid crystal at the interface of the substrate in contact with the liquid crystal, and the smectic liquid crystal phase is provided with selectivity at the minute nucleus generation position, and In the growth region after the nucleation, the alignment is formed due to the anisotropy in the above-mentioned growth direction even if there is no alignment regulating force at the interface between the substrate and the liquid crystal. Therefore, such a liquid crystal material is selectively arranged on a substrate by patterning or the like as in an alignment control layer 15a having a uniaxial alignment control force as shown in FIGS. It is particularly suitable for structures with a reduced proportion of layers.

The alignment control layer 15a having a uniaxial alignment regulating force with respect to the liquid crystal is provided in a predetermined pattern. As described above, the material and the surface of the layer 14a in contact with the liquid crystal between the line portions are provided. Due to the combination with the characteristics, the liquid crystal region in contact with the surface R1 of the line portion generates nuclei (Batnet generation) at the time of transition to the liquid crystal phase in the process of forming the liquid crystal alignment state as described with reference to FIGS. Function to be a part. That is, the surface R of the line portion of the orientation control layer 15a
The liquid phase-liquid crystal phase transition temperature of the liquid crystal region corresponding to 1 is the liquid phase-liquid layer transition temperature of the liquid crystal region at a portion not corresponding to the surface R1 of the line portion (a portion corresponding to the surface R2 between the line portions). Higher.

The orientation control layer 15a can be preferably formed by subjecting a film of a predetermined material provided on the substrate (on the layer 14a) to a uniaxial orientation treatment. Specifically, the solution is applied to the underlayer by solution coating, vapor deposition, sputtering, or the like, so that silicon monoxide, silicon dioxide, aluminum oxide, zirconia,
Magnesium fluoride, cerium oxide, cerium fluoride,
Inorganic substances such as silicon nitride, silicon carbide, boron nitride and polyvinyl alcohol, polyimide, polyimide amide, polyester, polyamide, polyester imide, polyparaxylene, polycarbonate, polyvinyl acetal, polyvinyl chloride, polystyrene,
After a film is formed using an insulating organic material such as polysiloxane, cellulose resin, melamine resin, urea resin, and acrylic resin, the surface is rubbed with a fibrous material such as velvet, cloth or paper. The obtained film is used. Alternatively, a film in which an oxide or a nitride such as Sio is deposited from an oblique direction of the substrate can be used.
The material for the alignment control layer is selected according to the type of the liquid crystal material.

In the case of using a chiral smectic liquid crystal, particularly a chiral smectic liquid crystal composition containing at least one kind of the above-mentioned fluorine-containing liquid crystalline compound, preferably, a polyimide comprising a repeating unit represented by the following general formula P is used. A rubbed film can be used. [Formula P] ^{(-K-P 11 -L 11 -M} 11 - (L 12) a -P 12 -)

[0044]

[Outside 1] And L ¹¹ and L ¹² are each independently

[0045]

[Outside 2] Or an alkylene group having 1 to 20 carbon atoms, wherein P ¹¹ ,
P ¹² represents an imide bond. M ¹¹ represents a single bond or —O— on the cover, and a represents 0, 1, or 2. )

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

[0047]

[Outside 3]

[0048]

[Outside 4]

[0049]

[Outside 5]

The orientation control layer 15a is provided by patterning it into a desired shape at the time of or after the formation of the film, for example, the shape shown in FIG. As a method of performing patterning after forming the film, for example, mask etching, lift-off, UV ashing, or the like can be employed. Also,
A patterning method using an organic material having photosensitivity as a material for the orientation control layer can also be employed.
Offset printing, an inkjet method, a bubble jet method, or the like can be used as a method of patterning a film into a desired shape at the time of film formation.

The orientation control layer 15a is formed as a layer having a patterned uniaxial orientation by uniformly forming a film on the substrate 11a and selectively subjecting the film to a uniaxial orientation treatment such as a rubbing treatment. You can also get.

The pattern of the alignment control layer 15a preferably has a stripe shape as shown in FIG.
According to the degree of the uniaxial alignment regulating force of the alignment control layer, or according to the unit of optical modulation of the liquid crystal element or the size of the pixel,
It is also possible to select various shapes such as a lattice shape and an island shape. However, regarding the dimensions of the pattern of the alignment control layer 15a, at least the uniaxial alignment control force is set in consideration of both the uniformity of the alignment state in the device and the high speed of liquid crystal driving (switching) as described above. It is more preferable to set the total plane area of the region (surface R1) of the substrate having the alignment control layer 15a to be smaller than the total plane area of the region where the alignment control layer is not provided on the substrate.

The relationship between the pattern shape of the alignment control layer 15a having the uniaxial alignment regulating force and the axial direction of the uniaxial alignment regulating force (the direction of the uniaxial alignment treatment) also indicates the alignment characteristics of the liquid crystal material and the alignment control layer. It can be determined according to the uniaxial orientation regulating force or the like.

When a liquid crystal exhibiting a smectic liquid crystal phase is used as the liquid crystal 11, as shown in FIGS. 4 (A) to 4 (C), the alignment control layer 15a is formed in a stripe shape, and a uniaxial alignment treatment is performed in parallel with the stripe direction. When the direction is set and the alignment state is formed, particularly when the line distance of the alignment control layer 15a is excessively large, there is no uniaxial alignment control force on the substrate surface for a wide liquid crystal region between the lines. As shown in FIG. 4C, the branch generated from the smectic liquid crystal phase is not linear, but may grow by refraction, and the smectic layer may be bent. As a result, after cooling the entire surface of the device until it becomes a smectic liquid crystal phase, the alignment control layer 15a having a uniaxial alignment regulating force exists.
In the liquid crystal region near the center between the lines, there is a possibility that the smectic layer direction becomes non-uniform. On the other hand, as shown in FIGS. 3A to 3C, when the alignment control layer 15a is formed into a stripe shape and the uniaxial alignment processing direction is set perpendicular to the stripe direction to form an alignment state, As shown in FIG. 3C, the branch generated from the smectic liquid crystal phase grows substantially linearly along the stripe line of the alignment control layer 15a, and the smectic layer is also easily formed uniformly in the line direction. Therefore,
When a liquid crystal exhibiting a smectic liquid crystal phase is used as the liquid crystal 11, it is more preferably continuous or substantially continuous in the direction of the formed smectic layer in the sense of maintaining uniformity in the layer direction during the growth of the branch during alignment formation. A stripe pattern perpendicular to the axial direction of the uniaxial alignment regulating force (for example, the rubbing axis in the rubbing process described above).

When the pattern of the orientation control layer 15a is a stripe pattern as shown in FIG. 1, the longitudinal direction is the same as the direction of the above-mentioned smectic layer (along the axial direction of the uniaxial orientation regulating force). Wherein the length of the smectic layer in the normal direction of one stripe (line) portion of the alignment control layer is such that the alignment control layer between adjacent stripes (lines) of the alignment control layer is It is preferable that the length of the smectic layer in the portion not provided is shorter than the length in the normal direction.

When the pattern of the orientation control layer 15a is a stripe pattern as shown in FIG. 1, setting the interval between the lines is important in relation to the obtained orientation state. In particular, in the case of a stripe pattern substantially similar (parallel) in the axial direction of the uniaxial alignment regulating force as shown in FIG. 4, particularly by making the interval between stripe lines smaller, as shown in FIG. The area in which the bones are generated increases, and when the branches grow from the bones, the growth distance before joining the branches grown from the bones on the adjacent lines becomes shorter. Thus, particularly in the case of using a liquid crystal exhibiting a smectic liquid crystal phase, the uniformity of the smectic layer in the layer direction is improved. However, as described above, the area in which the alignment control layer 15a made of an insulating material is in contact with the liquid crystal is reduced as much as possible, and the liquid crystal region to which a voltage is applied to the liquid crystal without passing through the liquid crystal is enlarged. It is necessary to provide a certain distance between these lines.

For example, in the case of the structure as shown in FIGS. 3 and 4, it is preferable to set the line width to about 2 to 20 μm and to set the line interval in the range of 10 to 50 μm.

Also, the thickness of the stripe pattern should be 50 to
5000 °, preferably 200 to 1000 °.

On the other hand, the layer 14a constituting the surface R2 in contact with the liquid crystal 11 between the line portions of the alignment control layer 15a is:
Considering the relationship between the material used for the alignment control layer 15a, its characteristics, and the like, so that the alignment forming process shown in FIGS. 3 to 5 can be realized, the uniaxial alignment control force is larger than the surface R1 of the alignment control layer 15a. Is weak or practically has no uniaxial alignment regulating force on the liquid crystal, and the liquid crystal driving characteristics, particularly the insulating properties that do not affect the driving characteristics of the chiral smectic liquid crystal, are suppressed, and the effect on the liquid crystal molecules is small. Materials and processing conditions are selected and used.

In order to form a layer having substantially no uniaxial alignment regulating force as the layer 14a, for example, an inorganic film such as a metal oxide to which a uniaxial alignment regulating force cannot be substantially imparted even by a rubbing treatment or the like. It is preferable to use a material having high hardness such as. In this regard, in the structure shown in FIG. 2, the layer 14a can be omitted and the pattern-shaped orientation control layer 15a can be provided on the transparent electrode 13a made of ITO or the like.

The layer 14a has a surface R2 in order to favorably proceed the alignment forming process as shown in FIGS.
In the above, the interaction of liquid crystal molecules is reduced as compared with the surface R1 of the alignment control image 15a having the uniaxial alignment regulating force. Therefore, the surface R2 of the layer 14a is
In the direction of poor wettability with liquid crystal (stronger property of repelling droplets), in the direction of increasing contact angle, in the direction of decreasing surface energy dispersion term (γd), or increasing the surface energy hydrogen bonding term It is preferable to select a material, or a forming method and a processing method thereof as necessary according to the direction. Thus, the liquid phase-liquid crystal phase transition temperature of the liquid crystal region corresponding to the surface R1 of the line portion of the alignment control layer 15a is a portion corresponding to the surface R2 between the line portions). By setting the temperature higher than the temperature, it becomes possible to realize the above-described favorable alignment forming process.

More specifically, as the layer 14a, a material such as a sol-gel type silica film or an organically modified silica film having a surface energy dispersion term relatively lower than that of the orientation control layer 13a polyimide can be used.

Further, as the layer 14a, the orientation control layer 15
In addition to having a small effect on liquid crystal molecules as compared with the material used for a, the volume resistance value should be in the range of 1 × 10 ⁴ to 1 × 10 ¹⁰ Ωcm in order to improve the driving characteristics of the liquid crystal. preferable. In order to obtain such characteristics, for example, if necessary, a film made of a polycrystalline or amorphous metal oxide, a film made of a polycrystalline or amorphous semiconductor, and a fine particle (conductive fine particle) formed of an insulating base material Alternatively, a film dispersed in a binder can be used. The film made of the polycrystalline or amorphous metal oxide, the film made of the 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 of an oxide of a Group 12 element such as ZnO, CdO, ZnCdOx, GeO ₂ , SnO ₂ , GeS
Films of oxides of Group 4 elements and Group 14 elements such as nOx, TiO ₂ , ZrO ₂ , and TiZrOx can be given.

Examples of the film made of the polycrystalline or amorphous semiconductor include a film of a Group 14 semiconductor such as Si and SiC.

As the fine particles, for example,
Examples include oxides of Group IV elements, oxides of Group IV elements, oxides of Group IV elements, and fine particles of Group 14 semiconductors.

As the conductivity controlling impurity added to the polycrystalline or amorphous metal oxide, the polycrystalline or amorphous semiconductor or the fine particles as necessary, the conductive doping depending on the oxide of the Group 12 element is used. The property control impurities include, for example, Group 13 elements such as B, Al, Ga, and In as n-type impurities (donors / impurities that enhance electron conduction) and p-type impurities (impurities / impurities that increase hole conductivity). Tribe, 11
It is used for group elements such as Cu, Ag, Au, and Li.
Examples of the conductivity control impurities doped into the oxides and semiconductors of Group 14 elements include P, As, Sb, and Bi as Group 15 elements as n-type impurities and B and Group 13 elements as P-type impurities. Al, Ga, In and the like can be mentioned.

For such conductivity control impurities,
A donor is used when the surface potential of the substrate having the orientation control layer containing the material to which the impurity is added is positive, and an acceptor is used when the surface potential is negative. Combination) and the crystal state (the crystal defect density), but the concentration of free electrons or free holes of the material in the state where impurities are added is 1.0 × 10 ¹¹ to 1. 0 × 10 ¹⁴ atm /
It is preferable to set it to about cm ³ . In the case where a polycrystalline or amorphous material is used as a base material to which impurities are added, 1.0 × 1
0 ^{17 to} 1.0 × 10 ²⁰ atm / cm ³ (about 0.01 to 1% with respect to the base material) is set as an actual addition amount.

Examples of a material serving as a binder for dispersing the fine particles include SiOx, TiOx, and ZrO.
x, other oxide melting base materials, siloxane polymers and the like.

On the other hand, with respect to the alignment control layer 15b on the opposing substrate 12b, a uniaxial alignment regulating force is provided or another alignment control ability is provided according to the characteristics of the liquid crystal material used.

In the case where a liquid crystal material exhibiting a phase transition series such as an isotropic phase-smectic phase without using the cholesteric phase described above is used, the alignment control layer 15a having a uniaxial alignment control force on one substrate 12a is opposed to the other substrate. 12b
It is preferable that the alignment control layer 15b in the above is a layer having substantially no uniaxial alignment control force. In this case, the alignment control layer 15b more preferably has the same function as the layer 14a having a small interaction with the liquid crystal molecules on the side of the opposing substrate 12a as described above, and a material usable as the layer 14a is used. Particularly preferably, the same material as that of the layer 14a is used. In this manner, the insulating property is suppressed at most of the interface between the two substrates substantially in contact with the liquid crystal 11, and the liquid crystal,
In particular, the driving characteristics of the chiral smectic liquid crystal are improved.

In addition, in the liquid crystal element having the above structure, apart from the alignment control layers 15a and 15b and the layer 14a, an insulating film as a layer for preventing a short circuit between opposing substrates, a layer made of another organic material, an inorganic A layer made of a material may be provided.

The spacer 16 determines the distance between the substrates (cell gap), and for example, silica beads or the like are used. In addition to the spacer 15, the substrate 11
Adhesive particles made of a resin material such as an epoxy resin may be dispersed between the substrates in order to improve the adhesiveness between a and 11b.

However, the smectic liquid crystal display element has a problem that the display burn-in characteristic when the same image is continuously displayed for a long time is relatively large as compared with the nematic liquid crystal display element. This problem is a problem common to smectic liquid crystals, but a display burn-in problem is particularly observed in ferroelectric liquid crystals having bistability. It can be understood that the display burn-in phenomenon which is a problem in the smectic liquid crystal, particularly the ferroelectric liquid crystal, is caused by an electrical factor and an orientational factor.

First, in the ferroelectric liquid crystal, spontaneous polarization induces uneven distribution of ions, resulting in an electrical asymmetry and a loss of bistability. Observed. This can be said to be a problem specific to ferroelectric liquid crystals.

On the other hand, it is considered that the image sticking phenomenon is a problem of the molecular alignment at the interface between the surface of the alignment control film and the liquid crystal. This is a phenomenon that applies to all liquid crystal elements, but in liquid crystal elements, the molecular orientation direction of the bulk near the center between the substrates changes the interface molecular orientation direction, and as a result, display characteristics are observed as display burn-in. It is. That is, in a liquid crystal element in which at least one substrate is subjected to a uniaxial alignment treatment, liquid crystal molecules in the vicinity of the substrate interface having a uniaxial alignment regulating force are arranged on the average in a direction in which the alignment is easy, but the bulk is Are influenced by the direction of the electric field applied to the liquid crystal element, and the arrangement direction of these molecules is shifted. At that time, the liquid crystal molecules as a continuum in the thickness direction of the liquid crystal between the substrates reduce the increase in elastic free energy caused by the distortion of the molecular alignment direction between the substrate interface and the bulk, so that the orientation direction of the interface molecules themselves is reduced. Will change. At this time, the amount of change in the orientation of the interface molecules is considered to be more remarkable in a liquid crystal material having a larger continuum characteristic such as a larger elastic constant of Frank. Therefore, it is considered that the smectic liquid crystal, which is a higher-order liquid crystal phase, has relatively poor display burn-in characteristics as compared with the nematic liquid crystal.

Therefore, in the liquid crystal device of the present invention, in order to improve the above-described display burn-in characteristic, a liquid crystal device is provided between a pair of substrates.
The liquid crystal portion has a first liquid crystal region in which liquid crystal molecules near the substrate interface and the bulk liquid crystal molecules between the substrates are in a substantially continuous alignment state, and a bulk liquid crystal molecule between the liquid crystal molecules near the substrate interface and the substrate does not. It is preferable that the second liquid crystal region be in a continuous alignment state.

An element having such first and second liquid crystal regions is selectively provided with an alignment control layer having a uniaxial alignment regulating force on at least one of the substrates as described with reference to FIGS. It can be realized by the provided element.

A liquid crystal device having such first and second liquid crystal regions will be described with reference to FIG.

In the figure, a liquid crystal element 10 has a liquid crystal 20.
Are sandwiched between substrates 22a and 22b having electrodes 23a and 23b for applying an electric field to the liquid crystal and alignment control layers 25a and 25b for controlling the alignment state of the liquid crystal. In such an element, the liquid crystal 26 is formed on the substrate by appropriately selecting the material of the alignment control layer 25a (and / or 25b) in contact with the liquid crystal and controlling the surface state and characteristics of the interface (R21, R22) in contact with the liquid crystal. Liquid crystal molecules in a region L11 near the interface and bulk liquid crystal molecules L12 in a region L12 between the substrates
Are in a substantially continuous alignment state, and
The region L between the liquid crystal molecules in the region L21 near the substrate interface and the substrate
In this case, 22 bulk liquid crystal molecules are constituted by a second liquid crystal region L2 in a discontinuous alignment state.

The operation of the liquid crystal device will be described.

As described above, the image sticking phenomenon in the liquid crystal element is considered to be a phenomenon resulting from a change in the orientation direction of interfacial molecules for reducing an increase in elastic free energy caused by bulk orientation distortion. That is, the burn-in phenomenon can be said to occur when all of the liquid crystal portions in the device thickness direction such as the bulk portion and the interface portion between the substrates of the device behave as an elastic continuum.

Therefore, in the liquid crystal element having the structure shown in FIG. 16, in the liquid crystal region L2, the liquid crystal molecules in the region L21 near the interface of the alignment control layer 25a and the region L2 between the substrates are different.
Since the bulk liquid crystal molecules in 22 have a discontinuous alignment state, the occurrence of the display burn-in phenomenon is suppressed.
Specifically, the liquid crystal alignment state in the region L21 is completely different from the bulk liquid crystal alignment state in the region L22, and the molecular alignment is controlled so that a continuum as a molecular group cannot be formed. More specifically, in the region L21, the alignment direction of the liquid crystal molecules is completely random, and the region L22
In this example, the liquid crystal molecules are controlled so that the alignment direction is aligned in a uniaxial direction (the uniaxial alignment processing direction in the alignment control layer 25a). In the liquid crystal region L2, by adopting such an alignment state, the interface and the bulk become discontinuous alignment states, and the alignment state does not influence each other, that is, an element in which the alignment state does not change with time can be realized.

Note that L21, which is a region near the substrate interface constituting the liquid crystal region L2, and L2, which corresponds to the bulk portion,
2. With respect to L11 which is a region near the substrate interface constituting the liquid crystal region L1 and a region L12 corresponding to the bulk portion, the regions L21 and L11 are located at the substrate interface (the orientation control layer 2).
100 ° from the interface between 5a (or 25b) and liquid crystal 20)
The regions L22 and L12 can be assumed to be a central portion between the substrates excluding the regions L21 and L11 from the substrate interface. The behavior of liquid crystal molecules in these regions is described in Appl. Phys.
Lett. Vol. 53 (24) P2397-2398
TIR (Total Internal Re)
fraction) method, SHG (Second Har)
(MonicGeneration) method.

Next, means for obtaining the above liquid crystal element,
In particular, adjustment of the orientation control layer 25a (25b) will be described. Usually, in a liquid crystal element, the molecular alignment direction of the entire cell is determined according to the alignment control direction applied to a pair of substrates.
That is, during the phase transition process from the liquid phase to the liquid crystal phase, the phase transition from molecules near the alignment control film to the liquid crystal phase. At that time, the molecules are arranged in accordance with the direction of the alignment treatment applied on the alignment control film, and when the cooling is further advanced, the phase transition to the liquid crystal phase extends to the bulk portion, and the entire cell becomes the liquid crystal phase. That is, in the ordinary liquid crystal element, since the molecular alignment is formed by the regulation of the interface, a continuous molecular alignment state is obtained between the interface and the bulk as in the region L1.

On the other hand, in order to obtain a discontinuous molecular arrangement state between the substrate interface and the bulk portion as in the above-mentioned region L2,
Both a portion having a uniaxial orientation regulating force (a portion subjected to a uniaxial orientation treatment) and a portion having substantially no or weak uniaxial orientation regulating force (a portion not subjected to a uniaxial orientation treatment) in the same substrate surface Is preferably provided. Specifically, the surface R21 in the orientation control layer 5a is a portion having a uniaxial orientation regulating force, and R22 is a portion having substantially no uniaxial orientation regulating force or a portion having a relatively weak uniaxial orientation regulating force as compared with R21. .

