JP2008256941A - Alignment-treated substrate for ferroelectric liquid crystal, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alignment-treated substrate for a ferroelectric liquid crystal, with which alignment of the ferroelectric liquid crystal is controlled without arranging a partition wall, and to provide a liquid crystal display element. <P>SOLUTION: The alignment-treated substrate for the ferroelectric liquid crystal is characteristically provided with: a substrate; an electrode layer formed on the substrate; a stripe shaped wettability changing pattern which is formed on the electrode layer and has alternately arranged lyophilic regions and lyophobic regions; and an alignment layer formed on the lyophilic regions. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an alignment-treated substrate for a ferroelectric liquid crystal used for a liquid crystal display element using a ferroelectric liquid crystal, and a liquid crystal display element.

  Liquid crystal display elements have been widely used from large displays to portable information terminals because of their thinness and low power consumption, and their development is actively underway. So far, liquid crystal display elements have been developed and put to practical use, such as TN mode, STN multiplex drive, and active matrix drive using thin layer transistors (TFTs) for TN, but these use nematic liquid crystals. In addition, the response speed of the liquid crystal material is as slow as several ms to several tens of ms, and it cannot be said that it is sufficiently compatible with moving image display.

  Ferroelectric liquid crystal (FLC) is a liquid crystal suitable for high-speed devices because its response speed is as short as μs order. Ferroelectric liquid crystal is widely known as a bistable one proposed by Clark and Lagerwol and having two stable states when no voltage is applied (upper part of FIG. 19).

In recent years, the state of a liquid crystal layer when a voltage is not applied has been stabilized in one state (hereinafter referred to as “monostable”). ) Is continuously changed, and the transmitted light intensity is analog-modulated so that gradation display is possible (Non-Patent Document 1, lower part of FIG. 19). As the liquid crystal exhibiting monostability, a ferroelectric liquid crystal that changes phase with the cholesteric (Ch) phase-chiral smectic C (SmC ^* ) phase in the temperature lowering process and does not pass through the smectic A (SmA) phase is usually used.

In addition, as the ferroelectric liquid crystal, a liquid crystal exhibiting a phase change between a cholesteric (Ch) phase, a smectic A (SmA) phase, and a chiral smectic C (SmC ^* ) phase in the temperature lowering process and exhibiting an SmC ^* phase via the SmA phase. There are materials. Among the ferroelectric liquid crystals currently reported, the liquid crystal material having a phase series that passes through the latter SmA phase is more than the former liquid crystal material that does not pass through the SmA phase. It is known that a ferroelectric liquid crystal having a phase sequence passing through the latter SmA phase usually has two stable states with respect to a single layer normal (FIG. 21 lower stage).

  Ferroelectric liquid crystals are difficult to align because they have higher molecular ordering than nematic liquid crystals. In particular, in a ferroelectric liquid crystal that does not pass through the SmA phase, two regions having different layer normal directions (hereinafter referred to as “double domain”) are generated (the upper part of FIG. 21). Such a double domain becomes a serious problem because black-and-white inversion is displayed during driving. On the other hand, the ferroelectric liquid crystal passing through the SmA phase has a chevron structure in which the distance between the smectic layers is reduced in the process of phase change and the smectic layer is bent to compensate for the volume change. As a result, domains having different major axis directions of liquid crystal molecules are formed, and alignment defects called zigzag defects and hairpin defects are likely to occur at the boundary surfaces. Such a defect causes a decrease in contrast due to light leakage.

As a method for improving the zigzag defect and the hairpin defect, a method is disclosed in which a plurality of linear partition walls are formed substantially parallel to the uniaxial alignment treatment direction of the alignment film to provide a linear space (for example, Patent Documents). 1). By confining the ferroelectric liquid crystal in this linear space, the flow of liquid crystal molecules is induced substantially parallel to the longitudinal direction of the linear partition. As a result, the orientation of the ferroelectric liquid crystal is improved, and an SmC ^* phase having no alignment defect is formed.

  As a method for improving the double domain, a method is disclosed in which a plurality of partition walls are formed between substrates so that the molecular direction in the monostable state of the ferroelectric liquid crystal and the extending direction of the partition walls are substantially the same. (For example, refer to Patent Document 2).

According to the method of providing these partition walls, not only the alignment control of the ferroelectric liquid crystal but also the impact resistance of the liquid crystal display element can be improved. Since the SmC ^* phase is very vulnerable to external impact, the high impact resistance is useful in a liquid crystal display element using a ferroelectric liquid crystal.

  In addition, as a liquid crystal sealing method, a vacuum injection method and a liquid crystal dropping (One Drop Fill: ODF) method are known. Patent Document 2 discloses that both a vacuum injection method and a liquid crystal dropping method can be applied as a method for encapsulating a ferroelectric liquid crystal when a liquid crystal display element provided with a partition wall is manufactured.

JP 2000-111184 A JP 2006-39519 A NONAKA, T., LI, J., OGAWA, A., HORNUNG, B., SCHMIDT, W., WINGEN, R., and DUBAL, H., 1999, Liq. Cryst., 26, 1599.

  When a liquid crystal display element using such a ferroelectric liquid crystal and provided with a partition is applied to a small display such as a portable information terminal, the line width of the partition needs to be relatively narrow. In general, a photolithography method using a photosensitive resin is known as a method for forming a partition, but it is difficult to form a partition with a very narrow line width by the photolithography method.

  In the liquid crystal display element provided with the partition walls, the ferroelectric liquid crystal is confined in the space partitioned by the partition walls, so that the cell gap changes due to expansion and contraction accompanying the temperature change of the ferroelectric liquid crystal. Unevenness may be visually recognized.

  The present invention has been made in view of the above problems, and mainly provides an alignment-treated substrate for a ferroelectric liquid crystal and a liquid crystal display element capable of controlling the alignment of the ferroelectric liquid crystal without providing a partition wall. Objective.

  In order to achieve the above object, the present invention provides a base material, an electrode layer formed on the base material, and a striped lyophilic region and liquid repellent region alternately formed on the electrode layer. There is provided an alignment-treated substrate for a ferroelectric liquid crystal, characterized by having a wettability change pattern arranged on the liquid crystal and an alignment film formed on the lyophilic region.

According to the present invention, since the alignment film is formed on the lyophilic region and the lyophobic region is exposed, a liquid crystal display element is produced using the alignment substrate for ferroelectric liquid crystal of the present invention. At that time, by utilizing the wettability difference between the alignment film and the liquid repellent region, the ferroelectric liquid crystal is sealed between the alignment film of the alignment substrate for the ferroelectric liquid crystal and the alignment film of the counter substrate, The ferroelectric liquid crystal can not be filled between the liquid-repellent region of the alignment substrate for ferroelectric liquid crystal and the counter substrate. Thereby, the ferroelectric liquid crystal can be sealed in the linear space without providing the partition, and the orientation of the ferroelectric liquid crystal can be improved as in the case where the conventional partition is provided.
Furthermore, in the liquid crystal display device using the alignment substrate for ferroelectric liquid crystal according to the present invention, the ferroelectric liquid crystal is filled between the liquid repellent region of the alignment substrate for ferroelectric liquid crystal and the counter substrate. Since the pressure is reduced, the followability to expansion / contraction associated with the temperature change of the ferroelectric liquid crystal can be improved. Further, the adhesion strength between the two substrates can be improved by the pressure difference between the decompressed portion in the decompressed state and the outside of the liquid crystal display element at the atmospheric pressure.

  In the above invention, a wettability changing layer in which wettability is changed by the action of a photocatalyst accompanying energy irradiation is formed between the electrode layer and the alignment film, and the wettability changing pattern is formed on the wettability changing layer surface. It may be formed. Since the wettability change layer changes the wettability by the action of the photocatalyst accompanying energy irradiation, the wettability change layer easily irradiates the surface of the wettability change layer by irradiating the wettability change layer with energy in a pattern. It is because it can form.

  Moreover, in the said invention, the resin layer containing a fluorine is formed in the surface between the patterns of the said alignment film on the said electrode layer, The said resin layer surface is the said liquid repellent area | region, and the said opening in the opening part of the said resin layer The electrode layer surface may be the lyophilic region. By irradiating the resin layer with plasma using a fluorine compound as an introduction gas, only the resin layer can contain fluorine. The surface of the resin layer can be easily made liquid-repellent and the electrode layer surface in the opening of the resin layer can be easily formed. This is because it can be a lyophilic region.

  Furthermore, in the present invention, it is preferable that the liquid repellent area is provided in a non-display area. As described above, since the ferroelectric liquid crystal is not filled between the liquid-repellent region of the alignment substrate for ferroelectric liquid crystal and the counter substrate, the liquid-repellent region is a non-display region that does not affect the image display. It is preferable that it is provided.

  In the present invention, a minute lyophilic region that connects the lyophilic region adjacent to the lyophobic region across the lyophobic region may be formed. Similar to the lyophilic region, the minute lyophilic region is a region having a relatively small contact angle with the liquid, and usually an alignment film is formed on the minute lyophilic region. Since the minute lyophilic region connects adjacent lyophilic regions, when the liquid crystal display element is produced using the ferroelectric liquid crystal alignment substrate of the present invention, the ferroelectric liquid crystal alignment substrate. The ferroelectric liquid crystal sealed between the lyophilic region and the counter substrate can be allowed to flow between the micro lyophilic region of the alignment substrate for ferroelectric liquid crystal and the counter substrate. Thereby, the variation in the amount of the ferroelectric liquid crystal sealed between the alignment film of the alignment substrate for ferroelectric liquid crystal and the alignment film of the counter substrate can be reduced.

  Furthermore, in the present invention, a reactive liquid crystal layer formed by immobilizing reactive liquid crystals may be formed on the alignment film. Since the reactive liquid crystal is aligned by the alignment film and the alignment state is fixed, the reactive liquid crystal layer can function as an alignment film for aligning the ferroelectric liquid crystal. Reactive liquid crystals are relatively similar in structure to ferroelectric liquid crystals, so they interact strongly with ferroelectric liquid crystals and control alignment more effectively than when only an alignment film is used. be able to.

  The present invention is also formed on the above-mentioned alignment substrate for ferroelectric liquid crystal, the second base material, the second electrode layer formed on the second base material, and the second electrode layer. The second alignment film is disposed so that the alignment film of the alignment substrate for ferroelectric liquid crystal and the second alignment film of the counter substrate face each other, and the alignment film and the second alignment film There is provided a liquid crystal display element characterized in that a ferroelectric liquid crystal is sandwiched therebetween.

According to the present invention, since the alignment substrate for ferroelectric liquid crystal described above is used, as described above, the ferroelectric is interposed between the alignment film of the alignment substrate for ferroelectric liquid crystal and the second alignment film of the counter substrate. The liquid crystal is enclosed, and the ferroelectric liquid crystal cannot be filled between the liquid-repellent region of the alignment substrate for the ferroelectric liquid crystal and the counter substrate. The alignment of the ferroelectric liquid crystal can be improved by enclosing the dielectric liquid crystal in a linear space.
Further, as described above, the ferroelectric liquid crystal is not filled between the liquid-repellent region of the alignment substrate for the ferroelectric liquid crystal and the counter substrate, and the pressure is reduced, so that the temperature of the ferroelectric liquid crystal is changed. The followability to expansion / contraction can be improved, and the occurrence of display unevenness can be suppressed. Further, the adhesion strength between the two substrates can be improved by the pressure difference between the decompressed portion in the decompressed state and the outside of the liquid crystal display element at the atmospheric pressure.

  In the present invention, the counter substrate may be the above-described alignment substrate for ferroelectric liquid crystal. In this case, it is preferable that the liquid-repellent regions of the alignment substrates for ferroelectric liquid crystal face each other. . This is because the region filled with the ferroelectric liquid crystal and the region not filled with the ferroelectric liquid crystal become clearer.

  In the present invention, by utilizing the difference in wettability of the wettability change pattern, it is possible to enclose the ferroelectric liquid crystal in a linear space without providing a partition wall, thereby improving the orientation of the ferroelectric liquid crystal. There is an effect that can be made. In addition, since the ferroelectric liquid crystal is not filled between the liquid-repellent region of the alignment substrate for the ferroelectric liquid crystal and the counter substrate, the pressure is reduced, so that the expansion and contraction due to the temperature change of the ferroelectric liquid crystal is prevented. There is an effect that the followability is improved and the adhesion strength between the two substrates can be improved.

  Hereinafter, the alignment substrate for ferroelectric liquid crystal and the liquid crystal display element of the present invention will be described in detail.

A. First, the alignment substrate for ferroelectric liquid crystal according to the present invention will be described.
The alignment substrate for ferroelectric liquid crystal according to the present invention comprises a base material, an electrode layer formed on the base material, a striped lyophilic region and a liquid repellent region formed on the electrode layer. It has a wettability change pattern arranged alternately and an alignment film formed on the lyophilic region.

The alignment substrate for ferroelectric liquid crystal of the present invention will be described with reference to the drawings.
FIG. 1 is a plan view showing an example of the alignment substrate for ferroelectric liquid crystal of the present invention, and FIG. 2 is a cross-sectional view taken along the line AA of FIG. As illustrated in FIGS. 1 and 2, in the alignment substrate 1 for ferroelectric liquid crystal, the electrode layer 3 is formed on the base material 2, and the wettability changing layer 4 is formed on the electrode layer 3. A wettability changing pattern in which stripe-like lyophilic regions 5a and liquid repellent regions 5b are alternately arranged is formed on the surface of the wettability changing layer 4, and an alignment film 6 is formed on the lyophilic region 5a. Yes. In FIG. 1, the base material and the electrode layer are omitted.

  FIG. 3 is a cross-sectional view showing an example of a liquid crystal display element using the alignment substrate for ferroelectric liquid crystal of the present invention. In the liquid crystal display element 30 illustrated in FIG. 3, two alignment substrates 1 and 1 ′ for ferroelectric liquid crystal face each other, and each of these alignment substrates 1 and 1 ′ for ferroelectric liquid crystal is opposed. A ferroelectric liquid crystal is sandwiched between the alignment films 6 and 6 ′ to form a liquid crystal layer 31. As described above, the alignment substrates 1 and 1 ′ for the ferroelectric liquid crystal have the electrode layers 3, 3 ′ and the wettability changing layers 4, 4 ′ formed on the substrates 2, 2 ′, respectively. A wettability changing pattern in which stripe-like lyophilic regions 5a, 5a 'and lyophobic regions 5b, 5b' are alternately arranged is formed on the surface of the property-changing layers 4, 4 ', and the lyophilic regions 5a, Alignment films 6 and 6 'are formed on 5a'. The two alignment processing substrates 1 and 1 'for ferroelectric liquid crystal face the respective alignment films 6 and 6', that is, the respective lyophilic regions 5a and 5a ', and the respective liquid repellent regions 5b and 5b. It is arranged so that ′ faces each other. Further, between the liquid repellent regions 5b and 5b ′, the ferroelectric liquid crystal is not filled, and a decompressed portion 32 is formed.

  For example, when producing a liquid crystal display element using the alignment substrate for ferroelectric liquid crystal according to the present invention, the ferroelectric liquid crystal is dropped on the alignment substrate for ferroelectric liquid crystal, as illustrated in FIG. In addition, the ferroelectric liquid crystal is dropped on the alignment film 6 and the liquid repellent region 5b of the alignment substrate 1 for ferroelectric liquid crystal. At this time, since the liquid repellent region 5 b is a region having a relatively large contact angle with the liquid, the ferroelectric liquid crystal hardly flows into the liquid repellent region 5 b and flows on the alignment film 6. Subsequently, the alignment substrate for ferroelectric liquid crystal on which the ferroelectric liquid crystal is dropped and the other alignment processing substrate for ferroelectric liquid crystal are opposed to each other, are superposed under reduced pressure, and are bonded through a sealing material. At this time, when the pressure between the two substrates is reduced in an inert gas atmosphere such as nitrogen gas or the air atmosphere, the liquid-repellent regions 5b and 5b ′ are bonded to each other as illustrated in FIG. The space between the two is filled with an inert gas or air without being filled with the ferroelectric liquid crystal, and becomes a decompressed portion 32. At this time, when the two substrates are evacuated, the space between the liquid-repellent regions 5b and 5b ′ is formed as a ferroelectric layer after the two substrates are bonded, as illustrated in FIG. The liquid crystal is not filled and is in a vacuum state, and a vacuum portion (reduced pressure portion) 32 is formed.

According to the present invention, the wettability change pattern in which stripe-like lyophilic regions and lyophobic regions are alternately arranged is formed, and the alignment film is formed only on the lyophilic region, and the lyophobic property Since the region is exposed, the ferroelectric liquid crystal can be enclosed in the linear space without providing a partition wall by utilizing the difference in wettability between the alignment film and the liquid repellent region. Thereby, the orientation of the ferroelectric liquid crystal can be improved as in the case where the conventional partition is provided.
In addition, since it is not necessary to provide a partition wall, the alignment substrate for ferroelectric liquid crystal of the present invention can be suitably used for a small display.

  Further, in the liquid crystal display device using the alignment substrate for ferroelectric liquid crystal of the present invention, the alignment substrate for ferroelectric liquid crystal and the counter substrate corresponding to the liquid-repellent region of the alignment substrate for ferroelectric liquid crystal. Since a reduced pressure part is provided between them, even if the ferroelectric liquid crystal expands or contracts as the temperature changes, the reduced pressure part can follow the volume change of the ferroelectric liquid crystal, and the cell gap is reduced. Can be kept constant. Thereby, it is possible to suppress the occurrence of display unevenness.

  Furthermore, in the liquid crystal display element using the alignment substrate for ferroelectric liquid crystal according to the present invention, the alignment for ferroelectric liquid crystal is caused by the pressure difference between the reduced pressure portion in a reduced pressure state and the outside of the liquid crystal display element at atmospheric pressure. A uniform pressure is always applied between the processing substrate and the counter substrate from the outside. For this reason, the adhesion strength between the alignment substrate for ferroelectric liquid crystal and the counter substrate can be increased.

Further, according to the present invention, since the wettability change pattern is formed, the alignment film can be easily patterned by utilizing the wettability difference between the lyophilic region and the liquid repellent region of the wettability change pattern. Can be formed.
Hereinafter, each structure of the alignment processing substrate for ferroelectric liquid crystal according to the present invention will be described.

1. Wettability change pattern The wettability change pattern in the present invention is formed on the electrode layer, and stripe-like lyophilic regions and lyophobic regions are alternately arranged.

  Here, the liquid repellent region refers to a region having a larger contact angle with respect to the liquid than the lyophilic region. Specifically, the contact angle with respect to the liquid in the liquid-repellent region is preferably 10 ° or more larger than the contact angle with respect to the liquid in the lyophilic region.

  In the liquid repellent region, it is preferable that a contact angle with respect to a liquid having a surface tension equivalent to the surface tension of the alignment film forming coating solution is larger by 40 ° or more. This is because if the contact angle with the liquid in the liquid repellent region is too small, the alignment film forming coating liquid may adhere to the liquid repellent region.

  In the lyophilic region, the contact angle with respect to a liquid having a surface tension equivalent to the surface tension of the coating liquid for forming an alignment film is preferably 30 ° or less, more preferably 10 ° or less. This is because if the contact angle with the liquid in the lyophilic region is too large, the alignment film-forming coating solution is difficult to spread and the alignment film may be lost.

  The contact angle with the liquid is measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions. 30 seconds later), and can be obtained from the result or in the form of a graph. In this measurement, a wetting index standard solution manufactured by Junsei Co., Ltd. is used as the liquid having various surface tensions.

  The formation position of the liquid repellent region is preferably a non-display region in a liquid crystal display element using the ferroelectric liquid crystal alignment substrate of the present invention. That is, the liquid repellent area is preferably provided in the non-display area. As illustrated in FIG. 3, the space between the liquid-repellent regions 5b and 5b ′ is not filled with ferroelectric liquid crystal, and an image cannot be displayed. It is preferable that a liquid repellent region is provided on the surface.

FIGS. 4 to 7 show examples in which the liquid repellent area is provided in the non-display area.
4 and 5 show examples in which the alignment substrate for ferroelectric liquid crystal of the present invention has a colored layer and a light shielding portion. 4 is a plan view, and FIG. 5 is a cross-sectional view taken along line BB in FIG. In the alignment substrate 1 for ferroelectric liquid crystal exemplified in FIGS. 4 and 5, the light shielding portion 11 is formed in a matrix on the base material 2, and the colored layer 12 is formed in the opening of the light shielding portion 11, The electrode layer 3 and the wettability changing layer 4 are formed on the colored layer 12, and the wettability changing pattern including the lyophilic region 5 a and the liquid repellent region 5 b is formed on the surface of the wettability changing layer 4. An alignment film 6 is formed on 5a. The area where the light shielding portions 11 are provided in a matrix is the non-display area 13, and the liquid repellent area 5 b is provided in the non-display area 13. In this case, the liquid repellent region is preferably disposed on the light shielding portion.
In FIG. 4, the base material, the light shielding portion, the colored layer, and the electrode layer are omitted.