In the case of an element constituted by a substrate having such a layer 25a having alignment control ability, the liquid phase-liquid crystal phase transition is caused by molecules near the interface of the liquid crystal region in the portion (R21) having uniaxial alignment regulating force. It is generated from (L11) and expands to a liquid crystal region (L2) corresponding to a portion where alignment is not regulated. The order of the phase transition is apparent from the fact that the liquid crystal element generally has a higher uniaxial alignment regulating force, and thus has a higher phase transition temperature to a liquid crystal phase. As described above, when the portion (R21) having the uniaxial orientation regulating force and the portion (R22) having substantially no uniaxial orientation regulating force are provided on the same substrate surface, particularly, the uniaxial orientation regulating force is substantially reduced. The bulk alignment (L22) of the liquid crystal region corresponding to the portion (R22) that does not have the effect is not affected by the interface (R22) of the liquid crystal region, but the portion (R2) having the adjacent uniaxial alignment regulating force.
The alignment can be performed according to the alignment of the bulk portion (L12) of the liquid crystal region corresponding to 1). Among them, particularly in a liquid crystal phase having high crystallinity such as a smectic liquid crystal, after a uniform alignment is formed in a liquid crystal region (L1) corresponding to a portion having a uniaxial alignment regulating force (R21), a portion where uniaxial alignment is not regulated ( Region (L2) corresponding to R22)
By performing crystal growth on the substrate, the entire cell can be uniformly aligned regardless of the presence or absence of alignment control at the substrate interface.

Since the smectic liquid crystal is a one-dimensional crystal with respect to the layer normal direction, the crystal growth direction at this time tends to progress toward the layer normal direction. Therefore, it is desirable that the portion (R21) having the uniaxial alignment regulating force is continuous or substantially continuous in the smectic layer direction. On the other hand, at this time, in the liquid crystal region (L2) corresponding to the portion (R22) where the uniaxial alignment is not regulated, the region near the interface (L2)
The orientation direction of the molecules in 1) is in a random direction.
This means that the molecules in the region near the interface (L21) undergo a phase transition from the molecules in the region near the interface (L21) to the liquid crystal phase first. This is because the alignment direction of the interface-neighboring region (L21), which is not necessarily uniaxially controlled, is forced to be in a random direction because the molecular arrangement is performed to some extent under the restriction described above. Thus, the bulk portion (L2
A liquid crystal element exhibiting a discontinuous alignment state (liquid crystal region L2) in the thickness direction of the liquid crystal 10, in which 2) is uniformly aligned and a region near the interface (L21) is randomly aligned, can be realized.

Regarding the interface R22 of the alignment control layer 5a corresponding to the liquid crystal region of L2, the surface state is determined by calculating the surface roughness of the arithmetic average roughness Ra of 2 nm or more and the root mean square roughness Rms.
Has a surface roughness of 2.5 nm or more, or a surface roughness of 5% or more.

By doing so, the rising angle (pretilt angle) of the molecules in the vicinity of the interface R22 and in the liquid crystal region (L21) becomes an angle based on the surface unevenness, so that the pretilt angle also becomes a random angle in the layer near the interface. Become. That is, the liquid crystal region (L21) and the bulk region (L22) near the substrate interface not only in the in-plane direction of the substrate (azimuth direction) but also in the rising direction from the substrate (polar angle direction).
Thus, a discontinuous molecular arrangement can be obtained, so that the effect of suppressing display burn-in is further increased.

Here, the arithmetic mean roughness Ra represents the average value of the absolute value of the deviation from the center plane to the surface in the quantitative plane, and the root mean square roughness Rms refers to the mean surface roughness from the central plane in the quantitative plane. Represents the parallel root of the mean of the squares of the deviations up to. The surface roughness is expressed by the following equation according to the relationship with the surface area S 'including the surface irregularities when a film having the irregularities on a certain area S exists.

Surface roughness = (S'-S) / S

In the liquid crystal device having the structure as shown in FIG. 16, for example, a portion of the liquid crystal 10 is divided into a plurality of units of a real driving region which are separated from each other, and these are all or selectively used for the liquid crystal in the real driving region. Can be used in such a manner as to be driven. In a liquid crystal display device, such an actual driving area corresponds to a so-called pixel. In such an embodiment of the liquid crystal element, it is preferable that at least the actual driving region corresponds to the second liquid crystal region L2 and the space between the actual driving regions corresponds to the first liquid crystal region L1.

As described above, the first liquid crystal region (L1)
And the second liquid crystal region (L2) preferably has a portion (R
By providing 2) and a portion (R22) having substantially no or substantially small uniaxial alignment regulating force, it can be formed corresponding to these. Therefore, the structure shown in FIG. 1 and FIG. 2 and the structure of the substrate and the element to which the above-described member processing is applied allow the alignment forming process shown in FIGS. An element having such a first liquid crystal region (L1) and a second liquid crystal region (L2) can be obtained. A surface region R21 on the substrate to which the first liquid crystal region (L1) is provided in FIG. 16 is a surface region R1 substantially parallel to the substrate of the alignment control layer 15a having the uniaxial alignment regulating force in FIG. The surface region R22 on the substrate to which the second liquid crystal region L2 is provided in FIG. 16 corresponds to the surface region R2 between the lines of the layer 15a in FIG.

That is, in the liquid crystal device having the structure shown in FIG. 2, the alignment control layer (15a) having a uniaxial alignment regulating force, which usually has an insulating property, forms a nucleus (battone) serving as a starting portion for forming an alignment state. It is provided in a pattern shape necessary for supply, and as shown in FIG. 3 to FIG. 5, a uniform alignment state is reliably formed on the entire surface of the device by the alignment state forming process. Due to the relationship between the characteristics of the surface R1 of the control layer 15a and the surface R2 of the gap layer 14a, the liquid crystal region corresponding to R1 is in a state where the regions L11 and L12 are continuously arranged as the liquid crystal region L1 shown in FIG. , R2 correspond to FIG.
As in the liquid crystal region L2 shown in FIG. 6, the regions L21 and L22 are in a discontinuous alignment state.

In particular, in the element structure shown in FIG. 2, in order to form the first liquid crystal region L1 and the second liquid crystal region L2 shown in FIG. 16 well, the regions L21 and L22 are arranged in a discontinuous arrangement. Then, a surface R2 is formed.

The layer 14a has a surface condition of the above-mentioned predetermined roughness, for example, a direction in which the wettability with the liquid crystal is not good (the property of repelling droplets is strong), a direction in which the contact angle is large, It is preferable to roughen and use a material in a direction in which the surface energy dispersion term (γd) becomes smaller or in a direction in which the surface energy hydrogen bonding term becomes larger.

In order to obtain the liquid crystal region L2 and to obtain desired electric characteristics and surface characteristics, it is particularly preferable to use the layer 14a.
A film in which the above-described fine particles (conductive fine particles) are dispersed in an insulating base material and a binder is used. The conductivity is adjusted by adding a conductive impurity as necessary to the fine particles.

In the element 1 having the above structure, preferably, the liquid crystal 11 is composed of a plurality of actual driving regions in which the liquid crystal between the substrates is separated from each other. In the actual driving region, a signal power supply (not shown) is provided. An electric field is applied to the liquid crystal 11 by the electrodes 12a and 12b in response to the switching signal from the switch, switching is performed, and light passing through the liquid crystal 11 is modulated, so that at least a bright state and a dark state are formed.

Further, in the liquid crystal region corresponding to the alignment control layer 15a (all the liquid crystal regions in the thickness direction of the element corresponding to the region R1), the positions of the liquid crystal molecules in the region are fixed so as to show a dark state. It can also be converted.

In particular, the difference between the surface potential of the region R1 of the orientation control layer 15a and the surface potential of the orientation control layer 15b facing this region is reduced by 50%.
greater than 100 mV, preferably greater than 100 mV,
The position of the liquid crystal molecules is fixed so that a dark state is always shown in the region within the facing surface.

In a matrix type liquid crystal display device using a liquid crystal exhibiting ferroelectricity and having a pair of substrates having striped electrodes opposed to each other, a region corresponding to a region other than a portion where the electrodes of each substrate cross each other, that is, In the region between the pixels, the molecular alignment state of the liquid crystal cannot be controlled by the electric field, and light leakage may occur between the pixels and the contrast in display may be deteriorated. A material such as a black matrix such as a material is provided to shield light. However, the formation of the black matrix requires alignment and the like to correspond to the portions where the pixel electrodes intersect with each other, which leads to an increase in cost. The reflectance may increase, and the display quality may decrease.

Further, in a matrix type liquid crystal display device using an antiferroelectric liquid crystal, the alignment state of the liquid crystal between pixels may be slightly disturbed as compared with other regions. Also in this case, since light leakage between pixels may cause deterioration of display contrast, it is necessary to provide a member such as a black matrix made of a metal material on a substrate corresponding to the inter-pixel region as described above to shield light. And similarly, a reduction in display quality is adjusted. Therefore, by providing a region where the above-mentioned alignment state is fixedly formed corresponding to the inter-pixel region, a wide driving margin is realized while realizing uniform liquid crystal molecule alignment, and higher switching characteristics are realized. With a simple structure and between the actual driving regions,
In particular, light is reliably shielded between pixels in the display element, and a sufficient contrast can be ensured.

Next, a second embodiment of the liquid crystal device of the present invention will be described with reference to FIG. 2, the same reference numerals as those in FIG. 2 indicate the same members.

The basic structure of the liquid crystal element 101 according to the second embodiment shown in FIG. 17 is the same as that of the first embodiment shown in FIG. 2, and an electric field is applied to the liquid crystal 11 on the substrate 12a side. On the electrode 13a to be applied, an orientation control layer 15a is provided in a desired shape such as a stripe shape or a lattice shape via a base layer 14a, is in contact with the liquid crystal 11, and has an upper surface, that is, a surface substantially parallel to the substrate 12a. In the (region R1), the liquid crystal 11 has at least a uniaxial alignment regulating force. Further, in a region that does not correspond to the alignment control layer 15a, the region is in contact with the liquid crystal 11 on the surface (R2) where the layer 17a is not provided on the base layer 14a. Here, the layer 17a
Is formed of a material which is made of an insulating material or the like similarly to the orientation control layer 15a and which exerts a uniaxial orientation regulating force on the liquid crystal by performing an appropriate treatment.
By making the thickness extremely small as compared with the above, the uniaxial alignment regulating force on the liquid crystal on the surface (R2) is relatively small as compared with the surface (R1), so that the interaction with the liquid crystal is reduced. Note that, on the opposing substrate 12b, an alignment control layer 15b that is in contact with the liquid crystal and can contribute to the alignment control of the liquid crystal is formed on the electrode 11b that applies an electric field to the liquid crystal 11.

In the liquid crystal element 1 having the above structure, the liquid crystal 1
As in the first embodiment, by appropriately setting the alignment control layers 15a, 17a, and the alignment control layer 15b, the material of the liquid crystal 11, the processing method, the conditions, etc. As shown in the drawing, in the liquid crystal 11, in the phase transition process between the liquid phase and the liquid crystal phase of the liquid crystal when the temperature is lowered, the region of the alignment control layer 15 a from the region in contact with the surface region R <b> 1 (first region) in the direction parallel to the substrate changes to the liquid crystal phase. A phase transition occurs, and a liquid crystal phase transition region continuously grows in the axial direction of the uniaxial alignment regulating force (axial direction of the uniaxial alignment treatment) of the alignment control layer 15a, and further, the surface region R2 (second region) Then, the phase transition region expands, and an alignment state is formed. In particular, the relationship between the orientation control layer 15a and the uniaxial alignment regulating force of the surface of the layer 17a and the interaction with the liquid crystal, that is, the strength of the uniaxial alignment regulating force of the former surface is relatively increased, and the mutual interaction with the liquid crystal is increased. By increasing the action, the process of forming the above-described alignment state can be effectively obtained.

The alignment control layer 15a corresponding to the first region (R1) where the liquid crystal phase transition occurs first can be formed by using the same material and processing as in the first embodiment. . On the other hand, as the layer 17 corresponding to the region (R2) other than the first region (R1), for example, those exemplified as materials that can be used for the orientation control layer 15a can be used in the same manner. As a specific example, layer 1
After forming a material layer (film) for forming the orientation control layer 15a on the entire surface of the substrate 4a, conditions for patterning by the above-described method such as UV ashing are adjusted to selectively form the orientation control layer 15a. At the same time, the same material is used between the lines of the orientation control layer 15a.
A layer 17a having a smaller thickness than that of 5a can be obtained. In this case, in other words, the layer 17a is the orientation control layer 15
a is formed continuously with the protruding line with a reduced thickness between the protruding lines. By performing a uniaxial orientation treatment after such patterning, a strong uniaxial orientation regulating force is applied to the surface of the portion where the thickness of the orientation control layer 15a is large (corresponding to the first region (R1)). On the surface (corresponding to the second region R2), a relatively weak uniaxial alignment regulating force can be applied.

In the second embodiment, similarly to the first embodiment, a uniform alignment state can be reliably formed on the entire surface of the element by the processes shown in FIGS. In addition, when an insulating material is used for the alignment control layer 15a and the structure shown in FIG. 17 is formed by the patterning method such as the above-described UV ashing or the like, the insulation which becomes an obstacle to the driving of the liquid crystal can be obtained. Between the lines of the orientation control layer 15a having a uniaxial orientation regulating force made of a conductive material, there is only a layer 17a having a small thickness and the influence of the insulating property is suppressed, and the influence of the insulating layer is electrically small. The liquid crystal region to which a voltage is applied becomes large in the entire device, and in particular, the effective voltage applied to the liquid crystal during driving by a pulse voltage can be increased.

When the layer 17a forming the second region (R2) is an insulating layer, the thickness of the region (R2) is determined by using a smectic liquid crystal having spontaneous polarization as the liquid crystal.
Is used as the actual driving region of the liquid crystal element, it is important to set so that the switching of the liquid crystal molecules is not hindered by the reverse voltage that causes the spontaneous polarization of the liquid crystal between the substrates of the element. Specifically, it is preferable that the total thickness of the insulating layers of both substrates corresponding to the region (R2) including the layer 17a be less than d1 of the following formula A1.

(A1) d1 = Vth1 × ε / 2Ps Vth1: threshold voltage partially inverted by a unipolar pulse having a pulse width of 1 ms ε: total dielectric constant of insulating layers of both substrates corresponding to surface R2 Ps: used Spontaneous polarization of liquid crystal (per unit area)

The expression A1 represents the value of the reverse voltage Vrev = 2Ps * S / C and C = ε * S / when the switching of the liquid crystal begins to be inhibited by the reverse voltage generated by spontaneous polarization.
The thickness of the insulating layer at that time is obtained as d1 (C is the liquid crystal capacity in the corresponding region 2 and S is the area of the region).

On the other hand, as for the thickness of the orientation control layer 15a in the first region (surface R1), the total thickness of the insulating layers of both substrates corresponding to the surface region R1 including at least the layer 15a is d1 of the above formula A1. It is preferable to set it as above, and it is especially preferable to set it as d2 or more of the following formula A2.

(A2) d2 = Vth2.times..epsilon. / 2Ps Vth2: threshold voltage which is completely inverted by a unipolar pulse having a pulse width of 1 ms. .Epsilon .: total dielectric constant of insulating layers of both substrates corresponding to region R1. Ps: liquid crystal to be used. Spontaneous polarization (per unit area)

Further, the layer 17a is preferable depending on the material of the underlying layer 14a and also for reducing the chemical influence on the liquid crystal from the electrode 14a, in particular, the influence of the movement of ions from the lower layer.

Incidentally, the strength of the alignment regulating force referred to in the present invention is defined below. When a liquid crystal material is injected into a cell having no alignment regulating force, the molecular tension axis direction is generally oriented in a random direction unless a special external field such as a magnetic field or a temperature gradient is used. On the other hand, when a liquid crystal material is injected into a cell in which uniaxial alignment is controlled sufficiently firmly, the molecular long axis direction is generally aligned in a direction in which uniaxial alignment is controlled. The latter orientation is almost the same for both nematic and smectic liquid crystals, but the former orientation has a slight difference in texture between nematic and smectic. When the molecular long axis direction is oriented in a random direction, a smectic having a layer structure forms a random layer structure while exhibiting a geometric pattern called focal conic texture. In the present invention, the weak alignment control force in the smectic liquid crystal is the alignment control force of the cell when the smectic liquid crystal is injected into a cell whose uniaxial alignment is controlled, such a focal conic texture is expressed in a part of the cell. Is defined as weak. Similarly, when a smectic liquid crystal is injected into a cell whose uniaxial orientation is controlled, the above-mentioned focal conic texture does not exist at all, and when the layer structure is controlled in one direction in an orderly manner, the alignment control force of this cell is controlled by this liquid crystal. Define it as strong. Then, the relative strength is determined based on the existence ratio of the focal conic texture. Since the definition of the strength is determined by the orientation, the degree of the strength changes as the type of liquid crystal changes. That is, the strength of the alignment regulating force in the present invention is not uniquely determined by the cell, but defined by the combination of the cell and the liquid crystal.

FIG. 18 shows a third mode which is a further modification of the structure of the liquid crystal element of the second embodiment shown in FIG. The structure shown in FIG.
After selectively providing a layer 18a formed of the same material as that described above, a layer 19a which is applicable to the orientation control layer 15a with a small thickness from the upper side is formed on the entire surface, and a uniaxial orientation regulating force is applied. is there. In this case, the surface (region R1) of the layer 19a on the selectively provided layer 18a (on the line) and the layer 18a
In the surface (region R2) of the layer 19a between the lines a, the region R1 is the surface of the layer having a large total thickness of the material capable of providing the uniaxial alignment regulating force. The uniaxial alignment regulating force can be made relatively small and the interaction with the liquid crystal can be made small, and the same effect as in the second embodiment can be obtained.

In the second and third embodiments as described above, the surface condition of R1 and R2 is determined by selecting the material, thickness, and processing conditions of the orientation control layer 15a, the underlayer 14a, the layers 17a, 18a, and 19a. By adjusting the thickness of the underlayer 14a, the surface R1 becomes the surface R21 of the substrate as described in FIG. 16 and the surface R2 becomes the surface R22 in FIG. The liquid crystal regions L1 and L2 shown in the figure can also be formed.

Referring to FIG. 6, a fourth embodiment of the liquid crystal device of the present invention is shown. In the figure, the same reference numerals as those in FIGS. 1 and 2 denote the same members.

In the embodiment shown in the figure, the liquid crystal 1 is placed on the substrate 12a.
In addition to the orientation control layer 15a having a uniaxial orientation regulating force being selectively provided in a pattern shape in the surface region R1 contacting with the substrate 1, the orientation control layer 15b is similarly provided in a pattern shape on the opposing substrate 12b. Have been. Like the alignment control layer 15a, the alignment control layer 15b has a uniaxial alignment regulating force on the surface (R3) in contact with the liquid crystal. In particular, a material usable as the alignment control layer 15a and a uniaxial alignment treatment are selected. And applied. The line portions of the patterns of the alignment control layers 15a and 15b are aligned with each other and completely oppose each other, and the axes of the uniaxial alignment regulating force or the uniaxial alignment processing directions of both alignment control layers are the same.

In such an element, in addition to the substrate 12a side,
Also on the substrate 12b side, a process of forming an alignment state as shown in FIGS. 3 to 5 proceeds, and a liquid crystal alignment is obtained.

Therefore, the surface R4 in contact with the liquid crystal 11 between the lines of the alignment control layer 15b substantially corresponds to the region R with respect to the liquid crystal.
3 has a relatively strong uniaxial alignment regulating force or does not have a uniaxial alignment regulating force, and has a reduced effect on liquid crystal molecules. The layer 14b constituting this layer has an alignment control layer 15b. In consideration of the material to be used, its characteristics, and the like, the layer 14a on the opposite side is formed by applying a usable material and a processing method.

Further, in the above device, the orientation control layer 15a,
15b is selected, and the difference between the surface potentials of the opposing surfaces (R1, R3) is preferably 50 mV as described above.
The position of the liquid crystal molecules is set to be larger than that, preferably larger than 100 mV, so that a dark state is always shown in a region sandwiched therebetween.

In the above-described device, the regions R2 and R4 are formed by a thin layer different from the underlayer as in the second and third embodiments described above, and the uniaxial alignment control is performed as compared with the regions R1 and R3. The force may be weak and the effect on the liquid crystal molecules may be reduced.

FIG. 7 shows a fifth embodiment of the liquid crystal device of the present invention. In the figure, the same reference numerals as those in FIG. 21 denote the same members.

In the device having the structure shown in the figure, the electrodes 13a and 13b formed on the substrates 12a and 12b are formed in stripes, and they are opposed to each other in a matrix. It is a pixel in the element. Then, on the substrate 12a side, the orientation control layer 1 made of an insulating material and having a uniaxial orientation regulating force.
5a is provided in a pattern shape such that the line portions correspond to between the respective stripes of the electrode 13a on the same substrate. FIG. 8 shows the positional relationship of the pattern shape of the electrode 13a and the orientation control layer 15a on the substrate 12a side as viewed from above (other members are omitted in FIG. 8). Here, when the electrode 13a is a transparent electrode and a metal electrode is provided as described above, the orientation control layer 1 is also provided on the metal electrode.
It is preferable to make the line of 5a correspond.