6 and 7 show examples in which the alignment substrate for ferroelectric liquid crystal of the present invention has a gate electrode, a source electrode, a drain electrode, and a thin film transistor (TFT). 6 is a plan view, and FIG. 7 is a cross-sectional view taken along the line CC of FIG. In the alignment substrate 1 for ferroelectric liquid crystal exemplified in FIG. 6 and FIG. 7, the pixel electrode 21 as the electrode layer 3, the gate electrode 22 a and the source electrode 22 b arranged vertically and horizontally on the base material 2, A drain electrode 22c connected to the pixel electrode 21 and a TFT 23 serving as a switching element are formed, the wettability changing layer 4 is formed on the pixel electrode 21 and the like, and the lyophilic region 5a is formed on the wettability changing layer 4 surface. And the wettability change pattern which consists of the liquid repellent area | region 5b is formed, and the alignment film 6 is formed on the lyophilic area | region 5a. The region where the gate electrode 22 a, the source electrode 22 b, the drain electrode 22 c, and the TFT 23 are provided is the non-display region 13, and the liquid repellent region 5 b is provided in the non-display region 13. In this case, the liquid repellent region is preferably disposed on the source electrode.
In FIG. 6, the substrate is omitted, and the wettability changing layer, the wettability changing pattern, and the alignment film are partially omitted.

  The pattern shape of the lyophilic region and the liquid repellent region is a stripe shape, and the stripe-shaped lyophilic region and the liquid repellent region are alternately arranged and are usually arranged at equal intervals.

The pitch of the liquid repellent region is appropriately selected according to the pitch of the non-display region, for example, the pitch of the light shielding portion and the pitch of the source electrode. Specifically, the pitch of the liquid repellent region can be about 1 mm to 4 mm, preferably in the range of 1 mm to 3 mm, and more preferably in the range of 1.5 mm to 2.5 mm. If the pitch of the liquid repellent area is smaller than the above range, the display quality of the liquid crystal display element using the alignment substrate for ferroelectric liquid crystal according to the present invention is deteriorated due to poor alignment of the ferroelectric liquid crystal near the liquid repellent area. This is because there is a risk of lowering. Further, if the pitch of the liquid repellent regions is larger than the above range, it may be difficult to control the alignment of the ferroelectric liquid crystal.
The pitch of the liquid repellent area refers to the distance from the center to the center of the adjacent liquid repellent area.

  Further, the width of the liquid repellent region is appropriately selected according to the width of the non-display region, for example, the width of the light shielding portion or the width of the source electrode. Specifically, the width of the liquid repellent region can be about 3 μm to 50 μm, and preferably within a range of 5 μm to 20 μm.

  The pitch and width of the liquid repellent region can be confirmed using a scanning electron microscope (SEM).

  In the present invention, as illustrated in FIG. 8, the lyophilic region 5b is formed with a minute lyophilic region 8 connecting the adjacent lyophilic regions 5a across the lyophobic region 5b. Also good. Although not shown, an alignment film is usually formed on this microlyophilic region. In FIG. 8, the base material, the electrode layer, and the alignment film are omitted.

  When a liquid-repellent region is formed with a micro-lyophilic region, a ferroelectric liquid crystal alignment substrate is used when a liquid crystal display device is produced using the ferroelectric liquid crystal alignment substrate of the present invention. The ferroelectric liquid crystal can be allowed to flow between the alignment film formed on the minute lyophilic region and the counter substrate. For this reason, even if there is a variation in the amount of ferroelectric liquid crystal sealed between the alignment film formed on the lyophilic region of the alignment substrate for ferroelectric liquid crystal and the alignment film of the counter substrate, strong This variation can be reduced when the dielectric liquid crystal flows between the micro-lyophilic region of the alignment substrate for ferroelectric liquid crystal and the counter substrate. Thereby, the occurrence of display unevenness can be suppressed.

  As described above, in the liquid crystal display device using the alignment substrate for ferroelectric liquid crystal according to the present invention, the ferroelectric liquid crystal is caused by the pressure difference between the decompressed portion in the decompressed state and the outside of the liquid crystal display device in the atmospheric pressure. Therefore, a uniform pressure is always applied from the outside between the alignment processing substrate and the counter substrate. Thereby, the amount of ferroelectric liquid crystal sealed between the alignment substrate for ferroelectric liquid crystal and the counter substrate can be controlled uniformly. For this reason, the ferroelectric liquid crystal is efficiently allowed to flow between the micro-lyophilic region of the alignment substrate for ferroelectric liquid crystal and the counter substrate, and the variation in the amount of ferroelectric liquid crystal is effectively reduced. Can do it.

  The size of the minute lyophilic region may be any size as long as the ferroelectric liquid crystal can be circulated. In particular, in the longitudinal direction of the liquid-repellent region, the total length of each micro-lyophilic region formed in the liquid-repellent region with respect to the length of the liquid-repellent region (hereinafter referred to as the formation ratio of the micro-lyophilic region) Is preferably in the range of about 1% to 30%, more preferably in the range of 5% to 15%. This is because if the formation ratio is larger than the above range, the alignment of the ferroelectric liquid crystal may be impaired. If the formation ratio is smaller than the above range, the ferroelectric liquid crystal is less likely to flow between the alignment film formed on the micro-lyophilic region and the counter substrate, and the amount of the ferroelectric liquid crystal varies. This is because the effect of reducing the effect may not be sufficiently obtained.

  Here, as shown in FIG. 8, the formation ratio of the micro-lyophilic region is the sum of the length L of the liquid-repellent region 5b and the lengths M1, M2, and M3 of each micro-lyophilic region 8. The ratio (((M1 + M2 + M3) / L) × 100) with (M1 + M2 + M3).

  Further, the length of the micro-lyophilic region in the longitudinal direction of the liquid repellent region (for example, M1, M2, M3 in FIG. 8) is preferably about 0.01 mm to 0.3 mm, more preferably. Is in the range of 0.05 mm to 0.15 mm. This is because if the length of the minute lyophilic region is longer than the above range, the alignment of the ferroelectric liquid crystal may be impaired. Also, if the length of the micro-lyophilic region is shorter than the above range, the ferroelectric liquid crystal is less likely to flow between the micro-lyophilic region of the alignment substrate for ferroelectric liquid crystal and the counter substrate, This is because the effect of reducing variation in the amount of the ferroelectric liquid crystal may not be sufficiently obtained.

  Further, the number of micro-lyophilic regions is not particularly limited, and the number of micro-lyophilic regions formed in each liquid-repellent region may be one or plural. However, it is preferable that there are a plurality of them. This is because variation in the amount of ferroelectric liquid crystal can be effectively reduced by forming a plurality of micro-lyophilic regions in each liquid repellent region.

  Further, the number of minute lyophilic regions formed in each lyophobic region may be the same or different in all the lyophobic regions, but is preferably the same among them. This is because variations in the amount of ferroelectric liquid crystal can be further reduced.

  When a plurality of minute lyophilic regions are formed in each lyophobic region, the minute lyophilic regions may be formed at equal intervals or may be formed at different intervals. Preferably it is formed. This is because variations in the amount of ferroelectric liquid crystal can be further reduced.

  Further, when the minute lyophilic regions are formed at equal intervals, the positions where the minute lyophilic regions 8 are formed in all the liquid repellent regions 5b are the same as illustrated in FIG. Alternatively, as illustrated in FIG. 9, the position where the microlyophilic region 8 is formed may be different for each liquid repellent region 5b. Especially, it is preferable that the position where the microlyophilic region is formed in all the liquid repellent regions is the same. This is because variations in the amount of ferroelectric liquid crystal can be further reduced.

Further, in the case where a plurality of minute lyophilic regions are formed in each lyophobic region, the pitch of the minute lyophilic regions is not particularly limited, but may be about 0.1 mm to 5 mm. More preferably, it exists in the range of 0.5 mm-3 mm. This is because, if the pitch of the minute lyophilic region is within the above range, variation in the amount of ferroelectric liquid crystal can be effectively reduced.
In addition, the pitch of a micro lyophilic area | region means the distance from the center part of the micro lyophilic area | region which adjoins in one lyophobic area | region.

  The wettability change pattern in the present invention may be any pattern in which stripe-like lyophilic regions and liquid-repellent regions are alternately arranged, and two preferred embodiments can be mentioned. The first is a case where a wettability change pattern is formed on the surface of the wettability changing layer where the wettability changes due to the action of the photocatalyst accompanying energy irradiation. The second case is a case where the surface of the resin layer containing fluorine on the surface is a liquid repellent region, and the surface of the electrode layer in the opening of the resin layer is a lyophilic region. Each will be described below.

(1) Wettability changing layer In the present invention, as illustrated in FIGS. 1 and 2, the wettability in which the wettability changes between the electrode layer 3 and the alignment film 6 due to the action of a photocatalyst accompanying energy irradiation. The change layer 4 may be formed, and a wettability change pattern in which stripe-like lyophilic regions 5 a and liquid repellent regions 5 b are alternately arranged may be formed on the surface of the wettability change layer 4.

  In the wettability changing pattern formed on the wettability changing layer surface, the energy irradiated portion becomes a lyophilic region, and the non-energy irradiated portion becomes a liquid repellent region. That is, the lyophilic region is a region that has changed in a direction in which the contact angle with the liquid decreases due to energy irradiation.

  The wettability changing layer used in the present invention may not contain a photocatalyst or may contain a photocatalyst. Hereinafter, the case where the wettability changing layer does not contain a photocatalyst (first aspect) and the case where the wettability changing layer contains a photocatalyst (second aspect) will be described separately.

(I) 1st aspect The wettability change layer in this aspect is a photocatalyst process layer board | substrate with which the photocatalyst process layer containing a photocatalyst is formed on a base | substrate with energy irradiation with respect to a wettability change layer. It is a layer whose wettability changes so that the contact angle with the liquid is lowered by irradiating energy in a pattern after being arranged with a gap that can act as a photocatalyst. The wettability changing layer itself does not contain a photocatalyst. In this embodiment, since the wettability changing layer does not contain a photocatalyst, there is an advantage that the alignment substrate for ferroelectric liquid crystal of the present invention is not affected by the photocatalyst over time.

In this embodiment, as illustrated in FIG. 10, the photocatalyst processing layer substrate 51 in which the wettability changing layer 4 formed on the base material 2 and the electrode layer 3 and the photocatalyst processing layer 53 is formed on the substrate 52. Are arranged with a predetermined gap and irradiated with energy 56 through a photomask 55 (FIG. 10A), and the wettability of the energy irradiated portion on the surface of the wettability changing layer 4 is changed to make it lyophilic. By forming the region 5a, a wettability change pattern including the lyophilic region 5a and the liquid repellent region 5b can be formed (FIG. 10B). Then, an alignment film forming coating solution is applied on the lyophilic region 5a to form the alignment film 6 (FIG. 10C).
Hereinafter, the wettability changing layer, the photocatalyst processing layer substrate, and the wettability changing pattern forming method will be described.