The alignment state of the element having such a structure is basically determined by the processes shown in FIGS. 3 to 5 starting from the liquid crystal region corresponding to the uniaxial alignment control layer 15a, as in the first embodiment. It is formed. Further, in this embodiment, the alignment control layer 15a having an uniaxial alignment regulating force made of an insulating material that electrically obstructs driving of the liquid crystal is provided in the actual driving region of the liquid crystal due to the positional relationship with the electrode 13a on the same substrate. Alternatively, the effective voltage applied to the liquid crystal at the time of driving by the pulse voltage in the region substantially does not exist in the pixel portion can be increased. In this way, it is possible to achieve both uniform alignment and high-speed liquid crystal driving (switching). In particular, a remarkable effect is brought about with respect to the latter property. Further, when applied as a display element,
The pixel area to be driven effectively can be increased, and the aperture ratio can be improved.

In addition, in the device of the fifth aspect, the alignment control layer 15a corresponding to between the actual driving regions or between the pixels.
By selecting the material and processing method of the facing orientation control layer 15b, and preferably setting the difference in surface potential of the facing surface as described above, a dark state is shown between these actual driving regions or pixels. Then, the positions of the liquid crystal molecules in the same region are fixed. Thus, in both the substrates 12a and 12b, the contrast is improved without providing a light-shielding member made of metal or the like between the actual driving regions, and the reflectance on the display surface is reduced. In order to make this effect more conspicuous, an orientation control layer 15a as shown in FIG. 8 is added in the same direction as the line of the electrode stripe 13a in FIG. It is particularly preferable to form a grid-like pattern provided between the lines of the electrode stripe (13b) on the substrate (12b) side.

In the element having the above structure, the surface of the layer 14a between the lines of the alignment control layer 15a is covered with another thin layer different from the layer 14a as in the second and third embodiments described above. Compared with the surface of the layer 15a, the uniaxial alignment regulating force is weak and the action on the liquid crystal molecules can be reduced.

FIG. 9 shows a sixth embodiment of the liquid crystal device of the present invention. In the figure, the same reference numerals as those in FIGS. 1, 2 and 6 denote the same members.

In the device having the structure shown in the figure, the electrodes 13a and 13b formed on the substrates 12a and 12b are formed in stripes, these are opposed to each other in a matrix, and the intersections between the electrodes 13a and 13b correspond to the actual driving area or the display. It is a pixel in the element. Then, on the substrate 12a side, the orientation control layer 1 made of an insulating material and having a uniaxial orientation regulating force.
5a is provided in a pattern shape such that the line portions correspond to between the respective stripes of the electrode 13a on the same substrate. FIG. 8 shows the positional relationship of the pattern shape of the electrode 13a and the orientation control layer 15a on the substrate 12a side as viewed from above (other members are omitted in FIG. 8). On the other hand, substrate 1
On the 2b side, an alignment control layer 15b having a uniaxial alignment control force made of an insulating material in a pattern shape such that the line portions face the alignment control layer 15a on the substrate 12a side.
Is provided. FIG. 10 shows a positional relationship of the pattern shapes of the electrode 13b and the orientation control layer 15b on the substrate 12b side as viewed from above (other members are omitted in FIG. 10). Here, the electrodes 13a and 13b are transparent electrodes,
When a metal electrode is provided as described above, it is preferable that the line of the orientation control layers 15a and 15b also correspond to the metal electrode. For the orientation control layer 15a and the orientation control layer 15b, a material and a uniaxial orientation treatment that can be used as the orientation control layer 15a described in the first embodiment are particularly selected and applied. The directions of the uniaxial alignment treatment in both alignment control layers are preferably the same.

The alignment state of the device having such a structure is basically the same as in the fourth embodiment described above, except that the liquid crystal regions corresponding to the uniaxial alignment control layers 15a and 15b on both substrates are used as starting points in FIGS. It is formed by a process as shown in FIG. Furthermore, in this embodiment, the alignment control layers 15a and 15b made of an insulating material that is an obstacle to the driving of the liquid crystal and have a uniaxial alignment control force are provided on the electrodes 13
Due to the positional relationship between a and 13b, the effective voltage applied to the liquid crystal during driving by the pulse voltage in the actual driving region or the pixel portion of the liquid crystal can be increased without substantially existing in the actual driving region or the pixel portion. In this way, it is possible to achieve both uniform alignment and high-speed liquid crystal driving (switching). In particular, a remarkable effect is brought about with respect to the latter property. Further, when the present invention is applied to a display element, the area of a pixel to be driven effectively can be increased, and the aperture ratio is improved.

In the actual driving area of the liquid crystal, 14
The regions L21 and L21 of the liquid crystal region L2 as described with reference to FIG.
As shown in 22, the liquid crystal molecules in the liquid crystal region near the substrate interface and the liquid crystal molecules in the bulk region can form a discontinuous alignment state.

In this way, both the alignment state and uniformity and the high speed driving (switching) of the liquid crystal are realized, and the burn-in during driving is suppressed. Further, when the present invention is applied as a display element, the area of a pixel to be driven effectively can be increased, and the aperture ratio is improved.

In addition, in the device of the eighth aspect, the alignment control layer 15a corresponding to between the actual driving regions or between the pixels.
By selecting the material and processing method of the facing orientation control layer 15b, and preferably setting the difference in surface potential of the facing surface as described above, a dark state is shown between these actual driving regions or pixels. Then, the positions of the liquid crystal molecules in the same region are fixed. In this way, in both the substrates 12a and 12b, the reflectance on the display surface is suppressed and the contrast is improved without providing a light-shielding member made of metal or the like between the actual driving regions. In order to make this effect more conspicuous, an orientation control layer 15a as shown in FIG. 8 is added to a substrate (FIG. 8) having a line portion in the same direction as that of the electrode stripe 13a in FIG. A grid pattern corresponding to the space between the lines of the electrode stripe (13b) on the 12b) side is formed. The alignment control layer 15b as shown in FIG.
In addition to the direction perpendicular to the line direction of the electrode stripe 13b, the electrode stripe 13b has the same direction as the line direction of the electrode stripe 13b.
It is particularly preferable to form a lattice pattern corresponding to the space between the lines 3b.

In the element having the above structure, the second and third elements described above are also used.
As in the third embodiment, the surfaces of the layers 14a and 14b between the respective lines of the orientation control layers 15a and 15b are changed to the layers 14a and 14b.
And another orientation control layer 15a, 15b
In this case, the uniaxial alignment regulating force is weaker than that of the surface, and the action on liquid crystal molecules can be reduced.

In the device according to the fifth and sixth embodiments, the electrodes 12a and 12b of both substrates form a matrix electrode structure, and can perform pattern display and pattern exposure. For example, a personal computer, a workstation, etc. It is suitably used as a light valve for displays, printers and the like.

In the fifth and sixth embodiments, in order to obtain a better alignment state, the alignment control layers 15a and 15a
5b can also be provided in the above-mentioned actual driving area or pixel where the electrodes 13a and 13b intersect. The thickness of the alignment control layer provided in the actual driving region or the pixel is preferably set to be larger in the above range (50 to 5000 °), more preferably 500 ° or more, and the liquid crystal region corresponding to the alignment control layer is set. To prevent the liquid crystal region from being completely driven by suppressing the voltage applied to the electrodes 13a, 13a,
The drive characteristics of the liquid crystal in the entire intersection of 13b are improved.

As the driving method of the liquid crystal element of the present invention, particularly for the simple matrix electrode arrangement as described in the fifth and sixth embodiments, for example, JP-A-59-193426, JP-A-59-193427, JP-A-60-156046
And Japanese Patent Application Laid-Open No. 60-156047.

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

FIG. 11 is a plan view showing an example of the arrangement of matrix electrodes in a liquid crystal element. The scanning lines (S1 to Sm) of the scanning electrode group 52 are provided on the liquid crystal element (panel) 51.
And the data lines (I1 to In) of the information electrode group 53 are wired so as to cross each other, and a liquid crystal is arranged between the scanning lines and the data lines. Then, each intersection of the scanning line and the data line becomes a pixel as one display unit, and a voltage is applied from the scanning line and the data line to drive the liquid crystal. In the third and fourth embodiments, the electrodes 13a and 13b provided on the substrates 12a and 12b respectively correspond to the electrodes 52 and 53 shown in FIG.

FIGS. 12 and 13 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. 12 is a reset write type waveform in which black display is set with a positive polarity with respect to the scan line side and the reset direction is set on the black display side. S0 represents a scanning signal waveform applied to the scanning line, I1 represents an information signal waveform (white display waveform) applied to the data line, and I2 represents an information signal waveform (black display waveform) applied to the data line. Also, (S0-I1) and (S
0-I2) is a voltage waveform applied to the selected pixel,
The pixel to which the voltage (S0-I1) is applied becomes a white display state, and the pixel to which the voltage (S0-I2) is applied becomes a black display state (reset is set to the black display side as described above).

(S2-I0) and (S3-
I0) is the drive waveform shown in FIG. 12, and is applied to the second and third pixels 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. 12 and 13, the write pulse width Δ applied to the pixels on the selected scanning line
The reset pulse for clearing one line is 5 / 2Δ
t, and a pulse that assists the reset pulse side after the write pulse is ΔΔt. Therefore, in the driving waveforms shown in FIGS. 12 and 13, the one-line scanning time (1H) is 4Δt minutes. However, as shown in FIG. 13, in addition to scanning without providing a time period in which the scanning waveforms overlap each other, a time period in which the scanning waveforms of two or more scanning lines (for example, adjacent scanning lines) overlap is provided (for example, It is also possible to shorten the practical one-line scanning time (1H) (for example, to 2Δt).

Each of the parameter scanning signal voltage VS, information signal VI, and driving voltage Vo of the driving waveforms shown in FIGS.
p (VS + VI), (bias ratio: VI / (VS + V
The values of I) and Δt are determined by the switching characteristics of the liquid crystal material used.

FIG. 14 shows that the above-mentioned bias ratio is fixed to 1 / 3.4, the driving voltage Vop (VS + VI) is fixed at 20 V, and the pulse width Δt is changed using the driving waveform shown in FIG. FIG. 9 shows a final change in transmittance T after application of a drive waveform (after selection application) in a corresponding pixel.

In the figure, the solid line indicates a white waveform (S0-I
1) (Black erasure (reset) white writing), the broken line is a case where a black waveform (S0-I2) (black erasure (reset) retention) is applied. When a solid white waveform (S0-I1) is applied, the state before the waveform of the corresponding pixel is applied is a black state, and writing to the white state can be performed completely with a pulse width of Δt1 or more. At Δt larger than Δt2, writing to the white state cannot be performed again (for example, the white display waveform (S0-I shown in FIG. 12).
The black state is restored by the application of the auxiliary pulse of the opposite polarity following the W pulse of 1)). In addition, a black waveform (S
In 0-I2), the state before the waveform of the pixel is applied is the opposite white state, and writing and holding to the black state are completely realized with a pulse width of Δt3 or more, and Δt
At Δt greater than 4, the black state cannot be maintained (the white state is achieved by the application of the reverse polarity holding pulse subsequent to the B pulse of the black display waveform (S0-I2) shown in FIG. 12). .

Normally, since Δt3 <Δt1, Δt1 is called the threshold pulse width, and the smaller of Δt2 and Δt4 (Δt4 in FIG. 14) is called the crosstalk pulse width (Δt3).
t2 is also called a white crosstalk pulse width, and Δt4 is also called a black crosstalk pulse width).

A white display waveform (the white display waveform (S) shown in FIG. 12 where matrix drive is performed by a drive waveform having a pulse width between the threshold pulse width and the crosstalk pulse width.
0-I1)), a reliable white display and a black waveform (FIG. 12)
The black display waveform (S0-I2) shown in (1) above enables reliable black display, and excellent white and black image display can be achieved only by the difference in polarity on the information signal side.

Although it is possible to increase the value of the crosstalk pulse width of Δt2 or Δt4 by increasing the bias ratio described above, increasing the bias ratio means increasing the amplitude of the information signal. However, it is not preferable in terms of image quality because flicker increases and contrast decreases. In our study, a bias ratio of about 1/3 to 1/5 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 Δt1 is used. And a parameter “M2” that represents the width of the value of the crosstalk pulse width Δt4 (Δt2 in some cases) from the center value by a ratio. M2 = 1/2 (Δt4−Δt1) / 1/2 (Δt4 + Δ
t1)

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.

In the evaluation of the drive characteristics (drive margin) shown in FIG. 14, the drive voltage Vop was fixed and the pulse width Δt was changed. On the contrary, the pulse width Δt was fixed and the drive voltage Vop was changed. Alternatively, both parameters may be changed.

In the present invention, for example, an active matrix substrate provided with a TFT or the like is used as one of the above-mentioned substrates, and active matrix driving is performed by a driving circuit, thereby enabling high-speed driving display.

Referring to FIGS. 19 to 21, an example using such an active matrix substrate will be described as another embodiment of the liquid crystal element of the present invention.

FIG. 19 schematically shows the element with a driving means, mainly focusing on the structure of one substrate (active matrix substrate).

In the configuration shown in FIG. 19, in a panel section 90 corresponding to a liquid crystal element, horizontal gate lines G1, G2... Corresponding to scanning lines connected to a scanning signal driver 91 as driving means, Are provided so as to be orthogonal to each other while being insulated from each other in the vertical direction in the drawing, corresponding to the information signal lines connected to the information signal driver 92 as means. And a thin film transistor (TF
T) 94 and a pixel electrode 95 are provided (only a 5 × 5 pixel area is shown in the figure for simplicity). Note that an MIM element can be used as the switching element in addition to the TFT. Are connected to the gate electrode (not shown) of the TFT 94, and the source lines S1, S2
Are connected to a source electrode (not shown) of the TFT 94,
The pixel electrode 95 is a drain electrode (not shown) of the TFT 94.
It is connected to the. In this configuration, the gate lines G1, G2,... Are, for example, line-sequentially scanned and selected by the scanning signal driver 91, and a gate voltage is supplied. The information signal driver 92 writes each pixel from the information signal driver 92 in synchronization with the scanning selection of the gate lines. The information signal voltage according to the information is applied to the source line S1,
S2... And applied to each pixel electrode via the TFT.

An alignment control layer 96 having at least a uniaxial alignment control force for liquid crystal is provided in a portion other than the pixel electrode serving as an actual driving region, for example, in a region surrounded by a broken line along the source lines S1, S2. Note that the arrangement of the orientation control layer 96 in FIG. 19 shows the positional relationship with respect to each member in the active matrix substrate, and can be actually provided on one or both of the active matrix substrate and the counter substrate. . Further, the orientation control layer 96 is not limited to those arranged along the source lines S1, S2,... But may be arranged in a grid along the gate lines G1, G2,. It can also be provided.

FIG. 20 shows an example of a sectional structure of each pixel portion (for one bit) in the panel configuration as shown in FIG. In the structure shown in FIG.
Matrix substrate 30 provided with the common electrode 3 and the common electrode 3
A liquid crystal layer 61 having spontaneous polarization is sandwiched between the opposing substrates 70 provided with the liquid crystal elements 2 to form a liquid crystal capacitance (Clc) 60.

As for the active matrix substrate 30, an example using an amorphous Si TFT as the TFT 94 is shown. The TFT 94 is formed on a substrate 31 made of glass or the like, and has gate lines G1, G2,.
Nitride (SiN) on the gate electrode 32 connected to
An a-Si layer 34 is provided via an insulating film (gate insulating film) 33 made of a material such as x).
4, a source electrode 37 and a drain electrode 38 are provided separately from each other via n ⁺ a-Si layers 35 and 36, respectively. The source electrode 37 is connected to the source line S1 shown in FIG.
, And the drain electrode 38 is connected to a pixel electrode 95 made of a transparent conductive film such as an ITO film. Also, T
The channel protective film 3 is formed on the a-Si layer 34 in the FT 94.
9 is coated. The TFT 94 is turned on by applying a gate pulse to the gate electrode 32 during a period when the gate line is selected for scanning.

Further, in the active matrix substrate 30, the insulating film 33 (continuously formed with the insulating film on the gate electrode 32) is formed by the pixel electrode 95 and the storage capacitor electrode 41 provided on the glass substrate side of the electrode. A storage capacitor (CS) 40 is provided in parallel with the liquid crystal layer 60 by a structure sandwiching the film. The storage capacitor electrode is formed of a transparent conductive film such as an ITO film because the aperture ratio is reduced when its area is large.

The TFT 9 of the active matrix substrate 30
The layer 43 is provided on the pixel electrode 95 and the pixel electrode 95 to control the alignment state of the liquid crystal.

In the region on the layer 43 corresponding to the TFT 94, an alignment control layer 96a having a uniaxial alignment regulating force is provided.
Is selectively provided.

On the other hand, on the opposite substrate 70, a common electrode 72 and a layer 73 for controlling the alignment state of the liquid crystal are laminated on a transparent substrate 71 of glass or the like with the same thickness as the entire surface. , T of the opposing active matrix substrate
An alignment control layer 96b having a uniaxial alignment regulating force is selectively provided in a region corresponding to the position where the FT 94 is arranged.

In the above configuration, as the orientation control layers 96a and 96b, for example, a film obtained by performing a uniaxial orientation treatment on a film having an insulating property similarly to the orientation control layer 15a having the structure shown in FIG. On the other hand, by forming the underlying layers 43 and 73 by applying the same materials and processing conditions as those of the layers 14a and 14b having the structure shown in FIG. And R
3 was obtained, and the actual driving region was changed to surface regions R2 and R4 having a small alignment regulating action on liquid crystal molecules,
In particular, when a smectic liquid crystal is used, an alignment state can be formed in a process as shown in FIGS.

The panel structure is sandwiched between a pair of polarizing plates whose polarization axes are orthogonal to each other (not shown).

In the panel configuration shown in FIGS. 19 and 20, a substrate provided with a polycrystalline Si (p-Si) TFT can be used as an active matrix substrate. FIG. 21 shows an equivalent circuit of a pixel portion of the panel shown in FIG.

Referring to FIGS. 21 and 22, an active matrix drive using a chiral smectic liquid crystal having bistability in the liquid crystal device having the above structure will be described.

FIG. 22A shows a case where attention is paid to one pixel.
3 shows a voltage applied to one gate line serving as a scanning line connected to the pixel. In the liquid crystal element having the above structure, the gate line G
, G2,... Are selected in a line-sequential manner, for example, a predetermined gate voltage Vg is applied to one gate line during the selection period Ton, a voltage Vg is applied to the gate electrode 32, and the TFT 94 is turned on. In a non-selection period Toff corresponding to a period in which another gate line is selected, no voltage is applied to the gate electrode 32, and the TFT 94 is in a high resistance state (off state).
A predetermined same gate line is selected for each Toff, and a gate voltage Vg is applied to the gate electrode 32.

FIG. 22B shows the voltage Vs applied to the information signal line (source line) of the pixel. FIG.
As shown in (a), the gate electrode 32 in each selection period Ton.
When a gate voltage is applied to the pixel, a predetermined source voltage (information signal voltage) Vs is applied from the source lines S1, S2,.
(The reference potential is the potential Vc of the common electrode 72).

Here, since the TFT 95 is in the ON state, the voltage Vs applied to the source electrode 37 is applied to the pixel electrode (95) via the drain electrode 38, and the liquid crystal capacitance (Clc) 31 and the storage capacitance 32 (Cs) is charged, and the potential of the pixel electrode becomes the information signal voltage Vs. Subsequently, the non-selection period Toff of the gate line belonging to the pixel
Since the TFT 94 has a high resistance (off state) in
During this non-selection period, the liquid crystal cell (liquid crystal capacitance Clc) 60
In addition, the storage capacitor (Cs) 40 maintains the state in which the charge charged during the selection period Ton is accumulated, and holds the voltage. Then, a voltage is applied to the liquid crystal layer 61 of the pixel throughout the frame, and switching occurs in the liquid crystal portion of the pixel, and a desired optical state (white state) is obtained.

In the selection period Ton of the subsequent frame, a source voltage (−Vs) having a voltage value Vs substantially the same as that of the previous frame and having the opposite polarity is applied to the source electrode 37. At this time, the TFT 94 is on, and the pixel electrode 9
5, a voltage -Vs is applied, and a liquid crystal capacitance (Clc) 60
Then, the storage capacitor 40 (Cs) is charged, and the potential of the pixel electrode becomes the information signal voltage −Vs. Subsequently, during the non-selection period Toff, the TFT 94 has a high resistance (off state).
c) The selection period Ton for 60 and the storage capacity (Cs) 40
The state where the electric charge charged in is stored, and the voltage is held. Then, a medium resistance voltage is applied to the liquid crystal layer 61 in the pixel throughout the frame period, and the pixel is switched by this voltage to obtain a desired optical state (black state).

FIG. 22C shows the voltage value Vpix actually held in the liquid crystal capacitor and the storage capacitor of the pixel and applied to the liquid crystal layer 61 as described above, and FIG. FIG. 1 schematically shows the actual optical response (optical response in the case of a transmission type liquid crystal element). As shown in FIG.
The applied voltages throughout the frame are at the same level (absolute value) whose polarity is just inverted. On the other hand, as shown in (d), an optical state according to Vs is obtained in the first frame, and an optical display state according to -Vs is obtained in the second frame.

[0174]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples (experimental examples), but the present invention is not limited to the following examples.

Example 1 Preparation of Liquid Crystal Composition A liquid crystal composition L was prepared using the following liquid crystal compounds (A) to (E).
C-1 was prepared. (Compound used)

[0176]

[Outside 6]

Preparation of Cell A matrix cell (simple matrix type cell) used in Examples was prepared as follows.

Cell 1-A A pair of 1.1 mm-thick glass substrates each having a stripe-patterned ITO film (thickness: about 70 nm, line width: 16 μm, interval between adjacent lines: 4 μm) formed as transparent electrodes. Prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. A polyimide (precursor) having the following repeating unit is applied on the silica layer by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
Heat baking was performed for a time to obtain a polyimide film having a thickness of 5 nm.

[0180]

[Outside 7]

Subsequently, the polyimide on the substrate was subjected to a rubbing treatment with a nylon cloth as a uniaxial orientation treatment. The conditions of the rubbing treatment were as follows: using a rubbing roll in which nylon (NF-77 / manufactured by Teijin) was attached to a roll having a diameter of 10 cm, a pushing amount of 0.3 mm, and a feeding speed of 10 cm.
/ Sec, the number of rotations was 1000 rpm, and the number of times of feeding was 4 times.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Then, after pre-drying at 80 ° C. for 5 minutes,
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle diameter of 2.0 μm was formed on one of the substrates (the substrate on which the polyimide was applied) as a spacer.
m silica beads were scattered, and the other substrate was overlapped so that the electrodes of each substrate were orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), thereby producing a cell (empty cell).

The total thickness of the insulating film (silica layer and polyimide film) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 11 nm.

Cell 1-B Except that the thickness of the polyimide film was set to 2 nm,
A cell (empty cell) was produced in the same manner and under the same conditions as for the cell 1-A. The total thickness of the insulating film (silica layer and polyimide film) in the actual driving region (the portion where the electrodes of both substrates intersect) of the manufactured cell was 8 nm.

Cell 1-C Here, a cell (empty cell) having the cross-sectional structure shown in FIG. 7 was manufactured.

As a transparent electrode, a stripe pattern IT
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. Onto the silica layer, the same polyimide (precursor) as used in Cell 1-A was applied by spin coating.
Then, after pre-drying at 80 ° C for 5 minutes,
For 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, UV (λ = 365) was obtained using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developing solution (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-pressure mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
A portion (4 μm in width) where a stripe-shaped polyimide film is present on the substrate at a thickness of 50 nm corresponding to between the lines of the ITO film.
And a polyimide film pattern consisting of portions (width 16 μm) that did not exist at all corresponding to the lines of the ITO film.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment in the same manner and under the same conditions as those for the cell 1-A. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Then, after pre-drying at 80 ° C. for 5 minutes,
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was coated) as a spacer.
And the other substrate is superimposed so that the electrodes of each substrate are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as shown in FIG. Cell).

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 6 nm.

Cell 1-D The thickness of the polyimide film (polyimide film pattern) was 30 n.
A cell (empty cell) having a cross-sectional structure as shown in FIG. 7 was prepared in the same manner as in the case of the cell 1-C, except that m was set to m.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus fabricated was 6 nm.

Cell 1-E Here, a cell (empty cell) having a sectional structure shown in FIG. 9 was prepared.

[0197] A stripe pattern IT as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An sol-gel type ethanol solution of silica was applied to each of these glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes.
The coating was dried by heating at 0 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. The same polyimide (precursor) as that used in Cell A was applied on the silica layer by spin coating, followed by pre-drying at 80 ° C. for 5 minutes, followed by heating and baking at 200 ° C. for 1 hour. Was applied to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-8) was formed on the polyimide film on one glass substrate.
00) was spin-coated to a thickness of about 2 μm. Then, after performing pre-drying at 80 ° C. for 30 minutes, the mask width 4
The substrate was exposed to UV (λ = 365 nm) for 16 seconds using a stripe-shaped mask pattern having a thickness of 16 μm and an interval of 16 μm. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, an organic developer (MFCD-2 manufactured by Zipley Co., Ltd.)
After developing using 6) and washing with running water for 3 minutes,
Drying was performed at 0 ° C. for 10 minutes to obtain a resist film pattern corresponding to between the lines of the ITO film pattern. Subsequently, using a low-pressure mercury lamp, the substrate temperature was kept at 60 ° C., and the wavelength 2
UV ashing was performed at a UV intensity at which the light energy amount at 54 nm was 10 J / cm ² to remove the polyimide in the portion without the resist film. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. In this manner, the polyimide film is composed of a portion where the stripe-shaped polyimide film exists 50 nm (width 4 μm) corresponding to the space between the ITO film lines and a portion where the polyimide film does not exist at all (width 16 μm) corresponding to the ITO film line. A membrane pattern was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment in the same manner and under the same conditions as those for the cell 1-A. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

A positive resist (Tokyo Ohka OFPR-800) was spin-coated on the other glass substrate to a thickness of about 2 μm. Then 80
After pre-drying at 30 ° C. for 30 minutes, the substrate was exposed to UV (λ = 365 nm) for 16 seconds using a striped mask pattern having a mask width of 4 μm and an interval of 16 μm as shown in FIG. At this time, the mask pattern was arranged such that the mask portion was orthogonal to the line of the ITO film pattern of the substrate. Then, an organic developing solution (MFCD-
26), and washing with running water for 3 minutes.
Drying was performed at 00 ° C. for 10 minutes to obtain a resist film pattern having a line width of 4 μm and a line interval of 16 μm. continue,
UV ashing was performed in the same manner and under the same conditions as described above to remove the polyimide in the area without the resist film. Next, remover (Resist Strip N manufactured by Nagase & Co., Ltd.)
After stripping the resist film pattern using -320), the substrate was washed with running water and dried. In this way, the IT
A polyimide film pattern consisting of a portion (width 4 μm) in which a stripe-shaped polyimide film perpendicular to the O film line exists at 50 nm and a portion (width 16 μm) not present at all was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the case of the cell 1-A. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

On one substrate (first substrate), silica beads having an average particle size of 2.0 μm were sprayed as spacers.
On the other substrate, the electrodes of each substrate are orthogonal to each other to form a matrix electrode arrangement (arrangement as shown in FIG. 11), and the line portions of the polyimide film pattern on both substrates are completely opposed,
Positioning and bonding were performed so that the rubbing directions in the polyimide film were the same, thereby producing a cell (empty cell) having a cross-sectional structure as shown in FIG.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 6 nm.

Cell 1-F An ITO film having a stripe pattern as a transparent electrode (film thickness: about 70 nm, line width: 16 μm)
m, a pair of glass substrates having a thickness of 1.1 mm and having a spacing of 4 μm between adjacent lines was prepared.

An ethanol solution of sol-gel type silica was applied to these glass substrates by spin coating.
After pre-drying at 80 ° C. for 5 minutes,
After heating and drying for a period of time, a silica layer having a thickness of 3 nm was obtained.

Subsequently, a cell 1 was placed on the silica layer of these substrates.
A rubbing treatment was performed as a uniaxial orientation treatment by the same method and under the same conditions as in -A.

Next, silica beads having an average particle size of 2.0 μm are dispersed as spacers on one of the substrates, and the other substrate is arranged in a matrix electrode arrangement in which the electrodes of each substrate are orthogonal to each other (arrangement as shown in FIG. 11). Superimposed so that
A cell (empty cell) was prepared. The rubbing directions of the two substrates were set to be the same and parallel.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 6 nm.

Note that the size of the cells 1-A to 1-F is 2.5
cm × 3.5 cm (in the cells 1-C to 1-E, the side in the stripe direction of the ITO film coincident with the line of the polyimide film was 2.5 cm).

Each cell 1 manufactured by the above-described process was used.
-A to 1-F, the liquid crystal composition LC-1 was injected at a temperature of an isotropic phase, the liquid crystal was cooled to a temperature at which a chiral smectic liquid crystal phase was exhibited, and a chiral smectic liquid crystal element sample 1 exhibiting bistability was obtained. A to 1-E were prepared. When this cooling process was observed in a polarizing microscope (100 times), in the cells 1-C to 1-E, the alignment state due to the generation and growth of the battone as shown in FIG. 3 from around the transition temperature to the smectic A phase. The formation process of was observed.

The samples were evaluated for 1) alignment uniformity and 2) M2 margin (M2).

1) Evaluation of Uniformity of Alignment A voltage was applied to the liquid crystal element in the state of a chiral smectic liquid crystal phase to switch the chiral smectic liquid crystal to one state, and (1) was visually observed with a polarizing microscope.
00 times) and the uniformity of orientation was evaluated. Table 1 shows the results.

[0214]

[Table 1]

2) Measurement of M2 Margin (M2) A method of measuring the M2 margin will be described. First, a cell was installed between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1 / 3.3 bias, 1 /
The M2 margin was measured using (equivalent to 1000 duty). A dark state (black display) and a light state (white display) are written while changing the applied pulse waveform length Δt, and the range of the applied pulse waveform length Δt in which the bright and dark states can be written is as shown in FIG. In the case of
M2 = (Δt4−Δt1) /
(Δt4 + Δt1), the M2 margin was evaluated by varying the temperature of the samples A to E by several points.

The results are shown in Table 2 below.

The element B has an M2 margin only in a normally switching region (only a region in a good orientation state), and the elements 1-C to 1-E have an M2 margin in a region where no striped polyimide is arranged. Margin. In addition, since the entire surface of the element 1-F was randomly oriented, the drive margin could not be measured.

[0218]

[Table 2]

From this result, it can be seen that, with respect to the element sample 1-A, the M2 margin at room temperature or higher is large, but the drive margin on the low temperature side is significantly deteriorated. This is expected to be due to the effect of the anti-electric field on the low temperature side. On the other hand, with respect to the element B having poor orientation, although the value of the M2 margin is small as a whole, the element 1-B has a thinner alignment film thickness (thickness of the polyimide film) than the element 1-A, and the Since the capacity is large, the amount of decrease in the margin on the low temperature side is small. On the other hand, element 1-
C, 1-D, and 1-E denote the actual driving region where the electrodes of both substrates face each other, that is, the effective switching region, in which no polyimide exists, so that the electric capacity of the orientation control layer is large, and the amount of decrease in the margin at the low temperature side Is getting smaller.

As described above, the portion where the alignment control layer having the uniaxial alignment regulating force is present and the portion where the alignment layer is not present are mixed on the substrate, and the alignment state is formed from the liquid crystal region in contact with the portion of the alignment control layer. As a result, it was proved that a good driving margin characteristic can be realized by obtaining a uniform alignment property, and by eliminating the alignment control layer having the uniaxial alignment regulating force in the actual driving region of the liquid crystal.

(Example 2) In this example, a commercially available antiferroelectric liquid crystal material CS-4000 (manufactured by Chisso Corporation) was used as the liquid crystal composition.

Further, three types of empty cells used in Example 2 were produced as follows.

Cell 2-G As a transparent electrode, a pair of 1.1 mm-thick glass substrates formed with a stripe-patterned ITO film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm) was formed. Prepared.

An ethanol solution of sol-gel type silica was applied to both of these glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes, followed by 20 minutes.
The coating was dried by heating at 0 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, a commercially available polyimide material (SP-
710DMAC (dimethylacetamide) / IRA (isopropyl alcohol) = 1/1 / Toray) is applied by spin coating, and then pre-dried at 80 ° C. for 5 minutes, and then heated and baked at 200 ° C. for 1 hour. Applied film thickness 50
nm of a polyimide coating was obtained.

Subsequently, with respect to the polyimide films on both substrates,
Rubbing treatment with a nylon cloth was performed as a uniaxial orientation treatment under the same method and conditions as in the case of Cell 1-A. The rubbing direction was set for each of the two substrates so that the rubbing directions had the relationship described below when the substrates were opposed to each other.

Subsequently, silica beads having an average particle size of 1.4 μm were sprayed as spacers on one of the substrates, and both substrates were arranged in a matrix electrode arrangement in which electrodes were orthogonal to each other (FIG. 11).
And the rubbing direction of the upper substrate is opposed to the rubbing direction of the lower substrate so as to make an angle of 16 ° counterclockwise, thereby producing a cell (empty cell).

Cell 2-H A cell (empty cell) was prepared in the same manner and under the same conditions as for the cell 2-G, except that the thickness of the polyimide film was set to 5 nm.

Cell 2-I As a polyimide, a commercially available polyimide material (SP-71) was used.
0 / Toray Co., Ltd.), silica beads having an average particle size of 1.4 μm as a spacer, UV ashing conditions were 60 ° C., wavelength 254 nm, energy amount 13 J / c.
except that the m ^2, by the same method and conditions as in cell 1-E of Example 1 to prepare a cell (empty cell).

Each cell 2 manufactured by the process described above
-G to 2-I, an antiferroelectric liquid crystal material CS-4000 is injected at an isotropic phase temperature, and the liquid crystal is cooled to a temperature showing a chiral smectic liquid crystal phase, and a chiral smectic liquid crystal element showing bistability Samples 2-G to 2-I were produced. Observing this cooling process with a polarizing microscope,
In the cell 2-I, generation of batone and formation process of an alignment state by growth were observed from around the transition temperature to the smectic A phase as shown in FIG.

For these samples, 1) evaluation of alignment uniformity and 2) evaluation of response speed were performed in the same manner as in Example 1.

1) Evaluation of alignment uniformity The results are shown in Table 3.

[0232]

[Table 3]

2) Measurement of Response Speed A method of measuring the response speed will be described. First, a cell is placed between polarizing plates arranged in crossed Nicols, and at 30 ° C.,
A direct current of 18 V is applied as a DC offset voltage to the cell in the state indicating the antiferroelectric state. Next, a single pulse having a pulse width of 100 μs was applied while gradually increasing the voltage, and a voltage value required for switching from the antiferroelectric state to the ferroelectric state was obtained. The results are shown in Table 4 below. It should be noted that the response voltage of the element 2-H was set only in the region where normal switching was performed.

[0234]

[Table 4]

From these results, it can be seen that, in a device using a liquid crystal exhibiting antiferroelectricity, the voltage applied to the liquid crystal layer is effectively increased as the thickness of the orientation control layer is reduced. It is understood that the voltage value may be low.

In Example 2, in an element using a liquid crystal exhibiting antiferroelectricity, a portion where an alignment control layer having a uniaxial alignment regulating force is present on a substrate and a portion where the alignment layer is not present are mixed. By forming an alignment state from the liquid crystal region corresponding to the portion of the alignment control layer to obtain a uniform alignment, further by not having an alignment control layer having such uniaxial alignment regulating force in the actual driving region of the liquid crystal, It has been proved that the drive voltage can be reduced, that is, the response can be made faster when the drive characteristics are compared at the same voltage.

Example 3 A cell (simple matrix type cell) used in this example was manufactured as follows.

Cell 3-B A pair of 1.1 mm-thick glass substrates each formed with a stripe-patterned ITO film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm) as transparent electrodes were formed. Prepared.

On one side of this glass substrate, 50% by weight of antimony-doped SnOx ultrafine particles (particle size: 100 °) was added and dispersed in a sol-gel type silica base material in an ethanol solution having a solid content of 10% by weight. Is applied by spin coating, then pre-dried at 80 ° C. for 5 minutes, and then dried by heating at 200 ° C. for 1 hour to a film thickness of 200 n.
m was obtained. A cell 1 is placed on the fine particle dispersion layer.
The same polyimide (precursor) as that used in -A was applied by spin coating, and then pre-dried at 80 ° C. for 5 minutes, and then baked at 200 ° C. for 1 hour to form a film having a thickness of 5 nm. A polyimide coating was obtained.

Next, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1.

On the other glass substrate, 50% by weight of antimony-doped SnOx ultrafine particles (particle size: 100 °) were added and dispersed in a sol-gel type silica base material in an ethanol solution having a solid concentration of 10% by weight. Was applied. Thereafter, pre-drying was performed at 80 ° C. for 5 minutes, and then heat drying was performed at 200 ° C. for 1 hour to obtain a fine particle dispersion layer having a thickness of 200 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which the polyimide was applied) as a spacer.
m silica beads were scattered, and the other substrate was overlapped so that the electrodes of each substrate were orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), thereby producing a cell (empty cell).

Cell 3-C Here, a cell (empty cell) having a sectional structure shown in FIG. 7 was prepared.

As a transparent electrode, a stripe pattern IT
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

On one side of this glass substrate, an ethanol solution having a solid concentration of 10% by weight was prepared by adding and dispersing 30% by weight of antimony-doped SnOx ultrafine particles (particle diameter: 100 °) in a sol-gel type silica base material. Coating is performed by spin coating, followed by pre-drying at 80 ° C. for 5 minutes, and then heating and drying at 200 ° C. for 1 hour to form a film having a thickness of 200 nm.
Was obtained. On this layer, the cell 1 of Example 1
The same polyimide (precursor) as that used in -A was applied by a spin coating method, and then pre-dried at 80 ° C. for 5 minutes, and then heated and baked at 200 ° C. for 1 hour to form a film having a thickness of 50 nm. A polyimide coating was obtained.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, UV (λ = 365) was obtained using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developing solution (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-pressure mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
A portion (4 μm in width) where a stripe-shaped polyimide film is present on the substrate at a thickness of 50 nm corresponding to between the lines of the ITO film.
And a polyimide film pattern consisting of portions (width 16 μm) that did not exist at all corresponding to the lines of the ITO film.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the case of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

On the other glass substrate, an ethanol solution having a solid content of 10% by weight was prepared by adding and dispersing antimony-doped SnOx ultrafine particles (particle size: 100 °) in a sol-gel type silica matrix at a weight ratio of 30%. Coating was performed by spin coating. After that, pre-drying was performed at 80 ° C. for 5 minutes, and then heat drying was performed at 200 ° C. for 1 hour to form a film having a thickness of 200 nm.
To obtain a fine particle dispersion layer.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was applied) as a spacer.
And the other substrate is superimposed so that the electrodes of each substrate are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as shown in FIG. Cell).

Cell 3-D Here, a cell (empty cell) having the cross-sectional structure shown in FIG. 7 was manufactured.

[0251] IT of a stripe pattern as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

Ethanol having a solid content of 10% by weight was added to one of the glass substrates and dispersed by adding 50% by weight of antimony-doped SnOx ultrafine particles (particle diameter: 100 °) in a sol-gel type silica base material. The solution was applied by a spin coating method to obtain a fine particle dispersed layer having a thickness of 200 nm. The same polyimide (precursor) as that used in the cell 1-A of Example 1 was applied on the fine particle dispersion layer by spin coating, and then pre-dried at 80 ° C. for 5 minutes. Baking for 1 hour at 200 ° C, 50nm thick
Was obtained.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, UV (λ = 365) was obtained using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developing solution (MFCD-26 manufactured by Zipley Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-pressure mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy amount at a wavelength of 254 nm is 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
A portion (4 μm in width) where a stripe-shaped polyimide film is present on the substrate at a thickness of 50 nm corresponding to between the lines of the ITO film.
And a polyimide film pattern consisting of a portion (width 16 μm) which does not exist at all between the lines of the ITO film.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as those for the cell 1-A. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

On the other glass substrate, an ethanol solution having a solid content of 10% by weight was prepared by adding 50% by weight of antimony-doped SnOx ultrafine particles (particle diameter 100 °) to a sol-gel type silica base material and dispersing the same. Apply, film thickness 20
A fine particle dispersion layer of 0 nm was obtained.

Subsequently, a spacer having an average particle diameter of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was coated) as a spacer.
And the other substrate is superimposed so that the electrodes of each substrate are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as shown in FIG. Cell).

Cell 3-E A pair of 1.1 mm-thick glass substrates formed with a stripe-patterned ITO film (about 70 nm in thickness, 16 μm in width of one line, and 4 μm in space between adjacent lines) formed as a transparent electrode. Prepared.

An ethanol solution having a solid content of 10% by weight was prepared by adding 30% by weight of antimony-doped SnOx ultrafine particles (particle diameter 100 °) to a sol-gel type silica base material and dispersing them in the glass substrate. Coating is performed by a coating method, and then, pre-drying is performed at 80 ° C. for 5 minutes, and then heating and drying is performed at 200 ° C. for 1 hour.
To obtain a fine particle dispersion layer.

Subsequently, the fine particle dispersion layers of both substrates were subjected to a rubbing treatment as a uniaxial orientation treatment in the same manner and under the same conditions as in the cell 1-A.

Next, a spacer having a mean particle size of 2.0 μm was formed on one of the substrates (the substrate on the side subjected to the rubbing treatment) as a spacer.
m silica beads were scattered, and the other substrate was overlapped so that the electrodes of each substrate were orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), thereby producing a cell (empty cell). The substrates were bonded so that the rubbing directions of the substrates were parallel and the same.