(Wettability change layer)
The material used for the wettability changing layer in this embodiment is not particularly limited as long as the wettability is changed by the action of the photocatalyst upon energy irradiation, but is not easily degraded or decomposed by the action of the photocatalyst. A binder having a chain and an organic substituent that is decomposed by the action of a photocatalyst is preferred. As this binder, organopolysiloxane etc. can be mentioned, for example. Among these, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group.

  Examples of such an organopolysiloxane include (1) an organopolysiloxane that exerts great strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (2) water repellency and oil repellency. Organopolysiloxanes such as organopolysiloxanes obtained by crosslinking excellent reactive silicones can be used, and those described in JP2000-249821A and JP2003-195029A can be used.

  Further, the wettability changing layer may contain a surfactant, a decomposed substance, and other additives that cause the wettability change of the energy irradiation portion or assist the wettability change. As these additives, for example, those described in JP 2000-249821 A and JP 2003-195029 A can be used.

  The thickness of the wettability changing layer is preferably in the range of 0.001 μm to 1 μm, more preferably in the range of 0.01 μm to 0.1 μm, from the relationship of the wettability change rate by the photocatalyst.

(Photocatalyst treatment layer substrate)
The photocatalyst processing layer substrate in this embodiment has a base and a photocatalyst processing layer formed on the base and containing at least a photocatalyst.

  The photocatalyst treatment layer contains a photocatalyst. The photocatalyst treatment layer is not particularly limited as long as the photocatalyst in the photocatalyst treatment layer changes the wettability of the wettability changing layer surface. For example, the photocatalyst treatment layer may be composed of a photocatalyst and a binder, or may be composed of a photocatalyst alone. In the case of a photocatalyst treatment layer composed of only a photocatalyst, the efficiency with respect to the change in wettability of the wettability change layer surface is improved, which is advantageous in terms of cost such as shortening of the treatment time. Moreover, in the case of the photocatalyst processing layer which consists of a photocatalyst and a binder, it has the advantage that formation of a photocatalyst processing layer is easy.

As a photocatalyst used in the present invention, known as a photo semiconductor, for example, titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ). Bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ). These photocatalysts may be used alone or in combination of two or more.

  In the present invention, titanium dioxide is preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide has an anatase type and a rutile type, and both can be used. Among these, anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.

  Examples of the anatase type titanium dioxide include hydrochloric acid peptization type anatase type titania sol (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd., ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitrate peptization type Anatase-type titania sol (TA-15 (average particle diameter: 12 nm) manufactured by Nissan Chemical Co., Ltd.) and the like can be mentioned.

  Since the photocatalytic reaction occurs more effectively as the particle size is smaller, it is preferable that the particle size of the photocatalyst is smaller. Specifically, the average particle size of the photocatalyst is preferably 50 nm or less, and particularly preferably 20 nm or less.

The mechanism of action of the photocatalyst typified by titanium dioxide in the photocatalyst treatment layer is not necessarily clear, but the photocatalyst causes an oxidation-reduction reaction by irradiation of energy, and superoxide radical (.O ₂ ⁻ ) or hydroxy radical It is considered that active oxygen species such as (.OH) are generated and the generated active oxygen species change the chemical structure of the organic matter. In the present invention, it is considered that this active oxygen species acts on the organic matter in the wettability changing layer disposed in the vicinity of the photocatalyst treatment layer.

  Further, when the photocatalyst treatment layer is composed of a photocatalyst and a binder, the binder used preferably has a high binding energy such that the main skeleton is not decomposed by photoexcitation of the photocatalyst. As such a binder, for example, an organopolysiloxane or an amorphous silica precursor can be used, and those described in JP 2000-249821 A or JP 2003-195029 A can be used. it can.

  When the photocatalyst treatment layer is composed of a photocatalyst and a binder, the content of the photocatalyst in the photocatalyst treatment layer can be set within a range of 5 to 60% by weight, and preferably within a range of 20 to 50% by weight. Is within.

  Moreover, the photocatalyst processing layer may contain a surfactant and other additives. As these additives, for example, those described in JP 2000-249821 A and JP 2003-195029 A can be used.

  The thickness of the photocatalyst treatment layer is preferably in the range of 0.05 to 10 μm.

  The wettability of the photocatalyst treatment layer surface may be lyophilic or lyophobic.

  As the formation position of the photocatalyst treatment layer, for example, the photocatalyst treatment layer may be formed on the entire surface of the substrate, or the photocatalyst treatment layer may be formed in a pattern on the substrate. When the photocatalyst treatment layer is formed in a pattern, the photocatalyst treatment layer is arranged with a predetermined gap with respect to the wettability changing layer, and when irradiating energy, pattern irradiation is performed using a photomask or the like. The wettability of the wettability changing layer surface can be changed by irradiating the entire surface. In addition, since the wettability changes only on the surface of the wettability change layer that actually faces the photocatalyst treatment layer, the energy irradiation direction is such that energy is applied to the portion where the photocatalyst treatment layer and the wettability change layer face. Any direction is acceptable. Furthermore, the energy to be irradiated is not limited to parallel light such as parallel light.

  The substrate used for the photocatalyst processing layer substrate is appropriately selected for transparency depending on the energy irradiation direction described below. For example, when the electrode layer is opaque, the energy irradiation direction is necessarily from the photocatalyst processing layer substrate side. Further, for example, when a light shielding part is formed in a pattern on the photocatalyst processing layer substrate, and energy is irradiated in a pattern using the light shielding part, it is necessary to irradiate energy from the photocatalyst processing layer substrate side. Therefore, in these cases, the substrate needs to have transparency.

  Further, the base may be flexible, such as a resin film, or may not be flexible, such as a glass substrate.

  Although it does not specifically limit as a base | substrate, Since a photocatalyst processing layer board | substrate is used repeatedly, it has predetermined intensity | strength and the surface has favorable adhesiveness with a photocatalyst processing layer Are preferably used. Specifically, examples of the material constituting the substrate include glass, ceramic, metal, and plastic.

  On the photocatalyst processing layer substrate, a light shielding portion may be formed in a pattern. In the case of using a photocatalyst processing layer substrate having a patterned light-shielding portion, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, in this case, since alignment between the photocatalyst processing layer substrate and the photomask is unnecessary, it can be a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary. This is advantageous in terms of cost.

  As the formation position of the light shielding portion, for example, the light shielding portion may be formed in a pattern on the substrate, and the photocatalytic treatment layer may be formed so as to cover the light shielding portion, or the photocatalytic treatment layer is formed on the substrate, The light-shielding part may be formed in a pattern on the photocatalyst treatment layer, or the light-shielding part may be formed in a pattern on the surface of the base on which the photocatalyst treatment layer is not formed.

  When the light-shielding part is formed on the substrate and when the light-shielding part is formed on the photocatalyst processing layer, the photocatalyst processing layer and the wettability changing layer are compared with the case of using a photomask. Since the light shielding portion is disposed in the vicinity of the portion disposed with a gap, it is possible to reduce the influence of energy scattering in the substrate or the like. For this reason, it becomes possible to perform pattern irradiation of energy very accurately.

  Further, when a light shielding part is formed on the photocatalyst processing layer, when the photocatalyst processing layer and the wettability changing layer are arranged with a predetermined gap, the thickness of the light shielding part is set to the distance of the gap. By making them coincide with each other, a light shielding portion can be used as a spacer for making the gap constant. That is, when the photocatalyst treatment layer and the wettability changing layer are arranged with a predetermined gap, the predetermined gap can be maintained by arranging the light shielding portion and the wettability changing layer in close contact with each other. . And in this state, a wettability change pattern can be accurately formed on the wettability change layer surface by irradiating energy from the photocatalyst processing layer substrate.

  Further, in the case where the light shielding part is formed on the surface of the base on which the photocatalyst treatment layer is not formed, for example, the photomask can be attached to the surface of the light shielding part to the extent that it can be attached and detached. This method is suitable for the case where the manufacturing is changed in a small lot.

(Method of forming wettability change pattern)
In this embodiment, the photocatalyst-treated layer substrate is disposed with a gap where the action of the photocatalyst accompanying energy irradiation can reach the wettability changing layer. Usually, the photocatalyst processing layer of the photocatalyst processing layer substrate and the wettability changing layer are arranged with a gap where the action of the photocatalyst accompanying energy irradiation can reach the wettability changing layer. The gap includes a state in which the photocatalyst processing layer and the wettability changing layer are in contact with each other.

  Specifically, the distance between the photocatalyst treatment layer and the wettability changing layer is preferably 200 μm or less. By disposing the photocatalyst treatment layer and the wettability changing layer at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. If the distance between the photocatalyst treatment layer and the wettability changing layer is wider than the above range, the active oxygen species generated by the photocatalytic action may not easily reach the wettability changing layer, and the wettability change rate may be slowed down. There is. Conversely, if the interval between the photocatalyst treatment layer and the wettability changing layer is too narrow, the active oxygen species generated by oxygen, water, and photocatalytic action will be difficult to desorb, resulting in a slow change in wettability. There is a possibility.

  In consideration of the fact that the pattern accuracy is very good, the sensitivity of the photocatalyst is high, and the efficiency of wettability change is good, the distance is more preferably in the range of 0.2 μm to 20 μm, and still more preferably. It is in the range of 1 μm to 10 μm.

  On the other hand, when manufacturing a liquid crystal display element having a large area of, for example, 300 mm × 300 mm, it is extremely difficult to provide the fine gap as described above between the photocatalyst processing layer substrate and the wettability changing layer. Therefore, when manufacturing a liquid crystal display element having a relatively large area, the gap is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 75 μm. By setting the gap to be in the above range, it is possible to suppress a decrease in pattern accuracy such as a blurred pattern, and it is possible to suppress deterioration of the sensitivity of the photocatalyst and deterioration of the wettability change efficiency. It is.

  In addition, when energy irradiation is performed on a relatively large area as described above, the gap setting in the positioning device between the photocatalyst processing layer substrate and the wettability changing layer in the energy irradiation device is within the range of 10 μm to 200 μm. In particular, it is preferable to set within the range of 25 μm to 75 μm. By setting the set value of the gap within the above range, the photocatalyst-treated layer substrate and the wettability changing layer are arranged without contact with each other without causing a significant decrease in pattern accuracy or a significant deterioration in the sensitivity of the photocatalyst. Because it can.

  In the present invention, such an arrangement state with a gap need only be maintained at least during energy irradiation.