Cell 3-F A pair of 1.1 mm-thick glass substrates formed with a stripe-patterned ITO film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm) as transparent electrodes were formed. Prepared.

To these glass substrates, an ethanol solution having a solid content of 10% by weight was added by dispersing 50% by weight of antimony-doped SnOx ultrafine particles (particle size: 100 °) in a sol-gel type silica base material at a weight ratio. And a film thickness of 20
A fine particle dispersion layer of 0 nm was obtained.

Subsequently, the fine particle dispersion layers of both substrates were subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the cell 1-A of Example 1.

Next, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on the side subjected to the rubbing treatment) as a spacer.
m silica beads were scattered, and the other substrate was overlapped so that the electrodes of each substrate were orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), thereby producing a cell (empty cell). The substrates were bonded so that the rubbing directions of the substrates were parallel and the same.

Cell 3-G Here, a cell (empty cell) having the cross-sectional structure shown in FIG. 9 was manufactured.

[0266] IT of a stripe pattern as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

To each of these glass substrates, an ethanol solution having a solid content of 10% by weight was prepared by adding and dispersing 30% by weight of antimony-doped SnOx ultrafine particles (particle size: 100 °) in a sol-gel type silica base material. Coating is performed by spin coating, and then pre-drying is performed at 80 ° C. for 5 minutes.
m was obtained. The same polyimide (precursor) as that used in the cell 1-A of Example 1 was applied on the fine particle dispersion layer by a spin coating method.
After pre-drying for 5 minutes, it was heated and baked at 200 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-8) was formed on the polyimide film on one glass substrate.
00) was spin-coated to a thickness of about 2 μm. Then, after performing pre-drying at 80 ° C. for 30 minutes, the mask width 4
The substrate was exposed to UV (λ = 365 nm) for 16 seconds using a stripe-shaped mask pattern having a thickness of 16 μm and an interval of 16 μm. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, an organic developer (MFCD-2 manufactured by Zipley Co., Ltd.)
After developing using 6) and washing with running water for 3 minutes,
Drying was performed at 0 ° C. for 10 minutes to obtain a resist film pattern corresponding to between the lines of the ITO film pattern. Subsequently, using a low-pressure mercury lamp, the substrate temperature was kept at 60 ° C., and the wavelength 2
UV ashing was performed at a UV intensity at which the light energy amount at 54 nm was 10 J / cm ² to remove the polyimide in the portion without the resist film. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. In this manner, the polyimide film is composed of a portion where the stripe-shaped polyimide film exists 50 nm (width 4 μm) corresponding to the space between the ITO film lines and a portion where the polyimide film does not exist at all (width 16 μm) corresponding to the ITO film line. A membrane pattern was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment in the same manner and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

A positive resist (Tokyo Ohka OFPR-800) was spin-coated on the other glass substrate to a thickness of about 2 μm. Then 80
After pre-drying at 30 ° C. for 30 minutes, using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm,
Exposure was performed for 16 seconds with UV (λ = 365 nm). At this time, the mask pattern was arranged such that the mask portion was orthogonal to the line of the ITO film pattern of the substrate. Thereafter, the resist film pattern was developed using an organic developing solution (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, and dried at 100 ° C. for 10 minutes to form a resist film pattern having a line width of 4 μm and a line interval of 16 μm. I got Subsequently, using a low-pressure mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus, a portion (4 μm in width) where a stripe-shaped polyimide film perpendicular to the ITO film line exists on the substrate at a thickness of 50 nm.
m) and a portion (16 μm in width) that does not exist at all.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment in the same manner and under the same conditions as those for the cell 1-A. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

As spacers on one substrate (first substrate), silica beads having an average particle size of 2.0 μm were scattered, and the other substrate was placed on a matrix electrode arrangement in which the electrodes of each substrate were orthogonal to each other (as shown in FIG. 11). Position) and the polyimide film pattern line portions on both substrates are completely opposed to each other so that the rubbing directions in the polyimide film are the same, and they are bonded together. (Empty cell) was prepared.

Cell 3-H Here, a cell (empty cell) having the cross-sectional structure shown in FIG. 9 was manufactured.

[0274] IT of a stripe pattern as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

Each of these glass substrates was added with 50% by weight of antimony-doped SnOx ultrafine particles (particle diameter: 100 °) in a sol-gel type silica base material and dispersed in ethanol solution having a solid concentration of 10% by weight. Was applied by spin coating to obtain a fine particle dispersion layer having a thickness of 200 nm. The same polyimide (precursor) as that used in the cell 1-A of Example 1 was applied on the fine particle dispersion layer by spin coating, and then pre-dried at 80 ° C. for 5 minutes. The resultant was baked at 200 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-8) was formed on the polyimide film on one glass substrate.
00) was spin-coated to a thickness of about 2 μm. Then, after performing pre-drying at 80 ° C. for 30 minutes, the mask width 4
The substrate was exposed to UV (λ = 365 nm) for 16 seconds using a stripe-shaped mask pattern having a thickness of 16 μm and an interval of 16 μm. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, an organic developer (MFCD-2 manufactured by Zipley Co., Ltd.)
After developing using 6) and washing with running water for 3 minutes,
Drying was performed at 0 ° C. for 10 minutes to obtain a resist film pattern corresponding to between the lines of the ITO film pattern. Subsequently, using a low-pressure mercury lamp, the substrate temperature was kept at 60 ° C., and the wavelength 2
UV ashing was performed at a UV intensity at which the light energy amount at 54 nm was 10 J / cm ² to remove the polyimide in the portion without the resist film. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. In this manner, the polyimide film is composed of a portion where the stripe-shaped polyimide film exists 50 nm (width 4 μm) corresponding to the space between the ITO film lines and a portion where the polyimide film does not exist at all (width 16 μm) corresponding to the ITO film line. A membrane pattern was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

A positive resist (Tokyo Ohka OFPR-800) was spin-coated on the other glass substrate to a thickness of about 2 μm. Then 80
After pre-drying at 30 ° C. for 30 minutes, using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm,
Exposure was performed for 16 seconds with UV (λ = 365 nm). At this time, the mask pattern was arranged such that the mask portion was orthogonal to the line between the lines of the ITO film pattern on the substrate. afterwards,
Developed using an organic developer (MFCD-26 manufactured by Ziprey), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, line width 4 μm, line interval 16 μm
Was obtained. Subsequently, using a low-pressure mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus, a portion where the stripe-shaped polyimide film orthogonal to the line of the ITO film exists on the substrate (width 4 μm) and a portion where the polyimide film does not exist at all (width 16 μm)
m) was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

On one substrate (first substrate), silica beads having an average particle size of 2.0 μm were sprayed as spacers.
On the other substrate, the electrodes of each substrate are orthogonal to each other, forming a matrix electrode arrangement (arrangement as shown in FIG. 11), and the line portions of the polyimide film pattern on both substrates are completely opposed, and the rubbing directions in the polyimide film are the same. So that
After positioning and bonding, a cell (empty cell) having a sectional structure as shown in FIG. 9 was produced.

The total thickness of the fine particle dispersed film in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 400 nm.

The size of the cells 3-B to 3-H is 2.5
cm × 3.5 cm (cells 3-C, 3-D, 3-G
In this case, the side in the stripe direction of the ITO film which coincides with the line of the polyimide film is 2.5 cm).

In the actual driving region (intersection of the electrodes of both substrates) of the cell 1-A manufactured in Example 1 and the cells 3-B to 3-H manufactured in Example 3, The surface roughness of each layer serving as a surface was measured. The measurement was performed by forming a film of 1800 ° on a glass substrate or an ITO film under the same conditions as those of the above layers in the cells A to I, and using an atomic force microscope (NanoScope IIIa AFM Dim).
extension 3000 units / Digital I
scanning range 3.0 using a probe made of Olympus Optical Co., Ltd.
The measurement was performed for μm × 3.0 μm. Scan speed is 0.8H
z, the measurement environment was room temperature and air.

The results are shown in Table 5 below.

[0285]

[Table 5]

On the surface of the polyimide film (5 nm) formed on the sol-gel type silica layer, Ra =
0.39 (nm), Rms = 0.49 (nm), surface roughness: 0.165%, fine particle dispersion layer (50% added)
On the surface of the polyimide film (5 nm) formed above, Ra = 1.61 (nm), Rms = 2.22 (nm),
The surface roughness was 3.53%, and the exposed surface of the fine particle dispersion layer in 3-C, 3-E and 3-G was Ra = 2.
57 (nm), Rms = 3.30 (nm), and surface roughness 5.514%.

Each cell 3 manufactured by the process described above
-B to 3-H and liquid crystal composition LC in cell 1-A of Example 1
-1 is injected at a temperature of an isotropic phase, the liquid crystal is cooled to a temperature at which a chiral smectic liquid crystal phase is exhibited, and chiral smectic liquid crystal element samples 1-A, 3-B to exhibit bistability are obtained.
3-H was produced. Observation of this cooling process in a polarizing microscope revealed that, in the cells 3-C, 3-D, 3-G, and 3-H, the generation of batone as shown in FIG. 3 near the transition temperature to the smectic A phase, The formation process of the orientation state by growth was observed.

For these samples, 1) evaluation of alignment uniformity, 2) M2 margin (M2), and 3) evaluation of display burn-in were performed.

1) Evaluation of alignment uniformity A voltage was applied to the liquid crystal element in a chiral smectic phase state to switch the chiral smectic liquid crystal to one state, and the alignment uniformity was evaluated by visual observation with a polarizing microscope. Was. Table 6 shows the results.

[0290]

[Table 6]

2) Measurement of M2 Margin (M2) A method of measuring the M2 margin will be described. First, a cell was installed between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1 / 3.3 bias, 1 /
The M2 margin was measured using (1000 duty). The dark state (black display) and the bright state (white display) were written while changing the length Δt of the applied pulse waveform, and the bright and dark states were changed. In a case where the range of the length Δt of the waveform of the applied pulse in which writing can be performed is as shown in FIG.
1) / (Δt4 + Δt1), and the above sample 1-A,
With respect to 2-B to 2-H, the temperature was changed at several points, and the M2 margin was evaluated.

The results are shown in Table 7 below.

Further, since the device samples 3-E and 3-F were all randomly oriented, the drive margin could not be measured.

[0294]

[Table 7]

From these results, it was found that the device samples 1-A and 3-
As for B, although the M2 margin at room temperature or higher is large, the driving margin on the low temperature side is significantly deteriorated. This is expected to be due to the effect of the anti-electric field on the low temperature side.

On the other hand, element samples 3-C, 3-D, 3-
For G and 3-H, since no polyimide film exists in the actual driving region, the influence of the anti-electric field is small, and the M2 margin on the low temperature side shows a value almost equal to that of room temperature.

As described above, the portion where the alignment control layer (polyimide film) having the uniaxial alignment control force exists on the substrate and the portion where the alignment layer does not exist are mixed, and the liquid crystal region in contact with the portion of the alignment control layer is removed. Proven that good driving margin characteristics can be realized by forming an alignment state to obtain uniform alignment and by eliminating the alignment control layer having the uniaxial alignment regulating force in the actual driving region of the liquid crystal. Was done.

3) Evaluation of display burn-in For element samples 1-A, 3-B to 3D, and 3-G to 3-H, stripe patterns of black display and white display are displayed using the driving waveforms shown in FIG. At 30 ° C for 100
After displaying the same pattern continuously for 0 hours, a driving condition (M2 margin) in which the entire cell was written in black and white was measured by the same method and under the same conditions as in the above 2). The ratio between the value of the M2 margin after 1000 hours and the value of the M2 margin before the burn-in test (before displaying the same pattern) was taken as the margin conservation rate after 1000 hours. In addition,
The measurement temperature of the storage rate was 30 ° C. The results are shown in Table 8 below.
Shown in

[0299]

[Table 8]

From these results, it can be seen that the margin preservation ratio is inversely proportional to the thickness of the polyimide film.
-D, 3-G, and 3-H exhibit very high margin preservation rates, that is, performance in which burn-in reduction is suppressed and drive characteristics are not deteriorated. In particular, it can be seen that the element sample in which the layer in contact with the liquid crystal in the actual driving region is made of conductive ultrafine oxide particles exhibits a very high margin preservation rate due to the effect of minute surface irregularities. Also, element sample 1-A
3 and 3B show that the element sample 3-B having a layer having minute surface irregularities even with the same polyimide film thickness has a higher margin preservation rate.

Example 4 A cell (simple matrix type cell) used in this example was manufactured as follows.

Cell 4-B A pair of 1.1 mm-thick glass substrates each having a stripe-patterned ITO film (about 70 nm in thickness, 16 μm in width of one line, and 4 μm in space between adjacent lines) formed as transparent electrodes were used. Prepared.

An ethanol solution of sol-gel type silica was applied to one side of this glass substrate by a speed coat method, followed by pre-drying at 80 ° C. for 5 minutes.
The coating was dried by heating at 0 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, a polyimide precursor (LP64,
An NMP / nBC = 1/2 solution (manufactured by Toray Industries, Inc.) is applied by a spin coating method, and then pre-dried at 80 ° C. for 5 minutes, and then baked at 300 ° C. for 1 hour to form a film having a thickness of 5 nm.
Was obtained.

Subsequently, the polyimide on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment under the same method and conditions as those for the polyimide film in the cell 1-A of Example 1.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Then, after pre-drying at 80 ° C. for 5 minutes,
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle diameter of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was applied) as a spacer.
m silica beads were scattered, and the other substrate was overlapped so that the electrodes of each substrate were orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), thereby producing a cell (empty cell).

The total thickness of the insulating film (silica layer and polyimide film) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 11 nm.

Cell 4-C Here, a cell (empty cell) having the sectional structure shown in FIG. 7 was prepared.

As a transparent electrode, a stripe pattern IT
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. Onto the silica layer, the same polyimide (precursor) as used in Cell 1-A was applied by spin coating.
Then, after pre-drying at 80 ° C for 5 minutes,
For 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, the mask width was 4 μm and the opening was 16 μm × 1.
Using a 6 μm lattice-like mask pattern, UV (λ =
(365 nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the film is developed using an organic developing solution (MFCD-26 manufactured by Ziprey), washed with running water for 3 minutes, and then dried at 100 ° C. for 10 minutes to form a lattice-like one side with an ITO film pattern. A resist film pattern corresponding to the interval between the lines was obtained. continue,
Using a low-pressure mercury lamp, the substrate temperature was maintained at 60 ° C., and UV ashing was performed at a UV intensity at which the amount of energy at a wavelength of 254 nm was 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. Next, the resist film pattern was stripped using a stripping solution (Nagase Sangyo Co., Ltd., resist slip N-320), washed with running water, and the substrate was dried. In this way, a portion (width 4 μm) where the lattice-like polyimide film having at least one side corresponding to the line between the ITO films exists on the substrate (a width 4 μm) and a portion (width 16 μm) where the polyimide film does not exist at all corresponding to the lines of the ITO film A polyimide film pattern was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment under the same method and conditions as in the case of the cell 1-A of Example 1.
The direction of the rubbing treatment was set perpendicular to the stripe direction of the electrodes on the substrate.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Thereafter, pre-drying was performed at 80 ° C. for 5 minutes. 200 ° C
Heat drying was performed for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was coated) as a spacer.
Of silica beads were sprayed. The substrate having the polyimide film pattern and the other substrate are arranged in a matrix electrode arrangement (arrangement as shown in FIG. 11) in which the electrodes are orthogonal to each other,
The electrodes of the other substrate are opposed to each other so as to correspond to one side (a direction perpendicular to the electrodes of the substrate having the polyimide film pattern) of the lattice-like polyimide film pattern on the opposite side, and a cross section as shown in FIG. A cell (empty cell) having the structure was manufactured.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 6 nm.

Cell 4-D Here, a cell (empty cell) having the cross-sectional structure shown in FIG. 7 was prepared.

[0317] IT of a stripe pattern as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as used in Cell 4-B was applied by spin coating.
Then, after pre-drying at 80 ° C. for 5 minutes,
For 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film so as to have a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, the mask width was 4 μm and the opening was 16 μm ×
Using a 16 μm lattice-like mask pattern, UV (λ
= 365 nm) for 16 seconds. At this time, the mask patterns were arranged such that the mask portions in one direction corresponded to the lines of the ITO film pattern on the substrate. afterwards,
Developed using an organic developer (MFCD-26 manufactured by Ziprey Co.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and formed a grid-like shape, one side of which is a line of an ITO film pattern. A corresponding resist film pattern was obtained.
Subsequently, using a low-pressure mercury lamp, the substrate temperature was maintained at 60 ° C., and the amount of energy at a wavelength of 254 nm was 12 J /
UV ashing was performed at a UV intensity of ² cm ² to remove the polyimide in the portion without the resist film. Next, remover (Resist Strip N manufactured by Nagase & Co., Ltd.)
After stripping the resist film pattern using -320), the substrate was washed with running water and dried. Thus, a portion (4 μm in width) where at least a 50-nm lattice-like stripe-like polyimide film corresponding to at least the space between the lines of the ITO film exists on the substrate.
m) and a polyimide film pattern consisting of a portion (width 16 μm) that does not exist at all corresponding to the line of the ITO film.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment under the same method and conditions as in the case of the cell 1-A of Example 1.
The direction of the rubbing treatment was set to a direction perpendicular to the stripe direction of the electrodes on the substrate.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Then, after pre-drying at 80 ° C. for 5 minutes,
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was applied) as a spacer.
Of silica beads were sprayed. The substrate having the polyimide film pattern and the other substrate are arranged in a matrix electrode arrangement (arrangement as shown in FIG. 11) in which the electrodes are orthogonal to each other,
The electrodes of the other substrate are opposed to each other so as to correspond to one side (a direction perpendicular to the electrodes of the substrate having the polyimide film pattern) of the lattice-like polyimide film pattern on the opposite side, and a cross section as shown in FIG. A cell (empty cell) having the structure was manufactured.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 6 nm.

Cell 4-F Here, a cell (empty cell) having a sectional structure shown in FIG. 9 was prepared.

[0325] Striped pattern IT as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

A sol-gel type ethanol solution of silica was applied to both of these glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes, followed by 20 minutes.
The coating was dried by heating at 0 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as that used in Cell 4-B was applied by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
The resultant was baked at 0 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film so as to have a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, the mask width was 4 μm and the opening was 16 μm ×
Using a 16 μm lattice-like mask pattern, UV (λ
= 365 nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Then, it develops using an organic developing solution (MFCD-26 made by Zipley),
After washing with running water for 3 minutes, drying was performed at 100 ° C. for 10 minutes to obtain a resist film pattern having a lattice shape and one side corresponding to the space between the lines of the ITO film pattern. continue,
Using a low-pressure mercury lamp, the substrate temperature was maintained at 60 ° C., and UV ashing was performed at a UV intensity at which the amount of energy at a wavelength of 254 nm was 12 J / cm ² , thereby removing a portion of the polyimide having no resist film. Next, a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-32)
After the resist film pattern was peeled off using 0), the substrate was washed with running water and dried. Thus, on the substrate, one side is IT
50 grid-like polyimide films corresponding to between O film lines
A polyimide film pattern consisting of a portion having a thickness of 4 nm (width 4 μm) and a portion not having a thickness (width 16 μm) corresponding to the line of the ITO film was obtained.

Subsequently, a rubbing treatment was applied to each of the polyimide film patterns of the pair of substrates as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment is as follows:
O film pattern stripe direction, the other substrate is ITO
The direction was set perpendicular to the film stripe.

On one substrate, silica beads having an average particle size of 2.0 μm were dispersed as spacers, and the other substrate was
Positioning and bonding are performed so that the lines of the grid-like polyimide film pattern completely face each other, and the rubbing direction in the polyimide film is the same, thereby producing a cell (empty cell) having a cross-sectional structure as shown in FIG. did.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 6 nm.

Cell 4-G Here, a cell (empty cell) having a sectional structure shown in FIG. 9 was produced.

[0332] IT of a stripe pattern as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to both of these glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes.
The coating was dried by heating at 0 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, on one of the substrates, the same polyimide (precursor) as that used in Cell 4-B was applied on the silica layer by spin coating, and then applied at 80 ° C.
After pre-drying for 5 minutes, it was heated and baked at 300 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm. On the other substrate, the cell 1-A of Example 1 was placed on the silica layer.
The same polyimide (precursor) as that used in the above was applied by spin coating, then pre-dried at 80 ° C. for 5 minutes, and then baked at 200 ° C. for 1 hour to form a film having a thickness of 50
nm of a polyimide coating was obtained.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide films of both substrates to a thickness of about 2 μm. Then, after performing pre-drying at 80 ° C. for 30 minutes, the mask width is 4 μm and the opening is 16 μm.
UV using a grid-shaped mask pattern of m × 16 μm
(Λ = 365 nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the film was developed using an organic developer (MFCD-26 manufactured by Ziprey), washed with running water for 3 minutes, and then dried at 100 ° C. for 10 minutes to form an ITO film pattern having a lattice shape on one side. A resist film pattern corresponding to the interval between the lines was obtained. Subsequently, using a low-pressure mercury lamp, the substrate temperature was maintained at 60 ° C.
The amount of energy at a wavelength of 254 nm was 12 J / cm ² for polyimide used in cell 4-B, and
The polyimide used in A was subjected to UV ashing at a UV intensity of 10 J / cm ² to remove a portion of the polyimide having no resist film. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus, on the substrate, there are a portion (width 4 μm) where the lattice-like polyimide film whose one side corresponds to the line between the ITO films exists and a portion (width 16 μm) which does not exist at all corresponding to the line of the ITO film. A polyimide film pattern was obtained.

Subsequently, a rubbing treatment was applied to each of the polyimide film patterns of the pair of substrates as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment is as follows:
O film pattern stripe direction, the other substrate is ITO
The direction was set perpendicular to the film stripe.

On one of the substrates, silica beads having an average particle size of 2.0 μm were dispersed as spacers, and the other substrate was
The alignment is performed so that the line portions of the grid-like polyimide film pattern completely face each other, and the rubbing direction in the polyimide film is the same, and the cells are bonded together to produce a cell (empty cell) having a cross-sectional structure as shown in FIG. did.

The total thickness of the insulating film (silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus fabricated was 6 nm.

The cells 4-B to 4-D, 4-F to 4-G
Was 2.5 cm × 3.5 cm.

The 4-B, 4-B produced by the above process
D, 4-F, 4-G, and cells 1-A, 1- of Example 1
The liquid crystal composition LC-1 was injected into F at an isotropic phase temperature, the liquid crystal was cooled to a temperature at which a chiral smectic liquid crystal phase was exhibited, and bistable chiral smectic liquid crystal element samples 4-B to 4-D, 4-F, 4-G, 1-A, 1-F
Was prepared. Observation of this cooling process in a polarizing microscope revealed that, in the cells 4-C, 4-D, 4-F and 4-G, the generation of batone as shown in FIG. 3 near the transition temperature to the smectic A phase, The formation process of the orientation state by growth was observed.

The surface potential of silica and polyimide constituting the surface of each cell in contact with the liquid crystal is described in
It was measured by the method described in -26247. Specifically, using a surface potentiometer (oscillating capacitance type surface potential type 320B type, manufactured by Trek), a film sample formed and rubbed under the same conditions as those of the above-mentioned cell was subjected to 1.0 × 10−
Under reduced pressure of 1 to 1.0 × 10 −3 torr, temperature of 80 to 1
The measurement was performed on the sample treated at 00 ° C. for 15 minutes to 2 hours.

The measurement results of the surface potential of each film are as follows.

Polysiloxane film: -80 mV (same value irrespective of rubbing treatment) Polyimide film used in cell 1-A: -100 mV Polyimide film used in cell 4-B: -210 mV

These samples were evaluated for the following items.

1) Evaluation of alignment uniformity A voltage was applied to the liquid crystal element to switch the chiral smectic liquid crystal to one state, and the alignment uniformity was evaluated by visual observation with a polarizing microscope under crossed Nicols. Except for Sample 1-F, a uniform alignment state was obtained over the entire surface.

2) Evaluation of molecular position after slow cooling Visual observation with a deflection microscope showed that
The molecular position immediately after cooling to the C ^* phase was evaluated. At this time, at the time of observation with a polarizing microscope under crossed Nicols, the position of a molecule tilted counterclockwise from the layer normal direction (rubbing treatment) is a first stable state (S1), and the position of a molecule tilted clockwise is a second stable state. State (S2) was defined. Note that cells C and D
In, the substrate provided with the polyimide film pattern was arranged on the upper side (observer side). The results are shown in Table 9 below.

[0347]

[Table 9]

3) Measurement of M2 Margin (M2) A method of measuring the M2 margin will be described. First, a cell between polarizing plates arranged in crossed Nicols was installed, and a driving waveform (Vop = 20 V, 1 / 3.3 bias, 1/1) shown in FIG.
M2 margin was measured using 000 duty). The dark state (black display) and the bright state (white display) are written while changing the applied pulse waveform length Δt,
In the case where the range of the length Δt of the applied pulse waveform for writing the bright and dark states is as shown in FIG. 15, the drive margin parameter is set to M2 = (Δt4−Δt1) / (Δt
4 + Δt1), and the above samples 1-A, 4-B to 4-
With respect to D, 4-F, and 4-G, the temperature was changed at several points, and the M2 margin was evaluated.

The results are shown in Table 10 below.

With respect to the devices 4-C and 4-D, the M2 margin in the region where the lattice-like polyimide film was not disposed was used. In addition, since the entire surface of the element 1-F was randomly oriented, the drive margin could not be measured.

[0351]

[Table 10]

From this result, it is found that the entire surface of the device sample 4-B has lost bistability, and only one of the states (the state on the light-shielded side under crossed Nicols) is in a monostable state. As a result, the drive margin could not be measured. It can be seen that the element sample 1-A has a large M2 margin at room temperature or higher, but has a significantly worse driving margin on the low temperature side. This is expected to be due to the effect of the anti-electric field on the low temperature side. On the other hand, samples 4-C, 4-D, 4-F, 4-
In G, since the polyimide film does not exist in the effective switching region (the actual driving region where the electrodes cross each other), the electric capacity of the orientation control layer is large, and the reduction amount of the margin on the low temperature side is small.

4) Measurement of Contrast (C / R) A method of measuring contrast will be described. First, a cell in which liquid crystal is injected is arranged between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1/3.
3 bias, 1/1000 duty)
The contrast was measured at 0 ° C. At this time, the dark state and the bright state are written while the applied pulse waveform length Δt is changed, and the range of the applied pulse waveform length Δt in which the bright and dark states are written becomes as shown in FIG. At the minimum writable pulse width (Δt1), the amount of transmitted light by photomultiplier was measured for each of light and dark, and the ratio was taken as the contrast. In addition, the installation angle of the cell with respect to the polarizing plate was adjusted to a position where the dark state became the darkest in the actual driving region when no electric field was applied.
The measurement range of the transmitted light amount is about 100 μm × about 100 μm.
m, and includes the amount of transmitted light in a portion between pixels (a portion between actual driving regions where electrodes intersect each other).

The results are shown in Table 11 below.

[0355]

[Table 11]

For the element samples 1-A, 4-C, and 4-F, the portions between the actual driving regions (between the pixels) are almost bistable, so that the white domain and the black domain are visually distributed at substantially the same area ratio. Since the white domain portion exists between the actual driving regions, light leakage occurs without responding to an external electric field. As a result, the contrast is very small.

On the other hand, in the element samples 4-D and 4-G, the difference between the surface potentials of the upper and lower substrates between the actual driving regions (between the pixels) is not well balanced. For this reason, the molecular positions between pixels are aligned in one direction, and by installing cells so that the molecular positions are in a light-shielding state under crossed Nicols, there is no light leakage from between pixels, and a device with sufficient contrast can be obtained. A sample was obtained.

As described above, the portion where the alignment control layer having the uniaxial alignment control force exists and the portion where the alignment layer does not exist are mixed on the substrate, and the alignment state is formed from the liquid crystal region in contact with the portion of the alignment control layer. As a result, it was proved that a good driving margin characteristic can be realized by obtaining a uniform alignment property, and by eliminating the alignment control layer having the uniaxial alignment regulating force in the actual driving region of the liquid crystal. Furthermore, by stabilizing the portion between the actual driving regions (between the pixels) in a dark state at all times, the contrast in the display in a natural body is improved.

(Example 5) Four types of empty cells used in Example 5 were produced as follows.

Cell 5-H A pair of 1.1 mm-thick glass substrates having a stripe-patterned ITO film (thickness: about 70 nm, line width: 45 μm, interval: 5 μm) formed as transparent electrodes, were prepared. Except that the film has a width of 5 μm for one line, a size of the opening of 45 μm × 45 μm, and a line in one direction is formed in a lattice pattern corresponding to a line between the lines of the ITO film. An empty cell having a cross-sectional structure shown in FIG. 7 in which the electrodes of both substrates form a matrix structure was produced by the same method and conditions as in the case of C (the material and thickness of the polyimide film were the same as those of the cell 4-C).

Cell 5-I A pair of 1.1 mm-thick glass substrates on which a stripe-patterned ITO film (thickness: about 70 nm, line width: 45 μm, interval: 5 μm) was formed as a transparent electrode was prepared. Cell 4-D except that the film has a width of 5 μm per line, the size of the opening is 45 μm × 45 μm, and lines in one direction are formed in a lattice pattern corresponding to the lines between the ITO films. An empty cell having a cross-sectional structure shown in FIG. 7 in which the electrodes of both substrates form a matrix structure was produced by the same method and under the same conditions as in the case of (the material and thickness of the polyimide film were the same as those of cell 4-D).

Cell 5-J A polyimide film was formed by forming a line having a width of 5 μm and an opening having a size of 20 μm × 20 μm.
FIG. 7 shows that the electrodes of both substrates form a matrix structure in the same manner and under the same conditions as in the case of the cell 5-H, except that they are formed in a grid pattern corresponding to the lines between the ITO films every other line. (The material and thickness of the polyimide film are the same as those of the cell 5-H.) In this cell, a stripe line of the polyimide film is provided even in a region where the pair of electrodes cross each other.

Cell 5-K A polyimide film was formed by forming a line having a width of 5 μm, an opening having a size of 20 μm × 20 μm, and forming one line in one direction.
FIG. 7 shows that the electrodes of both substrates form a matrix structure in the same manner and under the same conditions as in the case of the cell 5-I, except that every other electrode is formed in a lattice pattern corresponding to the line between the ITO films. (The material and thickness of the polyimide film are the same as those of the cell I). In this cell, a stripe line of the polyimide film is provided even in a region where the pair of electrodes cross each other.

Each cell 5-H produced by the above-described process
-5-K, the liquid crystal composition LC-1 was injected at an isotropic phase temperature, the liquid crystal was cooled to a temperature at which a chiral smectic liquid crystal phase was exhibited, and a chiral smectic liquid crystal element sample 5-H-5 exhibiting bistability was obtained. -K was produced. Observation of this cooling process in a polarizing microscope revealed that, in the cells 5-H to 5-K, the formation of an alignment state due to the generation and growth of butene as shown in FIG. 3 from the vicinity of the transition temperature to the smectic A phase. Was observed.

These samples were evaluated for the following items.

1) Evaluation of Uniformity of Alignment As in the case of Example 4, the uniformity of the alignment of the liquid crystal in the device was observed. The results are shown in Table 12 below.

[0367]

[Table 12]

In the device samples 5-H and 5-I, the distance between the lines of the polyimide film was relatively large, and the region having substantially no uniaxial alignment regulating force was too large.
In the center part of the pixel which is far away from the polyimide film, a part with disordered orientation has occurred.

2) Measurement of Contrast (C / R) The contrast of the element samples 5-J and 5-K was measured in the same manner as in Example 1.

The results are shown in Table 13 below.

[0371]

[Table 13]

In the element sample 5-K, the difference between the surface potentials of the upper and lower substrates in the portion between the actual driving regions (between the pixels) is not well balanced as compared with the sample 5-J. Therefore, the molecular positions between the pixels are aligned in one direction, and by installing the cell such that this molecular position is in a light-shielding state under crossed Nicols,
An element sample with sufficient contrast without light leakage from the portion between pixels could be obtained.

Example 6 A cell (simple matrix type cell) used in this example was manufactured as follows.

Cell 6-C Here, a cell (empty cell) having a sectional structure schematically shown in FIG.
Was prepared.

As a transparent electrode, a stripe pattern IT
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as that used in the cell 1-A of Example 1 was applied by a spin coating method, and then pre-dried at 80 ° C. for 5 minutes. The resultant was baked at 1 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, UV (λ = 365) was obtained using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developing solution (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-temperature mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 6 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
A portion where a stripe-shaped polyimide film exists on the substrate corresponding to a distance of 50 nm between lines of the ITO film (width of 4 μm;
1 and a portion corresponding to the line of the ITO film with a thickness of about 2 nm (width of 16 μm, FIG. 1).
(A portion corresponding to the layer 17a of No. 7).

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the case of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Then, after pre-drying at 80 ° C. for 5 minutes,
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was coated) as a spacer.
And the other substrate is overlapped so that the electrodes of the respective substrates are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as schematically shown in FIG. Empty cell).

The total thickness of the insulating films (polyimide layer and silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus manufactured was 8 nm.

Cell 6-D Here, a cell (empty cell) having a sectional structure schematically shown in FIG.
Was prepared.

[0383] IT of a stripe pattern as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as that used in the cell 1-A of Example 1 was applied by a spin coating method, and then pre-dried at 80 ° C. for 5 minutes. The resultant was baked at 1 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, UV (λ = 365) was obtained using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developing solution (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-temperature mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 10 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. At this point, a portion (4 μm in width) where a stripe-shaped polyimide film exists on the substrate corresponding to a distance of 50 nm between the lines of the ITO film.
m) and a polyimide film pattern consisting of a portion (width 16 μm) in which no polyimide film exists corresponding to the line of the ITO film.

Subsequently, the same polyimide (precursor) was further applied onto the polyimide film pattern by spin coating, and pre-dried at 80 ° C. for 5 minutes.
For 1 hour to obtain a polyimide film having a thickness of 2 nm. That is, on the substrate, a portion (width 4 μm, corresponding to the laminated portion of the layers 18a and 19a in FIG. 18) corresponding to the stripe-shaped polyimide film 52 nm corresponding to the interval between the ITO film lines and the ITO film line The portion where the polyimide film exists with a thin thickness of about 2 nm (width 16 μm, FIG.
(A portion corresponding to the layer 19a between the layers 18a).

Next, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the case of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating. Then, after pre-drying at 80 ° C. for 5 minutes,
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was coated) as a spacer.
And the other substrate is overlaid so that the electrodes of each substrate are orthogonal to each other and have a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as schematically shown in FIG. Empty cell).

The total thickness of the insulating films (polyimide layer and silica layer) in the actual driving region (the portion where the electrodes of both substrates intersect) of the cell thus fabricated was 8 nm.

The size of cells 6-C and 6-D is 2.5
cm × 3.5 cm (the side in the stripe direction of the ITO film coincident with the line of the polyimide film was 2.5 cm).

Each cell 6 manufactured by the above-described process was used.
-C, 6-D, and the liquid crystal composition LC-1 was injected into the cells 1-A and 1-B of Example 1 at an isotropic phase temperature, and the liquid crystal was cooled to a temperature showing a chiral smectic liquid crystal phase. Smectic liquid crystal device sample 6 exhibiting bistability
-C, 6-D, 1-A, 1-B were made. When this cooling process was observed in a polarizing microscope, Sample 6-C,
In 6-D, the formation of the bone and the formation process of the oriented state due to the growth as shown in FIG. 3 were observed from around the transition temperature to the smectic A phase.

The temperature characteristics of the liquid crystal composition LC-1 used in this example are shown in Table 14 below.

[0394]

[Table 14]

V _th1 and V _th2 were determined by using the values measured in a cell in which a pair of 2 μm-thick ITO substrates oriented by the temperature gradient method were opposed to each other, and d ₁ and d ₂ were obtained by the following equations. (Equation A1) d ₁ = V _th1 × ε / 2Ps (Equation A2) d ₂ = V _th2 × ε / 2Ps Note that the relative permittivity is 3.3 and the vacuum permittivity ε ₀ = 8.85.
Ε was calculated as × 10 ⁻¹² . Note that d ₁ and d ₂ correspond to the total thickness of the insulating films on both the upper and lower substrates in the cell.

The pulse width used in this measurement was determined as follows. Since the drive voltage at the time of selection in measuring the M2 margin in the embodiment is 20 V,
When the temperature characteristics of the threshold pulse width at V were measured,
1.6 μsec (40 ° C.), 27 μsec (25 ° C.),
100 μsec (10 ° C.) Therefore, when measuring the M2 margin in the embodiment, 1
Since a simple matrix waveform of / 1000 duty was used, V _th1 and V _th2 were measured using a rectangular wave having a pulse width of 1000 times as shown in the above table. That is, V _th1 was measured as a voltage value that was partially inverted during one frame, and V _th2 was measured as a voltage value that was completely inverted during one frame.

As is clear from the table, Example 6-
For cells using the liquid crystal composition used in C and 6-D, the total thickness of both substrate insulating films in the actual driving region was 8 at room temperature.
If it is less than nm, the inhibition of switching due to the reverse voltage when switching the liquid crystal having spontaneous polarization is prevented. However, in this embodiment, at least the thickness of the insulating film in the actual driving region is 8 nm. I'm looking forward to it.

Further, in Examples 6-C and 6-D, the thickness of the striped polyimide having a strong uniaxial alignment regulating force is at a level exceeding 25 nm (the maximum value of d2 in Table 14), which is preferable.

With respect to these samples, 1) evaluation of orientation uniformity, 2) evaluation of time-dependent change of ion amount in the cell,
3) M2 margin (M2) was measured.

1) Evaluation of Alignment Uniformity A voltage was applied to the liquid crystal element in the state of a chiral smectic liquid crystal phase to switch the chiral smectic liquid crystal to one state, and the alignment uniformity was evaluated by visual observation with a polarizing microscope. Was. Table 15 shows the results.

[0401]

[Table 15]

2) Time-dependent change in the amount of ions The amount of ions existing in the cell was measured. The measurement was carried out by using an ion density measurement system MTR-1 (manufactured by Toyo Technica Co., Ltd.) at room temperature. 30
After standing for a day, the measurement was performed, and the change with time in the amount of ions in the cell was measured. The result was 2.0 [nC / cm ² ] for all the device samples at the initial stage and after the initial stage, and there was no change between the initial ion amount and the ion amount after the lapse of time.

Next, as a comparative example, both the upper and lower substrates
A cell was prepared using a substrate in which O (and a glass substrate) was exposed, and a sample in which the same liquid crystal material was injected was subjected to the same evaluation. The initial ion amount was 2.0 [nC / cm ² ], and the amount of ions after the time is 1
0.0 [nC / cm ² ]. In this sample,
It can be seen that the amount of ions is greatly increased by leaving it to stand. This is considered to be due to the exudation of impurities from the ITO or glass substrate.

[0404] From these results, samples 1-A and 1-
Since the substrate including the actual driving region, such as B, 6-C, and 6-D, is covered with at least an insulating layer, the amount of ions in the cell due to leaching of ions from the substrate over time It can be seen that a significant increase can be suppressed.

3) Measurement of M2 Margin (M2) A method of measuring the M2 margin will be described. First, a cell was placed between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1 / 3.3 bias, 1 /
The M2 margin was measured using (1000 duty). FIG. 15 shows the range of the applied pulse waveform length Δt in which the dark state and the bright state are written while changing the applied pulse waveform length Δt, and the bright and dark states are written.
, M2 = (Δt2−Δt1) / (Δt
2 + Δt1).

Element 1-A, 1-B, 6-C, 6-D
The M2 margin was measured while varying the temperature for several points.

The above results are shown in Table 16 below.

[0408] For the elements 1-B and 6-C, the M2 margin was evaluated only in the normally switching region.

[0409]

[Table 16]

From this result, it can be seen that the sample 1-A has a large M2 margin at room temperature or higher, but has a significantly worse driving margin on the low temperature side. This is expected to be due to the effect of the anti-electric field on the low temperature side. On the other hand, with respect to the device sample 1-B having poor orientation, although the value of the M2 margin is small as a whole, the device sample 1-B has a smaller orientation film thickness and a larger electric capacity of the orientation control layer than the device A. In addition, the amount of decrease in the margin on the low temperature side is small. On the other hand, element sample 6-
C, the sample 6-D has a small orientation film thickness in the effective switching region, so that the electric capacity of the orientation control layer is large and the amount of decrease in the margin on the low temperature side is small. Further, since the orientation film thickness is small, the influence of the anti-electric field is small, and the reduction amount of the M2 margin on the low temperature side is small.

[0411] From the above results, uniformity can be obtained by mixing a region having a very strong orientation regulating force and a region having a weak orientation regulating force but having a reduced orientation film thickness to reduce the influence of the anti-electric field. It has been found that both a simple arrangement and good drive margin characteristics can be achieved.

(Example 7) A cell (simple matrix type cell) used in this example was produced as follows.

Cell 7-D Here, a cell (empty cell) having a sectional structure schematically shown in FIG.
Was prepared.

[0414] Striped pattern IT as a transparent electrode
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution having a solid content of 10% by weight was added to one side of this glass substrate, and 50% by weight of antimony-doped SnOx ultrafine particles (particle diameter: 100 °) was added and dispersed in a sol-gel type silica base material. Coating is performed by spin coating, followed by pre-drying at 80 ° C. for 5 minutes, and then heating and drying at 200 ° C. for 1 hour to form a film having a thickness of 200 nm.
To obtain a fine particle dispersion layer. Example 1 on the fine particle dispersion layer
The same polyimide (precursor) as that used in Cell 1-A was applied by spin coating, and then 80 ° C.
After pre-drying for 5 minutes, it was heated and baked at 200 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Thereafter, pre-drying was performed at 80 ° C. for 30 minutes, and then UV (λ = 36) using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
(5 nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developer (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-temperature mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 6 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
On the substrate, there is a portion (width 4 μm, corresponding to the layer 15a in FIG. 17) in which a stripe-shaped polyimide film exists 50 nm corresponding to the interval between the ITO film lines, and a film thickness of about 2 nm corresponding to the ITO film line. A polyimide film pattern consisting of existing portions (width 16 μm, corresponding to layer 17a in FIG. 17) was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

An ethanol solution having a solid concentration of 10% by weight was prepared by dispersing 50% by weight of antimony-doped SnOx ultrafine particles (particle size: 100 °) in a sol-gel type silica base material on the other glass substrate. Was applied by spin coating to obtain a fine particle dispersion layer having a thickness of 200 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was coated) as a spacer.
And the other substrate is overlapped so that the electrodes of the respective substrates are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as schematically shown in FIG. Empty cell).