  As a method of arranging such a very narrow gap uniformly and arranging the photocatalyst processing layer and the wettability changing layer, for example, a method using a spacer can be mentioned. In the method using the spacer, a uniform gap can be provided, and the portion where the spacer contacts is not affected by the photocatalyst on the surface of the wettability changing layer. By having this pattern, it becomes possible to form a predetermined wettability change pattern on the wettability change layer surface.

  In the present invention, the spacer may be formed as a single member, but it is preferable that the spacer is formed on the photocatalyst treatment layer of the photocatalyst treatment layer substrate in order to simplify the process. In this case, there are advantages as described in the section of the light shielding portion.

  The spacer only needs to have an action of protecting the wettability changing layer surface so that the photocatalytic action does not reach the wettability changing layer surface. For this reason, the spacer does not need to have a shielding property against the irradiated energy.

  Further, after the photocatalyst treatment layer and the wettability changing layer are arranged with a predetermined gap, the wettability changing pattern is formed on the surface of the wettability changing layer by pattern irradiation with energy from a predetermined direction.

  The wavelength of light used for energy irradiation is usually set in a range of 450 nm or less, preferably in a range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst treatment layer is titanium dioxide, and light having the above wavelength is preferred as energy for activating the photocatalytic action by the titanium dioxide.

Examples of light sources that can be used for energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
Moreover, as a method of irradiating energy in a pattern, using these light sources and irradiating a pattern through a photomask, a method of drawing and irradiating in a pattern using a laser such as an excimer or YAG is used. You can also.

The energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for changing the wettability of the wettability changing layer surface by the action of the photocatalyst in the photocatalyst treatment layer.
At this time, it is preferable to irradiate energy while heating the photocatalyst treatment layer. This is because the sensitivity can be increased and the wettability can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

  The energy irradiation direction is determined by whether or not a light shielding portion is formed on the photocatalyst processing layer substrate. For example, when a light shielding part is formed on the photocatalyst processing layer substrate and the base of the photocatalyst processing layer substrate is transparent, energy irradiation is performed from the photocatalyst processing layer substrate side. Further, in this case, when the light shielding portion is formed on the photocatalyst processing layer and this light shielding portion functions as a spacer, the energy irradiation direction may be from the photocatalyst processing layer substrate side or from the substrate side. May be. Also, for example, when the photocatalyst treatment layer is formed in a pattern, the energy irradiation direction can be any as long as the energy is applied to the portion where the photocatalyst treatment layer and the wettability changing layer face as described above. It may be a direction. Similarly, in the case of using the above-described spacer, the energy irradiation direction may be any direction as long as energy is irradiated to the portion where the photocatalyst processing layer and the wettability changing layer face. Further, for example, when a photomask is used, energy is irradiated from the side where the photomask is disposed. In this case, the side on which the photomask is arranged needs to be transparent.

  After the energy irradiation, the photocatalyst processing layer substrate is removed from the wettability changing layer.

(Ii) 2nd aspect The wettability change layer in this aspect is a layer which contains a photocatalyst and wettability changes so that a contact angle with a liquid may fall by the effect | action of the photocatalyst accompanying energy irradiation. In this embodiment, since the wettability changing layer contains a photocatalyst, there is an advantage that the wettability can be changed efficiently.

  In this embodiment, as illustrated in FIG. 11, energy 56 is irradiated to the wettability changing layer 4 formed on the substrate 2 and the electrode layer 3 through the photomask 55 (FIG. 11A). ) By changing the wettability of the energy irradiated portion on the surface of the wettability changing layer 4 to form the lyophilic region 5a, a wettability changing pattern composed of the lyophilic region 5a and the lyophobic region 5b is formed. (FIG. 11 (b)). Then, an alignment film forming coating solution is applied on the lyophilic region 5a to form the alignment film 6 (FIG. 11C).

  The wettability changing layer is not particularly limited as long as it contains a photocatalyst, and may be, for example, a single layer containing a photocatalyst and a material whose wettability is changed by the action of the photocatalyst. The layer containing a material whose wettability is changed by the photocatalyst and the layer containing the photocatalyst may be laminated. When the wettability changing layer is a single layer containing a photocatalyst and a material whose wettability changes due to the action of the photocatalyst, the wettability changes due to the action of the photocatalyst contained in the layer itself. The wettability can be changed efficiently. In addition, when the wettability changing layer is formed by laminating a layer containing a material whose wettability is changed by the photocatalyst and a layer containing the photocatalyst, the layer containing the photocatalyst and the alignment film are not brought into direct contact with each other. Therefore, the alignment film can be prevented from being influenced by the photocatalyst over time.

  When the wettability changing layer is a single layer containing a photocatalyst and a material whose wettability changes due to the action of the photocatalyst, the material that changes the wettability used for this wettability changing layer can be used for energy irradiation. The material is not particularly limited as long as the wettability is changed by the action of the photocatalyst, but has a main chain that is difficult to be degraded and decomposed by the action of the photocatalyst and has an organic substituent that is decomposed by the action of the photocatalyst. A binder is preferred. As this binder, the binder described in the section of the wettability changing layer of the first aspect can be used.

  Note that the photocatalyst is the same as that described in the first aspect, and therefore the description thereof is omitted here.

  Content of the photocatalyst in the said wettability change layer can be set in the range of 5 to 60 weight%, Preferably it exists in the range of 20 to 40 weight%.

  Further, the thickness of the wettability changing layer is preferably 0.001 μm to 1 μm, more preferably 0.01 μm to 0.1 μm, in view of the wettability change rate by the photocatalyst.

  On the other hand, when the wettability changing layer is a laminate of a layer containing a material whose wettability is changed by the photocatalyst and a layer containing a photocatalyst, it is used for a layer containing a material whose wettability is changed by the photocatalyst. The material is not particularly limited as long as the wettability is changed by the action of the photocatalyst associated with energy irradiation, but has a main chain that is not easily degraded or decomposed by the action of the photocatalyst. Binders with organic substituents that are decomposed are preferred. Note that the layer containing a material whose wettability is changed by the photocatalyst is the same as the wettability changing layer of the first aspect, and thus the description thereof is omitted here.

  Further, the layer containing the photocatalyst is not particularly limited as long as it contains the photocatalyst. For example, the layer containing the photocatalyst may be composed of a photocatalyst and a binder, or may be composed of a single photocatalyst. There may be. In addition, about the layer containing a photocatalyst, since it is the same as that of the photocatalyst processing layer of the said 1st aspect, description here is abbreviate | omitted.

  In this embodiment, the wettability changing layer is irradiated with energy from a predetermined direction to form a wettability changing layer on the wettability changing layer surface. In addition, about energy irradiation etc., since it is the same as that of what was described in the said 1st aspect, description here is abbreviate | omitted.

(2) Resin layer In the present invention, a resin layer containing fluorine is formed on the surface between the alignment film patterns on the electrode layer, the resin layer surface is a liquid repellent region, and the electrode layer in the opening of the resin layer The surface may be a lyophilic region.

  12 and 13 show an example in which a resin layer containing fluorine is formed on the surface. 12 is a plan view, and FIG. 13 is a cross-sectional view taken along the line DD of FIG. In the alignment substrate 1 for ferroelectric liquid crystal exemplified in FIGS. 12 and 13, the electrode layer 3 is formed on the base material 2, and the resin layer 7 containing fluorine on the surface is striped on the electrode layer 3. The surface of the resin layer 7 is a liquid-repellent region 5b, and the surface of the electrode layer 3 in the opening of the resin layer 7 is a lyophilic region 5a. The stripe-shaped lyophilic region 5a and the liquid-repellent region A wettability change pattern in which 5b are alternately arranged is formed, and an alignment film 6 is formed on the lyophilic region 5a.

  In the present invention, the surface of the resin layer can be made to contain fluorine by irradiating the resin layer surface with plasma using a fluorine compound as an introduction gas. The surface of the electrode layer in the part can be a lyophilic region.

  Generally, a metal, a metal oxide, etc. are used for an electrode layer. In plasma irradiation using a fluorine compound as an introduction gas, a fluorine compound can be introduced only into an organic substance. Therefore, fluorine can be selectively introduced into a resin layer composed of a resin that is an organic substance. It can be liquid repellent. Thereby, the contact angle with the liquid on the resin layer surface can be made relatively higher than the contact angle with the liquid on the electrode layer surface.

  For example, as shown in FIG. 14, the resin layer 7 formed in a stripe shape on the base material 2 and the electrode layer 3 is irradiated with plasma 57 using a fluorine compound as an introduction gas (FIG. 14 (a)). By introducing fluorine into the surface of the layer 7 to make it liquid repellent, the surface of the resin layer 7 can be made the liquid repellent region 5b, and the surface of the electrode layer 3 in the opening of the resin layer 7 can be made the lyophilic region 5a. (FIG. 14B). Then, an alignment film forming coating solution is applied on the lyophilic region 5a to form the alignment film 6 (FIG. 14C).

  In the wettability change pattern formed on the surface of the electrode layer on which the resin layer is formed, as described above, the resin layer surface becomes a liquid repellent region, and the electrode layer surface in the opening of the resin layer is lyophilic. Become an area. That is, the liquid repellent region is a region that has changed in a direction in which the contact angle with the liquid is increased by plasma irradiation using a fluorine compound as an introduction gas.

Examples of the fluorine compound used as the introduction gas include carbon fluoride (CF ₄ ), fluorine nitride (NF ₃ ), sulfur fluoride (SF ₆ ), CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , and C _5. F ₈ and the like.

  Moreover, you may mix and use a fluorine compound and other gas as introduction gas. As other gas, nitrogen, oxygen, argon, helium etc. can be mentioned, for example. Among these, nitrogen is preferably used. When nitrogen is used, the mixing ratio of nitrogen is preferably 60% or more.

  The plasma irradiation method is not particularly limited as long as the method can irradiate the plasma using a fluorine compound as an introduction gas and make the resin layer surface liquid-repellent. For example, under reduced pressure Plasma irradiation may be performed, and plasma irradiation may be performed under atmospheric pressure. Among these, it is preferable to perform plasma irradiation under atmospheric pressure. In this case, it is advantageous in terms of cost, production efficiency, etc., without requiring a decompression device or the like.

  The plasma irradiation conditions are appropriately selected depending on the irradiation apparatus or the like. Examples of the atmospheric pressure plasma irradiation conditions include the following. For example, a general plasma irradiation apparatus can be used as the power output. At this time, the distance between the irradiated plasma electrode and the resin layer is preferably about 0.2 mm to 20 mm, and more preferably about 1 mm to 5 mm. The flow rate of the fluorine compound used as the introduction gas is preferably about 1 L / min to 20 L / min, and the flow rate of nitrogen flowing simultaneously with the fluorine compound is preferably about 1 L / min to 50 L / min. . The substrate transport speed at this time is preferably about 0.5 m / min to 2 m / min.