The size of cell 7-D is 2.5 cm ×
3.5 cm (I coincided with the polyimide film line)
The side in the stripe direction of the TO film is 2.5 cm).

In the actual driving region (intersection of the electrodes of both substrates) of the cell 7-D manufactured in this embodiment, the surface roughness of each layer serving as the substrate surface in contact with the liquid crystal was the same as that of the third embodiment. The measurement was performed under the method and conditions. On the surface of the fine particle dispersion layer on one substrate side, which was covered with a thin (2 nm thick) polyimide layer, the arithmetic average roughness Ra = 3.53,
The root mean square roughness Rms is 4.21 and the surface roughness is 5.32. The arithmetic mean roughness Ra 4.28 (nm) and the root mean square roughness Rms of the exposed surface of the fine particle dispersion layer of the other substrate are:
5.38 and surface roughness = 6.911.

[0422] The cell 7-
D. Further, the liquid crystal composition LC-1 is injected into the cells 1-A and 1-B of Example 1 and the cell 6-C of Example 6 at an isotropic phase temperature, and the liquid crystal exhibits a chiral smectic liquid crystal phase. After cooling to a temperature, chiral smectic liquid crystal element samples 7-D, 1-A, 1-B and 6-C exhibiting bistability were prepared.
Observation of this cooling process in a polarizing microscope revealed that in Sample 7-AB, the generation of badnes and the formation process of an alignment state due to growth as shown in FIG. 3 were observed from around the transition temperature to the smectic A phase.

[0423] These samples were evaluated for 1) evaluation of alignment uniformity, 2) measurement of M2 margin (M2), and 3) evaluation of display burn-in.

1) Evaluation of Alignment Uniformity A voltage is applied to the liquid crystal element in the state of a chiral smectic liquid crystal phase to switch the chiral smectic liquid crystal to one state, and the alignment uniformity is evaluated by visual observation with a polarizing microscope. Was. The results are shown in Table 17 (samples 1-A, 1-B and 6-C are the same as in Example 6).

[0425]

[Table 17]

2) Measurement of M2 Margin (M2) A method of measuring the M2 margin will be described. First, a cell was placed between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1 / 3.3 bias, 1 /
The M2 margin was measured using (1000 duty). When the range of the applied pulse waveform length Δt in which the dark state and the bright state can be written and the bright and dark states can be written while changing the applied pulse waveform length Δt is as shown in FIG. 15, M2 = ( Δt2-Δt1) /
(Δt2 + Δt1).

The above device samples 1-A, 1-B, 7-D
The M2 margin was measured while varying the temperature for several points (for Example 1-A, 1-B, and 6-C, Example 6 was used).
Etc.).

The results are shown in Table 18 below.

For the element 1-B, the M2 margin was evaluated only in a normally switched region.

[0430]

[Table 18]

[0431] From this result, it can be seen that in Sample 1-A, although the M2 margin at room temperature or higher is large, the drive margin on the low temperature side is significantly deteriorated. This is expected to be due to the effect of the anti-electric field on the low temperature side. On the other hand, with respect to the device sample 1-B having poor orientation, although the value of the M2 margin is small as a whole, the device sample 1-B has a smaller orientation film thickness and a larger electric capacity of the orientation control layer than the device A. In addition, the amount of decrease in the margin on the low temperature side is small. On the other hand, element sample 7-
In D, since the thickness of the insulating layer in the effective switching region is small, the electric capacity of the orientation control layer is large, and the decrease in the margin on the low temperature side is small.

3) Evaluation of display burn-in For element samples 1-A and 7-D, a stripe pattern of black and white display was displayed using the drive waveforms shown in FIG. After the same pattern was displayed, the driving conditions (M2 margin) where the entire cell could be written in black and white were measured by the same method and conditions as in 2) above (samples 1-A and 6-C were implemented). (Similar to the evaluation in Example 3). The ratio between the value of the M2 margin after 1000 hours and the value of the M2 margin before the burn-in test (before displaying the same pattern) was taken as the margin conservation rate after 1000 hours. The measurement temperature of the storage rate was 30 ° C. The results are shown in Table 19 below.

[0433]

[Table 19]

From the above results, the margin preservation ratio tends to increase as the thickness of the polyimide in the actual driving region decreases, and the sample 7-containing a layer made of oxide fine particles provided with conductivity. As for D, it is clear that a very high margin holding ratio can be obtained due to the effect of minute surface irregularities on the surface in contact with the liquid crystal in the actual driving region.

From the above results, it is possible to obtain a uniform region by mixing a region having a very strong alignment regulating force and a region having a weak alignment regulating force but having a reduced orientation film thickness to reduce the effect of the anti-electric field. It has been found that both a simple arrangement and good drive margin characteristics can be achieved.

Example 8 A cell (simple matrix type cell) used in this example was manufactured as follows.

Cell 8-D In the fabrication of the cell 4-B in Example 4, the other conditions were the same except that the thickness of the polyimide film on one substrate was 2 nm, and the cell having a matrix electrode structure ( Empty cell). The total thickness of the insulating films (silica layer and polyimide film) in the actual driving region (the intersection of the electrodes of both substrates) in the cell was 8 nm.

8-F Here, a cell (empty cell) having a sectional structure schematically shown in FIG.
Was prepared.

As a transparent electrode, a stripe pattern IT
1.1 mm formed with an O film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm)
A pair of thick glass substrates was prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, and then pre-dried at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as that used in the cell 4-B of Example 4 was applied by spin coating, and then pre-dried at 80 ° C. for 5 minutes, and then 200 The resultant was baked at 1 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Thereafter, pre-drying was performed at 80 ° C. for 30 minutes, and then UV (λ = 36) using a stripe-shaped mask pattern having a mask width of 4 μm and an interval of 16 μm.
(5 nm) for 16 seconds. At this time, the mask pattern was arranged such that the mask portion corresponded between the lines of the ITO film pattern of the substrate. Thereafter, the resist film is developed using an organic developer (MFCD-26 manufactured by Ziprey Co., Ltd.), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and resist film corresponding to the line between the ITO film patterns. Got the pattern. Subsequently, using a low-temperature mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 8 J / cm ² , thereby removing the polyimide without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
On the substrate, there is a portion (width 4 μm, corresponding to the layer 15a in FIG. 17) in which a stripe-shaped polyimide film exists 50 nm corresponding to the interval between the ITO film lines, and a film thickness of about 2 nm corresponding to the ITO film line. A polyimide film pattern consisting of existing portions (width 16 μm, corresponding to layer 17a in FIG. 17) was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the case of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating.
A 3 nm-thick silica layer was obtained.

The total thickness of the insulating film (silica layer and polyimide film) in the actual driving region (the portion where the electrodes of both substrates intersect) in the cell thus fabricated was 8 nm.

Subsequently, a spacer having an average particle size of 2.0 μm was formed on one of the substrates (the substrate on which polyimide was applied) as a spacer.
And the other substrate is overlapped so that the electrodes of the respective substrates are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11), and a cell having a cross-sectional structure as schematically shown in FIG. Empty cell).

The size of the cell 8-F is 2.5 cm ×
3.5 cm (I coincided with the polyimide film line)
The side in the stripe direction of the TO film is 2.5 cm).

Cell 8-G A pair of 1.1 mm-thick glass substrates each formed with a stripe-patterned ITO film (thickness: about 70 nm, width of one line: 16 μm, interval between adjacent lines: 4 μm) as a transparent electrode were formed. Prepared.

An ethanol solution of sol-gel type silica was applied to one of the glass substrates by spin coating, followed by pre-drying at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as that used in the cell 4-B of Example 4 was applied by a spin coating method, and then pre-dried at 80 ° C. for 5 minutes. The resultant was baked at 1 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Then, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film so as to have a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, exposure was performed for 16 seconds by UV (λ = 365 nm) using a mask pattern having a mask width of 4 μm and an interval of 16 for 16 seconds. Then, an organic developer (MF, manufactured by Zipley Co., Ltd.)
After developing using CD-26) and washing with running water for 3 minutes, drying was performed at 100 ° C. for 10 minutes to obtain a striped resist film pattern corresponding to the interval between the lines of the ITO film pattern. Subsequently, using a low-temperature mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 12 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. In this way, a portion (4 μm in width) where the stripe-shaped polyimide film exists on the substrate corresponding to the distance between the lines of the ITO film at a thickness of 50 nm,
At the portion corresponding to the O film line, a polyimide film pattern consisting of a portion (width 16 μm) where no polyimide film was present was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as those of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction perpendicular to the stripe direction of the polyimide film.

An ethanol solution of sol-gel type silica was applied to the other glass substrate by spin coating, followed by pre-drying at 80 ° C. for 5 minutes.
The resultant was dried by heating at 1 ° C. for 1 hour to obtain a silica layer having a thickness of 3 nm. On the silica layer, the same polyimide (precursor) as that used in the cell 1-A of Example 1 was applied by a spin coating method, and then pre-dried at 80 ° C. for 5 minutes. The resultant was baked at 1 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 nm.

Next, a positive resist (Tokyo Ohka OFPR-800) was spin-coated on the polyimide film to a thickness of about 2 μm. Then, after pre-drying was performed at 80 ° C. for 30 minutes, using a mask pattern with a mask width of 4 μm and an interval of 16 μm, UV irradiation (λ = 365 nm) was performed.
Exposure was for 6 seconds. Thereafter, the film is developed using an organic developer (MFCD-26 manufactured by Ziprey), washed with running water for 3 minutes, dried at 100 ° C. for 10 minutes, and striped corresponding to the ITO film pattern between lines. Was obtained. Subsequently, using a low-temperature mercury lamp, the substrate temperature is maintained at 60 ° C., and UV ashing is performed at a UV intensity at which the light energy at a wavelength of 254 nm is 6 J / cm ² , thereby removing the polyimide in the portion without the resist film. did. Next, the resist film pattern was stripped off using a stripping solution (Nagase Sangyo Co., Ltd., resist strip N-320), washed with running water, and the substrate was dried. Thus,
A portion (4 μm in width) where a stripe-shaped polyimide film is present on the substrate at a thickness of 50 nm corresponding to between the lines of the ITO film.
Then, a polyimide film pattern consisting of a portion (width 16 μm) having a thickness of about 2 nm corresponding to the line of the ITO film was obtained.

Subsequently, the polyimide film pattern on the substrate was subjected to a rubbing treatment as a uniaxial orientation treatment by the same method and under the same conditions as in the case of the cell 1-A of Example 1. The direction of the rubbing treatment was set in a direction parallel to the stripe direction of the polyimide film.

Subsequently, as a spacer on one of the substrates,
Silica beads having an average particle size of 2.0 μm are scattered, and the other substrate is superimposed so that the electrodes of each substrate are orthogonal to each other in a matrix electrode arrangement (arrangement as shown in FIG. 11). A cell (empty cell) having a cross-sectional structure as schematically shown in FIG. 9 was prepared except for the presence of the film.

The size of the cell 8-G is 2.5 cm ×
It was 3.5 cm.

Each cell 8-
D, 8-F, 8-G and 1- produced in the above-described embodiment.
A, 1-B, 4-B, 6-C, the liquid crystal composition LC-1 is injected at an isotropic phase temperature, the liquid crystal is cooled to a temperature at which a chiral smectic liquid crystal phase is exhibited, and a chiral liquid exhibiting bistability is obtained. A smectic liquid crystal element sample was manufactured. Observation of this cooling process with a polarizing microscope revealed that cells 6-C and 8-
In F and 8-G, a process of forming an alignment state due to generation and growth of a butene as shown in FIG. 3 was observed from around the transition temperature to the smectic A phase.

The surface potential of polysiloxane and polyimide constituting the surface of each cell in contact with the liquid crystal was measured by a method referring to the result measured in Example 4.

1) Evaluation of alignment uniformity A voltage was applied to the liquid crystal element to switch the chiral smectic liquid crystal to one state, and the alignment uniformity was evaluated by visual observation with a polarizing microscope under crossed Nicols. In Samples 1-B and 8-D, about half of the visual field was in the focal conic state, but in the other samples, the entire surface was uniform, which was uniform.

2) Evaluation of molecular position after slow cooling Visual observation with a polarizing microscope revealed that Sm
The molecular position immediately after cooling to the C ^* phase was evaluated (for cells 1-A, 4-B, 6-C, 8-F, 8-G). At this time, at the time of observation with a polarizing microscope under crossed Nicols, the position of a molecule tilted counterclockwise from the layer normal direction (rubbing treatment) is a first stable state (S1), and the position of a molecule tilted clockwise is a second stable state. State (S2) was defined. In the cells 6-C and 8-F, the substrate provided with the polyimide film pattern was arranged on the upper side (observer side). The results are shown in Table 20 below.

[0460]

[Table 20]

3) Measurement of M2 Margin (M2) A method of measuring the M2 margin will be described. First, a cell was installed between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1 / 3.3 bias, 1 /
The M2 margin was measured using (1000 duty). The dark state (black display) and the bright state (white display) are written while changing the applied pulse waveform length Δt, and the range of the applied pulse waveform length Δt in which the bright and dark states can be written is as shown in FIG. Is satisfied, the driving margin parameter is set to M2 = (Δt4−Δt1) /
With respect to the sample, the temperature was changed at several points as (Δt4 + Δt1), and the M2 margin was evaluated.

The results are shown in Table 21 below.

[0463]

[Table 21]

From this result, it can be seen that the element 1-A has a large M2 margin at room temperature or higher, but has a significantly worse driving margin on the low temperature side.
This is expected to be due to the effect of the anti-electric field on the low temperature side. On the other hand, as for the element 1-B having poor orientation, although the value of the M2 margin is small as a whole, the element 1-B has a smaller orientation film thickness and a larger electric capacity of the orientation control layer than the element 1-A. In addition, the amount of decrease in the margin on the low temperature side is small. On the other hand, in the elements 6-C and 8-G, the electric capacity of the orientation control layer in the effective switching region is large, and the reduction amount of the margin on the low temperature side is small. Further, since the orientation film thickness is small, the influence of the anti-electric field is small, and the reduction amount of the M2 margin on the low temperature side is small. Further, the elements 4-B, 8-D, and 8-D in which the alignment film LP64 exists in the actual driving region.
Regarding -F, the bistability was broken (only one of them was in a stable monostable state), and switching could not be performed sufficiently.

4) Measurement of Contrast (C / R) A method of measuring contrast will be described. First, a cell into which liquid crystal was injected was placed between polarizing plates arranged in crossed Nicols, and a driving waveform (Vop = 20 V, 1/3.
3 bias, 1/1000 duty)
The contrast was measured at 0 ° C. At this time, while changing the length Δt of the applied pulse waveform, the dark state and the bright state are written, respectively, and when the range of the applied pulse waveform Δt in which the bright and dark states can be written becomes as shown in FIG. At the minimum writable pulse width (Δt1), the amount of transmitted light by photomultiplier was measured for each of light and dark, and the ratio was taken as the contrast. In addition, the installation angle of the cell with respect to the polarizing plate was set to a position where the dark state becomes the darkest in the actual driving region when no electric field was applied. The measurement range of the amount of transmitted light is about 100 μm × about 10 μm.
The distance was set to 0 μm, and the amount of transmitted light in a portion between pixels (a portion between actual driving regions where electrodes intersect each other) was included.

Samples 1-A, 6-C,
For 8-G, the measurement of contrast was possible. The results are shown in Table 21 below.

[0467]

[Table 22]

In elements 1-A and 6-C, the white domain and the black domain are distributed at substantially the same area ratio because the inter-pixel portion is almost bistable, and the white domain portion exists between the pixels. Therefore, light leakage occurs without responding to an external electric field. As a result, the contrast is very small. On the other hand, in the element 8-G, only the portion between pixels is asymmetric because the surface potentials of the upper and lower substrates in the portion between pixels are not balanced. Therefore, the molecular positions between the pixels are aligned in one direction, and the cells are installed so that the molecular positions are in a light-shielding state under crossed Nicols, so that an element having sufficient contrast without light leakage from a portion between the pixels is obtained. be able to.

[0469]

As described in detail above, according to the present invention, a liquid crystal device having improved alignment uniformity and driving characteristics, particularly a liquid crystal device using a chiral smectic liquid crystal,
Provided is a liquid crystal element in which the orientation of a smectic liquid crystal phase is uniform, the temperature dependence of a driving margin is reduced, or high-speed response is realized.

[Brief description of the drawings]

FIG. 1 is a plan view showing a structure of a substrate used for a liquid crystal element according to one embodiment of the present invention.

FIG. 2 is a sectional view showing the structure of the liquid crystal element according to the first embodiment of the present invention.

FIGS. 3A to 3C are diagrams schematically showing an example of a process of forming a liquid crystal alignment state in a liquid crystal element of the present invention.

4A to 4C are diagrams schematically showing another example of a process of forming a liquid crystal alignment state in the liquid crystal element of the present invention.

5A to 5C are diagrams schematically showing still another example of the process of forming the alignment state of the liquid crystal in the liquid crystal element of the present invention.

FIG. 6 is a sectional view showing a structure of a liquid crystal element according to a fourth embodiment of the present invention.

FIG. 7 is a sectional view showing the structure of a liquid crystal device according to a fifth embodiment of the present invention.

8 is a view showing a positional relationship between an orientation control layer and electrodes on the substrate (12a) side shown in FIG.

FIG. 9 is a sectional view showing the structure of a liquid crystal element according to a sixth embodiment of the present invention.

10 is a diagram showing a positional relationship between an orientation control layer and electrodes on the substrate (12a) side shown in FIG.

FIG. 11 is a diagram showing an example of an electrode structure in an embodiment of the liquid crystal element of the present invention.

FIG. 12 is a diagram showing an example of a simple matrix driving method applied to the liquid crystal element of the present invention.

FIG. 13 is a diagram showing an example of a simple matrix driving method applied to the liquid crystal element of the present invention.

FIG. 14 is a diagram showing the relationship between the pulse width and the transmittance of liquid crystal when the driving method shown in FIGS. 12 and 13 is used.

FIG. 15 shows the results obtained by using a chiral smectic liquid crystal.
In the element having the characteristics shown in FIG. FIG. 4 is a diagram for explaining a drive margin.

FIG. 16 is a diagram schematically illustrating an example of an alignment state of the liquid crystal element of the present invention.

FIG. 17 is a sectional view showing the structure of a liquid crystal element according to a second embodiment of the present invention.

FIG. 18 is a sectional view showing a structure of a liquid crystal element according to a third embodiment of the present invention.

FIG. 19 is a diagram schematically illustrating an example of a planar structure of an active matrix substrate used for a liquid crystal element of the present invention.

FIG. 20 is a cross-sectional view illustrating a structure example of an active matrix type liquid crystal element of the present invention.

21 is a circuit diagram showing an equivalent circuit of the structure shown in FIG.

FIG. 22 is a diagram showing a driving waveform and a change in transmittance corresponding to the driving waveform in the case of an active matrix type liquid crystal element of the present invention.

[Explanation of symbols]

 Reference Signs List 1 liquid crystal element 11 liquid crystal 12a, 12b substrate 13a, 13b electrode 14a, 14b layer 15a, 15b alignment control layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Sho Makoto Mori 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Satoshi Miura 3-30-2 Shimomaruko, Ota-ku, Tokyo (72) Inventor Yasuyuki Watanabe 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (76)

[Claims] A first region having a liquid crystal between a pair of substrates and having a uniaxial alignment regulating force with respect to a liquid crystal provided at least selectively in contact with the liquid crystal on at least one substrate side;
A second region having a weak uniaxial alignment regulating force with respect to the liquid crystal compared to the first region outside the first region or having substantially no uniaxial alignment regulating force, wherein the liquid crystal is formed between the substrates. In the temperature drop, a transition from a portion in contact with the first region to a liquid crystal phase occurs in a liquid phase-liquid crystal phase transition process, and a liquid crystal phase transition region grows along a uniaxial orientation axis in the first region. ,
A liquid crystal element characterized in that a liquid crystal phase transition region is continuously enlarged in the second region to form an alignment state. 2. A liquid phase-liquid crystal phase transition temperature of a liquid crystal region in contact with a surface substantially parallel to a substrate surface of a first region having a uniaxial alignment regulating force, in a portion in contact with the second region. 2. The liquid crystal device according to claim 1, wherein the temperature is higher than a liquid phase-liquid crystal phase transition temperature of a liquid crystal region. 3. The liquid crystal shows a smectic liquid crystal phase,
During the temperature drop, a transition from a liquid crystal region in contact with a surface substantially parallel to the substrate surface of the first region having the uniaxial alignment regulating force to a smectic liquid crystal phase occurs in a phase transition process of the liquid crystal, and the first region has 2. The liquid crystal device according to claim 1, wherein the smectic liquid crystal phase transition region is continuously expanded along the uniaxial alignment axis direction to form an alignment state. 4. The liquid crystal is a chiral smectic liquid crystal that takes a phase transition from a liquid phase to a smectic liquid crystal phase. When the temperature is lowered, the liquid crystal is substantially in contact with the substrate in the selectively provided first region in the phase transition process of the liquid crystal. The transition from the liquid crystal region in contact with the plane parallel to the surface to the smectic liquid crystal phase occurs, and the smectic liquid crystal phase transition region continuously expands along the uniaxial orientation axis direction of the first region to form an alignment state. The liquid crystal device according to claim 1, wherein 5. The method according to claim 1, wherein the first region having the uniaxial alignment regulating force is selectively provided only on one of the substrates, and the liquid crystal is composed of a chiral smectic liquid crystal that takes a phase transition from a liquid phase to a smectic liquid crystal phase. During the phase transition process of the liquid crystal at the time of temperature drop, a transition from a liquid crystal region in contact with a surface of the first region substantially parallel to the substrate to a smectic liquid crystal phase occurs, and the first region extends along the uniaxial orientation axis direction. The liquid crystal device according to claim 4, wherein the smectic liquid crystal phase transition region is continuously expanded to form an alignment state. 6. The liquid crystal device according to claim 3, wherein the first region is selectively provided in a shape continuous in the same direction as the direction of the smectic layer constituting the liquid crystal. 7. The first region having a uniaxial alignment regulating force is an alignment control layer pattern of a pattern formed by a plurality of stripes whose longitudinal direction is the same as the direction of the smectic layer constituting the liquid crystal. 6. The liquid crystal device according to any one of items 3 to 5. 8. The smectic layer in a direction normal to a smectic layer portion of one stripe portion of the orientation control layer of the plurality of stripe patterns, and a smectic portion between adjacent stripes of the orientation control layer where the orientation control layer is not provided. The liquid crystal device according to claim 7, wherein the length is shorter than the length of the layer in the normal direction. 9. A substrate provided with a first region layer having a uniaxial alignment regulating force, wherein a total plane area of the first region layer is smaller than a total plane area other than the first region. 1
The liquid crystal element according to the above. 10. The liquid crystal device according to claim 1, wherein the first region having a uniaxial alignment regulating force is an alignment control layer obtained by rubbing an organic insulating film. 11. A substrate having a first region having a uniaxial alignment regulating force, wherein the first region layer and a material forming a layer in contact with a liquid crystal in the second region are made of different materials. Item 2. The liquid crystal element according to item 1. 12. The liquid crystal according to claim 1, wherein a layer in contact with the liquid crystal in the second region has substantially no uniaxial alignment regulating force, and a portion of the second region in contact with the liquid crystal is made of a vertical alignment material. element. 13. The liquid crystal device according to claim 12, wherein the portion of the second region in contact with the liquid crystal is made of at least one material selected from the group consisting of a silane coupling material, a fluorine-containing film, and organically modified silica. 14. The liquid crystal device according to claim 1, wherein one of the substrates is provided with an alignment control layer having substantially no uniaxial alignment control force, and the alignment control layer contacts the liquid crystal over the entire surface. 15. A substrate having a selectively formed first region having a uniaxial alignment regulating force, wherein a layer forming the second region is provided on the entire surface of the substrate, and the second region is formed. 2. An alignment control layer constituting a first region having a uniaxial alignment regulating force is selectively provided on a layer to be formed.
The liquid crystal element according to the above. 16. In the substrate having the selectively formed first region having a uniaxial alignment regulating force, a layer constituting the second region is provided on the entire surface of the substrate, and the second region is formed. 2. An alignment control layer constituting a first region having a uniaxial alignment regulating force is selectively provided on a layer to be formed.
4. The liquid crystal element according to 4. 17. The liquid crystal has a structure in which a terminal portion of a fluorocarbon and a hydrocarbon portion are bound by a central nucleus, and contains at least one fluorine-containing liquid crystal compound having a smectic intermediate phase or a latent smectic intermediate phase. 6. The liquid crystal device according to claim 3, which is a chiral smectic liquid crystal composition. 18. A stripe-shaped electrode group is provided on each of the pair of substrates, the electrode group of each substrate forms a matrix structure, and the first region having the uniaxial alignment regulating force is at least 2. The liquid crystal device according to claim 1, wherein the electrodes of the substrate are selectively provided at portions where the electrodes do not intersect. 19. The liquid crystal part, wherein the liquid crystal molecules near the substrate interface corresponding to the first region of the at least one substrate and the bulk liquid crystal molecules between the substrates are in a substantially continuous alignment state. Region, and the liquid crystal molecules near the substrate interface corresponding to the second region of the at least one substrate and the bulk liquid crystal molecules between the substrates are constituted by a second liquid crystal region in a discontinuous alignment state. The liquid crystal device according to claim 1. 20. The liquid crystal device according to claim 19, wherein at least one of the substrate surfaces corresponding to the second liquid crystal region has substantially no uniaxial alignment regulating force. 21. The liquid crystal device according to claim 19, wherein at least one of the second regions corresponding to the second liquid crystal region has a surface roughness with an arithmetic average roughness Ra of 2 nm or more. 22. A second region on the side of at least one substrate corresponding to the second liquid crystal region has a root mean square roughness Rms.
20. The liquid crystal device according to claim 19, wherein has a surface roughness of 2.5 nm or more. 23. The liquid crystal device according to claim 19, wherein at least one of the second regions on the substrate side corresponding to the second liquid crystal region has a surface roughness of 5% or more. 24. The liquid crystal part comprises a plurality of real driving regions separated from each other, the real driving region corresponds to the second liquid crystal region, and a region between the real driving regions is the second liquid crystal region. 20. The liquid crystal device according to claim 19, which corresponds to a first liquid crystal region. 25. A liquid crystal phase transition temperature of a first liquid crystal region in contact with the first region having the uniaxial alignment regulating force, and a liquid crystal phase transition temperature of a second liquid crystal region in contact with the second region.
20. The liquid crystal device according to claim 19, which is higher than a liquid crystal phase transition temperature. 26. The liquid crystal exhibits a smectic liquid crystal phase. When the temperature drops, the liquid crystal changes from a liquid crystal region in contact with a plane substantially parallel to the substrate of the first region having the uniaxial alignment regulating force in a phase transition process of the liquid crystal. 20. The liquid crystal display device according to claim 19, wherein a transition to a phase occurs, and the smectic liquid crystal phase transition region continuously expands along the uniaxial orientation processing direction of the first region to form an alignment state. Liquid crystal element. 27. The liquid crystal is a chiral smectic liquid crystal which takes a phase transition from a liquid phase to a smectic liquid crystal phase. When the temperature is lowered, the liquid crystal substantially becomes in contact with the substrate in the first region selectively provided in the phase transition process of the liquid crystal. The transition from the liquid crystal region to the smectic liquid crystal phase occurred in contact with the surface in the direction parallel to, and the smectic liquid crystal phase transition region was continuously expanded along the uniaxial orientation processing direction of the first region to form an alignment state. 20. The liquid crystal device according to claim 19, wherein: 28. The method according to claim 28, wherein the first region having the uniaxial alignment regulating force is selectively provided only on one of the substrates, and the liquid crystal is composed of a chiral smectic liquid crystal that takes a phase transition from a liquid phase to a smectic liquid crystal phase. In the course of the liquid crystal phase transition, the transition from the liquid crystal region in contact with the surface substantially parallel to the substrate in the first region to the smectic liquid crystal phase occurs at the time of the temperature drop, and the transition along the uniaxial alignment processing axis of the first region occurs. 20. The liquid crystal device according to claim 19, wherein the smectic liquid crystal phase transition region is expanded to form an alignment state. 29. The liquid crystal display according to claim 26, wherein the first region having the uniaxial alignment regulating force is selectively provided in a shape continuous in the same direction as the direction of the smectic layer constituting the liquid crystal. The liquid crystal element according to the above. 30. An alignment control layer pattern comprising a plurality of stripes having a longitudinal direction which is the same as the direction of the smectic layer constituting the liquid crystal, wherein the selectively formed first region having a uniaxial alignment regulating force is provided. Claims 26 to 2
9. The liquid crystal element according to any one of 8. 31. The alignment control layer is provided between adjacent stripes of the alignment control layer such that a length of the smectic layer in a normal direction of one stripe portion of the alignment control layer in the pattern including the plurality of stripes is provided. 31. The liquid crystal element according to claim 30, wherein the length of the smectic layer in the non-existent portion is shorter than the length in the normal direction. 32. A substrate provided with a first region having a uniaxial alignment regulating force, wherein a total plane area of the first region is smaller than a total plane area other than the first region.
The liquid crystal element according to the above. 33. The liquid crystal device according to claim 19, wherein the first region having a uniaxial alignment regulating force is a surface region of an alignment control layer obtained by rubbing an organic insulating film, which is substantially parallel to the substrate. 34. The liquid crystal device according to claim 33, wherein the organic insulating film is made of polyimide. 35. A second region on at least one substrate side corresponding to the second liquid crystal region has a volume resistance of 1.0 ×.
20. A layer comprising 10 ^{4 to} 1.0 × 10 ¹⁰ Ωcm.
The liquid crystal element according to the above. 36. A film formed of a polycrystalline or amorphous metal oxide, a film formed of a polycrystalline or amorphous semiconductor, wherein at least one second region corresponding to the second liquid crystal region on the substrate side comprises: 20. The liquid crystal device according to claim 19, comprising a film in which conductive fine particles are dispersed in an insulating base material. 37. A substrate having a first region having a uniaxial alignment regulating force, wherein a second region in contact with the second liquid crystal region has substantially no uniaxial alignment regulating force, and 20. The liquid crystal device according to claim 19, wherein an alignment control layer forming a first region having a uniaxial alignment regulating force is selectively provided on a layer forming a second region substantially free of the following. 38. A layer constituting a second region substantially free of a uniaxial alignment regulating force in contact with the second liquid crystal region,
The liquid crystal element according to claim 37, wherein the layer has a volume resistance of 1.0 × 10 ^{4 to} 1.0 × 10 ¹⁰ Ωcm. 39. A layer constituting a second region substantially not having a uniaxial alignment regulating force in contact with the second liquid crystal region,
38. The liquid crystal element according to claim 37, comprising a film made of a polycrystalline or amorphous metal oxide, a film made of a polycrystalline or amorphous semiconductor, and a film in which conductive fine particles are dispersed in an insulating base material. 40. A stripe-shaped electrode group is provided on each of the pair of substrates, and the electrode groups on each substrate form a matrix structure, and the first group has a selectively provided uniaxial alignment regulating force. 20. The liquid crystal device according to claim 19, wherein the region is selectively provided at least in a portion where the electrodes of each substrate do not intersect. 41. The liquid crystal has a structure in which a terminal portion of a fluorocarbon and a hydrocarbon portion are bonded by a central nucleus, and contains at least one fluorine-containing liquid crystal compound having a smectic intermediate phase or a potential smectic intermediate phase. The liquid crystal device according to any one of claims 26 to 28, which is a chiral smectic liquid crystal composition. 42. A pair of substrates having the liquid crystal is sandwiched between a pair of polarizing plates, modulates light passing through the liquid crystal element to indicate at least a bright state and a dark state, and selectively switches the at least one substrate. 2. The liquid crystal device according to claim 1, wherein the liquid crystal molecules corresponding to the provided first region having the uniaxial alignment regulating force have liquid crystal molecules fixed at positions where a dark state is indicated. 43. A liquid crystal between the substrates comprises a plurality of real driving regions which are separated from each other.
43. The liquid crystal device according to claim 42, wherein the first region having the uniaxial alignment regulating force is selectively provided. 44. A stripe-shaped electrode group is provided on each of the pair of substrates, and the electrode groups on each substrate are opposed to each other;
43. The liquid crystal device according to claim 42, wherein the first region having a matrix structure and having the uniaxial alignment regulating force is selectively provided at least in a portion where the electrodes of each substrate do not intersect. 45. The liquid crystal device according to claim 44, wherein the stripe-shaped electrode is formed by attaching a metal to a transparent conductive film. 46. The liquid crystal device according to claim 42, wherein a liquid phase-liquid crystal phase transition temperature of a liquid crystal region in contact with the first region is higher than a liquid phase-liquid crystal phase transition temperature of a liquid crystal region in contact with the second region. . 47. The liquid crystal exhibits a smectic liquid crystal phase, and a transition from a liquid crystal region in contact with the first region to a smectic liquid crystal phase occurs in a phase transition process of the liquid crystal when the temperature is lowered, and the first region is uniaxially oriented. 43. The liquid crystal device according to claim 42, wherein the smectic liquid crystal phase transition region is continuously expanded along the axial direction to form an alignment state. 48. The liquid crystal is a chiral smectic liquid crystal that undergoes a phase transition from a liquid phase to a smectic liquid crystal phase, and contacts a surface substantially parallel to the substrate in the first region during a phase transition process of the liquid crystal when the temperature is lowered. A transition from a liquid crystal region to a smectic liquid crystal phase occurs, and the smectic liquid crystal phase transition region continuously expands along the uniaxial orientation processing axis direction of the first region, and an alignment state is formed. 43. The liquid crystal device according to claim 42. 49. A first region having the uniaxial alignment regulating force is selectively provided only on one of the substrates, and the liquid crystal is composed of a chiral smectic liquid crystal that takes a phase transition from a liquid phase to a smectic liquid crystal phase. During the phase transition process of the liquid crystal at the time of temperature drop, a transition from a liquid crystal region in contact with a plane substantially parallel to the substrate of the first region to a smectic liquid crystal phase occurs, and the first region moves along a uniaxial alignment axis direction. 43. The liquid crystal device according to claim 42, wherein the smectic liquid crystal phase transition region is continuously expanded to form an alignment state. 50. The device according to claim 47, wherein the first region of the at least one substrate is selectively provided in a shape continuous in the same direction as the direction of the smectic layer constituting the liquid crystal. Liquid crystal element. 51. The selectively formed first region having a uniaxial alignment regulating force is formed of a plurality of stripes whose longitudinal direction is the same as the direction of the smectic layer constituting the liquid crystal. 50. The liquid crystal device according to any one of claims 47 to 49, comprising a pattern. 52. The alignment control layer is provided between adjacent stripes of the alignment control layer such that the length of the smectic layer in the normal direction of one stripe portion of the alignment control layer in the pattern including the plurality of stripes is provided. 52. The liquid crystal element according to claim 51, wherein the liquid crystal element is shorter than a length of the smectic layer in a normal direction in a portion where no smectic layer exists. 53. A substrate provided with a first region having a uniaxial alignment regulating force, wherein a total plane area of the first region is smaller than a total plane area other than the first region.
The liquid crystal element according to the above. 54. The liquid crystal device according to claim 1, wherein the first region having a uniaxial alignment regulating force is a surface region substantially parallel to a substrate on which an organic insulating film has been rubbed. 55. An alignment control layer forming the first region having the uniaxial alignment regulating force and a material forming a layer in contact with the liquid crystal in the second region are made of different materials.
2. The liquid crystal element according to 2. 56. A layer in contact with the liquid crystal in the second region has substantially no uniaxial alignment regulating force, and the layer in contact with the liquid crystal in the second region has conductive fine particles dispersed in a base material. The liquid crystal device according to claim 55, which is a film. 57. The liquid crystal device according to claim 42, wherein an alignment control layer having substantially no uniaxial alignment control force is provided on the other substrate, and the alignment control layer contacts the liquid crystal over the entire surface. 58. In the substrate having the first region, a layer forming the second region is provided on the entire surface of the substrate, and an alignment forming a first region having a uniaxial alignment regulating force is provided on the layer. 43. The liquid crystal device according to claim 42, wherein the control layer is selectively provided. 59. In the substrate having the first region, a layer forming the second region is provided on the entire surface of the substrate, and an alignment forming a first region having a uniaxial alignment regulating force is provided on the layer. 58. The liquid crystal device according to claim 57, wherein a control layer is selectively provided. 60. A liquid crystal composition comprising a fluorine-containing liquid crystal compound having a smectic intermediate phase or a latent smectic intermediate phase, wherein the liquid crystal has a structure in which a terminal portion of a fluorocarbon and a hydrocarbon portion are bonded by a central nucleus. 43. The liquid crystal device according to claim 42. 61. The at least one substrate,
2. The liquid crystal element according to claim 1, wherein a layer constituting the first region and a layer constituting the surface of the second region are made of the same material. 62. The thickness of a layer constituting the first region is larger than the thickness of a layer constituting the second region.
The liquid crystal element according to the above. 63. A layer constituting the first region and a layer constituting the second region are formed by forming a film having a uniform thickness and then patterning the film to selectively form the first region. 63. The liquid crystal device according to claim 62, wherein a function of the second region is provided. 64. A liquid crystal part comprising: a first liquid crystal region in which liquid crystal molecules near a substrate interface corresponding to the first region of the at least one substrate and a bulk liquid crystal molecule between the substrates are in a substantially continuous alignment state. The liquid crystal molecules near the substrate interface corresponding to the second region of the at least one substrate and the second liquid crystal region in which bulk liquid crystal molecules between the substrates are in a discontinuous alignment state. Item 64. The liquid crystal element according to any one of Items 61 to 63. 65. The liquid crystal part comprises a plurality of real driving regions separated from each other, the real driving region corresponds to the second liquid crystal region, and the region between the real driving regions is the liquid crystal region. 7. The device according to claim 6, which corresponds to a first liquid crystal region constituting the portion.
4. The liquid crystal element according to 4. 66. Both a layer constituting a first region of the substrate and a layer constituting a second region of the at least one substrate are provided on a layer in which conductive fine particles are dispersed in a base material. 65. The liquid crystal device according to claim 64, wherein: 67. A pair of substrates having the liquid crystal interposed between a pair of polarizing plates, modulating light passing through the liquid crystal element, indicating at least a bright state and a dark state, and at least one of the pair of substrates. 63. A liquid crystal portion corresponding to a selectively provided first region having a uniaxial alignment regulating force, in which liquid crystal molecules are fixed at a position where a dark state is indicated. A liquid crystal element according to any one of the above. 68. The liquid crystal part is composed of a plurality of real driving regions separated from each other and the first liquid crystal region is selectively provided between the real driving regions. Liquid crystal element. 69. A stripe-shaped electrode group is provided on each of the pair of substrates, and the electrode groups of each substrate face each other;
68. The liquid crystal device according to claim 67, wherein a first region having a matrix structure and having the uniaxial alignment regulating force is selectively provided at least in a portion where electrodes of each substrate do not intersect. 70. At least one of the pair of substrates is an active matrix substrate including a plurality of pixel electrodes and switching elements corresponding to the pixel electrodes, and a first region of the at least one substrate has at least the switching region. 2. The liquid crystal element according to claim 1, wherein the liquid crystal element is provided along the arrangement of the elements. 71. A liquid crystal having a liquid crystal between a pair of substrates, being in contact with the liquid crystal on at least one substrate side, and substantially parallel to a substrate having a uniaxial alignment regulating force with respect to at least the selectively provided liquid crystal. In a liquid crystal element having one region and a second region in which the uniaxial alignment regulating force on the liquid crystal is weak or has substantially no uniaxial alignment regulating force compared to the first region outside the first region. By gradually cooling the liquid crystal between the substrates from the liquid phase, a transition from a portion in contact with the first region to a liquid crystal phase occurs during a phase transition process between the liquid phase and the liquid crystal phase between the substrates when the temperature is lowered. A step of growing a liquid crystal phase transition region along a uniaxial orientation axis in the first region and continuously expanding the liquid crystal phase transition region in the second region to form an alignment state. Orientation control method. 72. A method for manufacturing a liquid crystal element having a liquid crystal between a pair of substrates, wherein at least one of the substrates is substantially parallel to a substrate having a uniaxial alignment regulating force with respect to at least a selectively provided liquid crystal. A pair of substrates having a first region and a second region having a weak uniaxial alignment regulating force for liquid crystal as compared to the first region outside the first region or having substantially no uniaxial alignment regulating force. Forming a cell by facing each other, injecting liquid crystal into the cell, and gradually cooling the liquid crystal between the substrates injected into the cell from the liquid phase, so that the liquid Causing a transition from a portion in contact with the first region to a liquid crystal phase in a phase transition process of the liquid crystal phase, and growing a liquid crystal phase transition region along a uniaxial alignment axis in the first region; Liquid crystal phase transition region is continuously expanded Forming a liquid crystal element. 73. A film made of a material forming the second region and a film made of a material forming the first region are formed on at least one of the first region and the second region. 73. The liquid crystal according to claim 72, wherein the liquid crystal is formed by selectively removing and patterning the film of the material constituting the first region after sequentially forming the layer, and exposing the second region in the removed region. Device manufacturing method. 74. The method according to claim 73, wherein the material forming the first region is an organic insulator, and patterning of the film of the material forming the first region is performed by UV ashing. . 75. A material constituting the surface of the first region and the surface of the second region is the same, and a film made of the material constituting the first and second regions is formed on at least one substrate. 73. The method according to claim 72, wherein the film is selectively removed and patterned to form a first region and a second region depending on whether or not the film is removed. 76. The method according to claim 75, wherein a material forming the first region and the second region is an organic insulator, and the film is patterned by UV ashing.