  The presence of fluorine introduced into the resin layer is the result of X-ray photoelectron spectroscopy (XPS: ESCALAB) used in X-ray photoelectron spectroscopy (also referred to as ESCA (Electron Spectroscopy for Chemical Analysis)). In the analysis by 220i-XL), it can be confirmed by measuring the proportion of fluorine element in all elements detected from the surface of the resin layer. At this time, the proportion of fluorine introduced into the resin layer is preferably 10% or more of all elements detected from the surface of the resin layer.

In addition, the resin layer has a contact angle with a liquid having a surface tension equivalent to the surface tension of the alignment film forming coating solution that is 1 ° or more higher than the contact angle with the liquid of the resin layer before plasma irradiation. Plasma irradiation is preferable.
The method for measuring the contact angle with the liquid is as described above.

  The height of the resin layer is usually about the same as the thickness of the alignment film, and is set to about 100 nm to 1000 nm.

  The material for forming the resin layer is not particularly limited as long as it is a resin, but among these, a photosensitive resin is preferably used. This is because the photosensitive resin is easy to pattern. The photosensitive resin is not particularly limited as long as it is generally used for a member of a liquid crystal display element.

  The method for forming the resin layer is not particularly limited as long as the resin layer can be formed at a predetermined position, and a general patterning method can be applied. For example, a photolithography method, an inkjet method, a screen printing method, and the like can be given.

2. Alignment film The alignment film used in the present invention is formed on the lyophilic region and controls the alignment of the ferroelectric liquid crystal.

  The alignment film is not particularly limited as long as the alignment of the ferroelectric liquid crystal can be controlled. For example, a rubbing alignment film subjected to rubbing treatment, a photo alignment film subjected to photo alignment treatment, or the like is used. Can be used. Among these, it is preferable to use a photo-alignment film. This is because the photo-alignment process is a non-contact alignment process, which is useful in that it does not generate static electricity or dust and can quantitatively control the alignment process. Hereinafter, the photo-alignment film will be described.

(1) Photo-alignment film A photo-alignment film is obtained by irradiating a substrate on which a constituent material of a photo-alignment film, which will be described later, is applied with light with controlled polarization to cause a photoexcitation reaction (decomposition, isomerization, dimerization). The liquid crystal molecules on the film are aligned by imparting anisotropy to the film.

  The constituent material of the photo-alignment film used in the present invention is particularly limited as long as it has an effect of aligning ferroelectric liquid crystals (photoalignment) by irradiating light and causing a photoexcitation reaction. It is not a thing. As such materials, there are large photoreactive materials that impart anisotropy to the photoalignment film by causing a photoreaction, and anisotropy is imparted to the photoalignment film by causing a photoisomerization reaction. It can be divided into photoisomerization type materials.

The wavelength region of the light that causes the photo-excited reaction of the constituent material of the photo-alignment film is preferably in the ultraviolet light range, that is, in the range of 10 nm to 400 nm, and more preferably in the range of 250 nm to 380 nm.
Hereinafter, the photoreactive material and the photoisomerization type material will be described.

(I) Photoreactive type First, a photoreactive type material will be described. As described above, the photoreactive material is a material that imparts anisotropy to the photoalignment film by causing a photoreaction. The photoreactive material used in the present invention is not particularly limited as long as it has such characteristics. Among these, the photo-alignment is caused by causing a photodimerization reaction or a photodecomposition reaction. A material that imparts anisotropy to the film is preferred.

  Here, the photodimerization reaction refers to a reaction in which a reaction site oriented in the polarization direction by light irradiation undergoes radical polymerization and two molecules are polymerized. This reaction stabilizes the orientation in the polarization direction and makes the photo-alignment film different. It is possible to impart directionality. The photolysis reaction is a reaction that decomposes molecular chains such as polyimide oriented in the polarization direction by light irradiation. This reaction leaves a molecular chain oriented in the direction perpendicular to the polarization direction, and is different from the photo-alignment film. It is possible to impart directionality. In the present invention, among these photoreactive materials, it is more preferable to use a material that imparts anisotropy to the photoalignment film by a photodimerization reaction because of high exposure sensitivity and a wide range of material selection. .

  The photoreactive material utilizing the photodimerization reaction is not particularly limited as long as it is a material that can impart anisotropy to the photoalignment film by the photodimerization reaction, but it is a radical polymerizable functional group. It is preferable to include a photodimerization reactive compound having dichroism that has different absorption depending on the polarization direction. This is because by radical polymerization of the reaction site oriented in the polarization direction, the orientation of the photodimerization reactive compound is stabilized and anisotropy can be easily imparted to the photo-alignment film.

  Examples of the photodimerization reactive compound having such characteristics include a dimerization reactive polymer having at least one reactive site selected from cinnamate ester, coumarin, quinoline, chalcone group and cinnamoyl group as a side chain. Can do.

  Among these, the photodimerization reactive compound is preferably a dimerization reactive polymer containing cinnamate, coumarin or quinoline as a side chain. This is because anisotropy can be easily imparted to the photo-alignment film by radical polymerization of α and β unsaturated ketone double bonds aligned in the polarization direction as reaction sites.

  The main chain of the dimerization reactive polymer is not particularly limited as long as it is generally known as a polymer main chain, but the reaction sites of the side chains such as aromatic hydrocarbon groups are not limited. It is preferable that it does not have a substituent containing a lot of π electrons that hinders the interaction.

  The weight average molecular weight of the dimerization reactive polymer is not particularly limited, but is preferably in the range of 5,000 to 40,000, and is preferably in the range of 10,000 to 20,000. Is more preferable. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. If the weight average molecular weight of the dimerization reactive polymer is too small, it may not be possible to impart appropriate anisotropy to the photo-alignment film. On the other hand, if it is too large, the viscosity of the coating liquid at the time of forming the photo-alignment film becomes high and it may be difficult to form a uniform coating film.

  As a dimerization reactive polymer, the compound represented by following formula (1) can be illustrated.

In the above formula, M ¹¹ and M ¹² each independently represent a monomer unit of a monopolymer or a copolymer. Examples thereof include ethylene, acrylate, methacrylate, 2-chloroacrylate, acrylamide, methacrylamide, 2-chloroacrylamide, styrene derivatives, maleic acid derivatives, and siloxane. M ¹² may be acrylonitrile, methacrylonitrile, methacrylate, methyl methacrylate, hydroxyalkyl acrylate or hydroxyalkyl methacrylate. x and y represent the molar ratio of each monomer unit in the case of a copolymer, and are numbers satisfying 0 <x ≦ 1, 0 ≦ y <1 and satisfying x + y = 1, respectively. It is. n represents an integer of 4 to 30,000. D ¹ and D ² represent a linking group unit.

R ¹ is a group represented by -A ^1- (Z ¹ -B ¹ ) _z -Z ^2- , and R ² is represented by -A ^1- (Z ¹ -B ¹ ) _z -Z ^3-. It is a group. Here, A ¹ and B ¹ are each independently a covalent single bond, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,3-dioxane-2, It represents 5-diyl or 1,4-phenylene which may have a substituent. Z ¹ and Z ² are each independently a covalent single bond, —CH ₂ —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CONR—, —RNCO—, —COO— or — Represents OOC-. R is a hydrogen atom or a lower alkyl group, and Z ³ is a hydrogen atom or an alkyl or alkoxy having 1 to 12 carbon atoms, which may have a substituent, cyano, nitro, or halogen. z is an integer of 0-4. E ¹ represents a photodimerization reaction site, and examples thereof include cinnamic acid ester, coumarin, quinoline, chalcone group, cinnamoyl group and the like. j and k are each independently 0 or 1.

  Specific examples of such a dimerization reactive polymer include compounds represented by the following formulas (1-1) to (1-4).

  More specific examples of the dimerization reactive polymer include compounds represented by the following formulas (1-5) to (1-8).

  In the present invention, as the photodimerization reactive compound, various photodimerization reaction sites and substituents can be selected from the above-mentioned compounds according to required characteristics. Moreover, the photodimerization reactive compound can also be used individually by 1 type or in combination of 2 or more types.

  In addition to the photodimerization reactive compound, the photoreactive material using photodimerization reaction may contain an additive within a range that does not interfere with the photoalignment property of the photoalignment film. Examples of the additive include a polymerization initiator and a polymerization inhibitor.

  The polymerization initiator or polymerization inhibitor may be appropriately selected from generally known compounds according to the type of the photodimerization reactive compound. The addition amount of the polymerization initiator or the polymerization inhibitor is preferably in the range of 0.001% by weight to 20% by weight, and in the range of 0.1% by weight to 5% by weight with respect to the photodimerization reactive compound. It is more preferable that This is because if the addition amount of the polymerization initiator or polymerization inhibitor is too small, the polymerization may not be started (prohibited), whereas if too large, the reaction may be inhibited.

  Examples of the photoreactive material utilizing photolysis reaction include polyimide “RN1199” manufactured by Nissan Chemical Industries, Ltd. Examples of the photoreactive material using photodimerization reaction include “ROP102” and “ROP103” manufactured by Rolic technologies.

(Ii) Photoisomerization type Next, a photoisomerization type material will be described. The photoisomerization type material here is a material that imparts anisotropy to the photo-alignment film by causing a photoisomerization reaction as described above, and is particularly limited as long as it has such characteristics. However, it is preferable to include a photoisomerization reactive compound that imparts anisotropy to the photoalignment film by causing a photoisomerization reaction. By including such a photoisomerization-reactive compound, a stable isomer among a plurality of isomers is increased by light irradiation, so that anisotropy can be easily imparted to the photo-alignment film. It is.

  The photoisomerization reactive compound is not particularly limited as long as it is a material having the above-mentioned characteristics, but has a dichroism that makes absorption different depending on the polarization direction, and can be irradiated by light irradiation. It is preferable that it causes an isomerization reaction. This is because anisotropy can be easily imparted to the photo-alignment film by causing isomerization of the reaction site oriented in the polarization direction of the photoisomerization-reactive compound having such characteristics.

  Further, the photoisomerization reaction in which the photoisomerization reactive compound is generated is preferably a cis-trans isomerization reaction. This is because either the cis isomer or the trans isomer is increased by light irradiation, whereby anisotropy can be imparted to the photo-alignment film.

  Examples of the photoisomerization-reactive compound include a monomolecular compound and a polymerizable monomer that is polymerized by light or heat. These may be selected as appropriate according to the type of ferroelectric liquid crystal used, but the anisotropy is imparted to the photo-alignment film by light irradiation, and then the anisotropy is stabilized by polymerizing. Therefore, it is preferable to use a polymerizable monomer. Among such polymerizable monomers, an acrylate monomer and a methacrylate monomer are preferable because anisotropy is imparted to the photo-alignment film and the polymer can be easily polymerized while maintaining the anisotropy in a good state. .

  The polymerizable monomer may be a monofunctional monomer or a polyfunctional monomer. However, since the anisotropy of the photo-alignment film due to polymerization becomes more stable, the bifunctional monomer It is preferable that

  Specific examples of such a photoisomerization-reactive compound include compounds having a cis-trans isomerization-reactive skeleton such as an azobenzene skeleton or a stilbene skeleton.

  In this case, the number of cis-trans isomerization reactive skeletons contained in the molecule may be one or two or more, but the alignment control of the ferroelectric liquid crystal becomes easy. Two are preferable.

  The cis-trans isomerization reactive skeleton may have a substituent in order to further enhance the interaction with the liquid crystal molecules. The substituent is not particularly limited as long as it can enhance the interaction with the liquid crystal molecules and does not interfere with the orientation of the cis-trans isomerization reactive skeleton, and examples thereof include a carboxyl group and a sulfonic acid. A sodium group, a hydroxyl group, etc. are mentioned. These structures can be appropriately selected depending on the type of ferroelectric liquid crystal used.

In addition to the cis-trans isomerization reactive skeleton, the photoisomerization reactive compound contains many π electrons such as aromatic hydrocarbon groups so that the interaction with the liquid crystal molecules can be further enhanced. It may have an included group, and the cis-trans isomerization reactive skeleton and the aromatic hydrocarbon group may be bonded via a bonding group. The bonding group is not particularly limited as long as it can enhance the interaction with the liquid crystal molecule. For example, —COO—, —OCO—, —O—, —C≡C—, —CH ₂ —CH _2- , —CH ₂ O—, —OCH ₂ — and the like can be mentioned.

  In addition, when using a polymerizable monomer as a photoisomerization reactive compound, it is preferable to have the said cis-trans isomerization reactive skeleton as a side chain. By having the cis-trans isomerization reactive skeleton as a side chain, the effect of anisotropy imparted to the photo-alignment film becomes larger, and is particularly suitable for controlling the alignment of ferroelectric liquid crystals Because it becomes. In this case, the aromatic hydrocarbon group or bonding group contained in the molecule is contained in the side chain together with the cis-trans isomerization reactive skeleton so that the interaction with the liquid crystal molecule is enhanced. It is preferable.

  Further, the side chain of the polymerizable monomer may have an aliphatic hydrocarbon group such as an alkylene group as a linking group so that the cis-trans isomerization reactive skeleton can be easily oriented.

  Among the photoisomerization reactive compounds of the monomolecular compound or polymerizable monomer as described above, the photoisomerization reactive compound used in the present invention is preferably a compound having an azobenzene skeleton in the molecule. This is because the azobenzene skeleton contains a lot of π electrons, and thus has a high interaction with liquid crystal molecules and is particularly suitable for controlling the alignment of ferroelectric liquid crystals.

  Hereinafter, the reason why an anisotropy can be imparted to the photo-alignment film by causing the azobenzene skeleton to undergo a photoisomerization reaction will be described. First, when the azobenzene skeleton is irradiated with linearly polarized ultraviolet light, the trans azobenzene skeleton having the molecular long axis oriented in the polarization direction is changed to a cis isomer as shown in the following formula.

  Since the cis isomer of the azobenzene skeleton is chemically unstable compared to the trans isomer, it thermally or absorbs visible light and returns to the trans isomer. Whether to become the right transformer body occurs with the same probability. Therefore, if the ultraviolet light is continuously absorbed, the ratio of the right-side trans isomer increases, and the average orientation direction of the azobenzene skeleton becomes perpendicular to the polarization direction of the ultraviolet light. In the present invention, by utilizing this phenomenon, the alignment direction of the azobenzene skeleton is aligned, anisotropy is imparted to the photo-alignment film, and the alignment of liquid crystal molecules on the film can be controlled.

  Among such compounds having an azobenzene skeleton in the molecule, examples of the monomolecular compound include compounds represented by the following formula (2).

In the above formula, R ⁴¹ each independently represents a hydroxy group. R ⁴² is _{^{- (A 41 -B 41 -A 41}} ) m - (D 41) n - represents a linking group represented ^{by, R 43} is _{^{(D 41) n - (A}} 41 -B 41 -A 41) _m represents a linking group represented by-. Here, A ⁴¹ represents a divalent hydrocarbon group, B ⁴¹ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NHCOO— or —OCONH—, and m represents Represents an integer of 0 to 3; D ⁴¹ represents a divalent hydrocarbon group when m is 0, and —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NHCOO— when m is an integer of 1 to 3. Alternatively, -OCONH- is represented, and n represents 0 or 1. R ⁴⁴ each independently represents a halogen atom, a carboxy group, a halogenated methyl group, a halogenated methoxy group, a cyano group, a nitro group, a methoxy group or a methoxycarbonyl group. However, the carboxy group may form a salt with an alkali metal. R ⁴⁵ each independently represents a carboxy group, a sulfo group, a nitro group, an amino group or a hydroxy group. However, the carboxy group or the sulfo group may form a salt with the alkali metal.

  Specific examples of the compound represented by the above formula include compounds represented by the following formulas (2-1) to (2-4).

  Moreover, as a polymerizable monomer which has the said azobenzene skeleton as a side chain, the compound represented by following formula (3) can be mentioned, for example.

In the above formula, each R ⁵¹ is independently (meth) acryloyloxy group, (meth) acrylamide group, vinyloxy group, vinyloxycarbonyl group, vinyliminocarbonyl group, vinyliminocarbonyloxy group, vinyl group, isopropenyloxy. Represents a group, isopropenyloxycarbonyl group, isopropenyliminocarbonyl group, isopropenyliminocarbonyloxy group, isopropenyl group or epoxy group. R ⁵² is _{^{- (A 51 -B 51 -A 51}} ) m - (D 51) n - represents a linking group represented ^{by, R 53} is _{^{(D 51) n - (A}} 51 -B 51 -A 51) _m represents a linking group represented by-. Here, A ⁵¹ represents a divalent hydrocarbon group, B ⁵¹ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NHCOO— or —OCONH—, and m represents Represents an integer of 0 to 3; D ⁵¹ represents a divalent hydrocarbon group when m is 0, and when m is an integer of 1 to 3, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NHCOO— Alternatively, -OCONH- is represented, and n represents 0 or 1. R ⁵⁴ each independently represents a halogen atom, a carboxy group, a halogenated methyl group, a halogenated methoxy group, a cyano group, a nitro group, a methoxy group or a methoxycarbonyl group. However, the carboxy group may form a salt with an alkali metal. R ⁵⁵ each independently represents a carboxy group, a sulfo group, a nitro group, an amino group or a hydroxy group. However, the carboxy group or the sulfo group may form a salt with the alkali metal.

  Specific examples of the compound represented by the above formula include compounds represented by the following formulas (3-1) to (3-4).

  In the present invention, various cis-trans isomerization reactive skeletons and substituents can be selected from such photoisomerization reactive compounds according to required characteristics. In addition, these photoisomerization reactive compounds can also be used individually by 1 type or in combination of 2 or more types.

  The photoisomerization type material used in the present invention may contain additives in addition to the above-mentioned photoisomerization reactive compound as long as the photoalignment property of the photoalignment film is not hindered. When a polymerizable monomer is used as the photoisomerization reactive compound, examples of the additive include a polymerization initiator and a polymerization inhibitor.

  The polymerization initiator or polymerization inhibitor may be appropriately selected from generally known compounds according to the type of photoisomerization reactive compound. The addition amount of the polymerization initiator or the polymerization inhibitor is preferably in the range of 0.001% by weight to 20% by weight, and in the range of 0.1% by weight to 5% by weight with respect to the photoisomerization reactive compound. More preferably, it is within. This is because if the addition amount of the polymerization initiator or polymerization inhibitor is too small, the polymerization may not be started (prohibited), whereas if too large, the reaction may be inhibited.

(Iii) Forming method of photo-alignment film In order to form the photo-alignment film in the present invention, first, a photo-alignment film-forming coating solution obtained by diluting the constituent material of the photo-alignment film with an organic solvent is applied and dried. In this case, the content of the photodimerization reactive compound or the photoisomerization reactive compound in the photoalignment film forming coating solution is preferably in the range of 0.05 wt% to 10 wt%. More preferably, it is in the range of 2 wt% to 2 wt%. If the content is less than the above range, it becomes difficult to impart appropriate anisotropy to the alignment film. Conversely, if the content is more than the above range, the viscosity of the photo-alignment film-forming coating solution increases. This is because it becomes difficult to form a uniform coating film.

  The method for applying the photo-alignment film forming coating solution is not particularly limited as long as it is a method capable of applying the photo-alignment film forming coating solution onto the lyophilic region. Coating method, roll coating method, rod bar coating method, spray coating method, air knife coating method, slot die coating method, wire bar coating method, dip coating method, blade coating method, micro gravure coating method, gravure coating method, casting method, inkjet Method, LB method, flexographic printing method, offset printing method, screen printing method and the like can be used.

  The thickness of the film obtained by applying the coating liquid for forming a photo-alignment film is preferably in the range of 1 nm to 2000 nm, more preferably in the range of 3 nm to 100 nm. This is because if the thickness of the film is thinner than the above range, sufficient optical alignment may not be obtained, and conversely, if the thickness is thicker than the above range, it may be disadvantageous in cost.

  Anisotropy is imparted to the obtained film by performing photo-alignment treatment. Specifically, by irradiating light with controlled polarization, an anisotropy can be imparted by causing a photoexcitation reaction. The wavelength range of the light to be irradiated may be appropriately selected according to the constituent material of the photo-alignment film to be used, but is preferably in the ultraviolet light range, that is, in the range of 100 nm to 400 nm, more preferably 250 nm. Within the range of ˜380 nm. The polarization direction is not particularly limited as long as it can cause the photoexcitation reaction.

  Further, when a polymerizable monomer is used as a constituent material of the photo-alignment film, among the photoisomerization-reactive compounds, after photo-alignment treatment, it is polymerized by heating and applied to the photo-alignment film. Anisotropy can be stabilized.

3. Electrode layer The electrode layer used for this invention will not be specifically limited if it is generally used as an electrode of a liquid crystal display element. The electrode layer may be transparent or opaque, and is appropriately selected according to the image display surface. In the liquid crystal display element using the alignment substrate for ferroelectric liquid crystal of the present invention, when the alignment substrate side for ferroelectric liquid crystal is the image display surface, the electrode layer is preferably transparent, and is made of a transparent conductor. Preferably it is configured. Preferred examples of the transparent conductor material include indium oxide, tin oxide, indium tin oxide (ITO), and the like.

  For example, when the alignment processing substrate for ferroelectric liquid crystal of the present invention is applied to an active matrix type liquid crystal display element using TFT, and the alignment processing substrate for ferroelectric liquid crystal is a TFT substrate, The electrode layer is a pixel electrode. On the other hand, when the alignment substrate for ferroelectric liquid crystal is a common electrode substrate, the electrode layer is a common electrode.

  Examples of the method for forming the electrode layer include chemical vapor deposition (CVD), physical vapor deposition (PVD) such as sputtering, ion plating, and vacuum deposition.

4). Base Material The base material used in the present invention is not particularly limited as long as it is generally used as a base material for liquid crystal display elements, and may be transparent or opaque.
For example, when the alignment processing substrate for ferroelectric liquid crystal of the present invention is applied to an active matrix type transmissive liquid crystal display element using TFTs, the alignment processing substrate for ferroelectric liquid crystal is either a TFT substrate or a common electrode substrate. Even so, the substrate is transparent. Further, the alignment substrate for ferroelectric liquid crystal of the present invention is applied to an active matrix type reflective liquid crystal display element using TFT, and the alignment substrate for ferroelectric liquid crystal is a common electrode substrate. In some cases, the substrate is transparent. On the other hand, when the alignment processing substrate for ferroelectric liquid crystal of the present invention is applied to an active matrix type reflective liquid crystal display element using TFT, and the alignment processing substrate for ferroelectric liquid crystal is a TFT substrate. The substrate is not required to be transparent.

  As a base material, a glass plate, a plastic plate, etc. are mentioned preferably, for example.

5. Colored layer In the present invention, a colored layer may be formed between the substrate and the electrode layer. When the colored layer is formed, in the liquid crystal display element using the alignment substrate for ferroelectric liquid crystal of the present invention, color display can be realized by the colored layer.

The colored layer is usually formed in a pattern and is composed of a red pattern, a green pattern, and a blue pattern. The arrangement of the colored patterns is not particularly limited as long as the colored patterns are arranged in an average when viewed macroscopically, and examples thereof include a stripe arrangement, a mosaic arrangement, and a delta arrangement.
Moreover, a colored layer is normally formed in the opening part of the light-shielding part mentioned later.

  The colored layer used in the present invention is not particularly limited as long as it is generally used as a colored layer of a color filter. For the colored layer, for example, a photosensitive resin composition containing a red, blue, or green pigment used in a normal pigment dispersion method or the like can be used.

6). Light Shielding Part In the present invention, a light shielding part may be formed in the non-display area. The light-shielding portion prevents light leakage from the vicinity of the wiring in a liquid crystal display element using the alignment substrate for ferroelectric liquid crystal, and prevents generation of a leakage current when the external light is incident on the TFT. It is provided for this purpose.

In the present invention, as described above, it is preferable that a liquid repellent region is disposed on the light shielding portion.
The light shielding portion is usually formed in a matrix. It is preferable that the liquid-repellent region is disposed corresponding to either the vertical line or the horizontal line of the matrix-shaped light shielding portion.

Examples of the material for forming the light shielding part include a resin containing a black colorant, or a metal or a metal compound such as chromium, chromium oxide, or chromium nitride. As the light-shielding part using a metal or a metal compound, for example, a CrO _x film (x is an arbitrary number) and a Cr film laminated in two layers may be used, and CrO with a further reduced reflectance. Three layers of an _x film (x is an arbitrary number), a CrN _y film (y is an arbitrary number), and a Cr film may be laminated.

  A light-shielding part using a resin containing a black colorant is formed by applying a photosensitive resin composition containing a black colorant to form a coating film, and patterning the coating film using a photolithography method. Can be formed.

  The light-shielding portion using a metal or a metal compound can be formed by forming a thin film by a sputtering method, a vacuum evaporation method, or the like, and patterning the thin film using a photolithography method. Further, the light shielding portion can be formed by using an electroless plating method, a printing method, or the like.

  The thickness of the light shielding portion can be about 0.2 μm to 0.4 μm when a sputtering method or a vacuum deposition method is used, and can be about 0.5 μm to 2 μm when a coating method or a printing method is used.

7). TFT
In the present invention, a TFT may be formed on the substrate. At least one TFT is formed in each pixel.

  The TFT used in the present invention has at least a semiconductor layer. The semiconductor layer is electrically connected to the gate electrode, the source electrode, and the drain electrode. As this semiconductor layer, a semiconductor layer generally used for a TFT can be used, and examples thereof include amorphous silicon, polysilicon, single crystal silicon, and the like.

  Examples of the method for forming the semiconductor layer include a CVD method, or a PVD method such as a sputtering method or an ion plating method.

8). Gate electrode, source electrode, and drain electrode In the present invention, the gate electrode and the source electrode may be formed vertically and horizontally on the substrate, and the drain electrode may be formed so as to connect the semiconductor layer and the pixel electrode. . The gate electrode, the source electrode, and the drain electrode are for driving the liquid crystal when a signal voltage is applied.

  In the present invention, as described above, the liquid repellent region is preferably disposed on the source electrode.

  A general metal electrode can be used as the gate electrode, the source electrode, and the drain electrode. Examples of the metal electrode include chromium, aluminum, tantalum, tungsten, titanium, molybdenum, and the like.

  As a method for forming the gate electrode, the source electrode, and the drain electrode, a CVD method, or a PVD method such as a sputtering method or an ion plating method can be given.

9. Reactive Liquid Crystal Layer In the present invention, as illustrated in FIG. 15, a reactive liquid crystal layer 9 formed by fixing reactive liquid crystals may be formed on the alignment film 6. The reactive liquid crystal is aligned by an alignment film. For example, the reactive liquid crystal layer can be formed by polymerizing the reactive liquid crystal by irradiating ultraviolet rays and fixing the alignment state. Since the reactive liquid crystal layer is formed by fixing the alignment state of the reactive liquid crystal in this way, it functions as an alignment film for aligning the ferroelectric liquid crystal. Further, since the reactive liquid crystal is fixed, it has an advantage that it is not affected by temperature or the like. In addition, reactive liquid crystals are relatively similar in structure to ferroelectric liquid crystals and have strong interaction with ferroelectric liquid crystals, so that alignment of ferroelectric liquid crystals is more effective than using alignment films alone. Can be controlled.

  The reactive liquid crystal used in the present invention preferably exhibits a nematic phase. This is because the nematic phase is relatively easy to control the alignment among the liquid crystal phases.

  The reactive liquid crystal preferably contains a polymerizable liquid crystal material. This is because the alignment state of the reactive liquid crystal can be fixed. As the polymerizable liquid crystal material, any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer, and a polymerizable liquid crystal polymer can be used, and among them, a polymerizable liquid crystal monomer is preferably used. The polymerizable liquid crystal monomer can be aligned at a lower temperature than other polymerizable liquid crystal materials, that is, a polymerizable liquid crystal oligomer and a polymerizable liquid crystal polymer, and has high sensitivity in alignment, and can be easily aligned. Because you can.

  The polymerizable liquid crystal monomer is not particularly limited as long as it is a liquid crystal monomer having a polymerizable functional group, and examples thereof include a monoacrylate monomer and a diacrylate monomer. These polymerizable liquid crystal monomers may be used alone or in combination of two or more.

  As a monoacrylate monomer, the compound represented by following formula (4) and (5) can be illustrated, for example.

In the above formula, A, B, D, E and F represent benzene, cyclohexane or pyrimidine, and these may have a substituent such as halogen. A and B, or D and E may be bonded via a bonding group such as an acetylene group, a methylene group, or an ester group. M ¹ and M ² may be any of a hydrogen atom, an alkyl group having 3 to 9 carbon atoms, an alkoxycarbonyl group having 3 to 9 carbon atoms, or a cyano group. Further, the acryloyloxy group at the end of the molecular chain and A or D may be bonded via a bonding group such as an alkylene group having 3 to 6 carbon atoms.

  Examples of the diacrylate monomer include compounds represented by the following formulas (6) and (7).

In the above formula, X and Y are hydrogen, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, alkyloxy having 1 to 20 carbons, alkyloxycarbonyl having 1 to 20 carbons, formyl, carbon number 1-20 alkylcarbonyl, C1-C20 alkylcarbonyloxy, halogen, cyano or nitro is represented. M represents an integer in the range of 2-20. In the above formula (6), X is preferably an alkyloxycarbonyl having 1 to 20 carbon atoms, methyl or chlorine, and especially an alkyloxycarbonyl having 1 to 20 carbon atoms, especially CH ₃ (CH ₂ ) ₄ OCO. It is preferable that

  Moreover, as a diacrylate monomer, the compound shown, for example to following formula (8) can be mentioned.

In the above formula, Z ³¹ and Z ³² are each independently independently directly bonded —COO—, —OCO—, —O—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—. , —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, wherein R ³¹ , R ³² and R ³³ are each independently hydrogen or carbon number 1 to 5 Represents alkyl. K and m represent 0 or 1, and n represents an integer in the range of 2 to 8. R ³¹ , R ³² and R ³³ are each independently alkyl having 1 to 5 carbons when k = 1, and each independently being hydrogen or alkyl having 1 to 5 carbons when k = 0. Preferably there is. R ³¹ , R ³² and R ³³ may be the same as each other.

  Specific examples of the compound represented by the above formula (8) include compounds represented by the following formula (8-1).

In the above formula, Z ²¹ and Z ²² are each independently directly bonded —COO—, —OCO—, —O—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—. _{, -OCH 2 -, - CH 2} O -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 - represents a. M represents 0 or 1, and n represents an integer in the range of 2-8.

  In the present invention, among the above, compounds represented by the above formulas (6) and (8) are preferably used. Specific examples of the compound represented by the above formula (8) include “Adeka Kiracol PLC-7183” and “Adeka Kiracol PLC-7209” manufactured by Asahi Denka Kogyo Co., Ltd. Examples of the acrylate monomer include “ROF-5101” and “ROF-5102” manufactured by Rolic technologies.

  In the present invention, among the polymerizable liquid crystal monomers, diacrylate monomers are preferred. This is because the diacrylate monomer can be easily polymerized while maintaining the orientation state in a good state.

  The polymerizable liquid crystal monomer described above does not have to exhibit a nematic phase. These polymerizable liquid crystal monomers may be used as a mixture of two or more kinds as described above, because the composition in which these are mixed, that is, the reactive liquid crystal may exhibit a nematic phase. It is.

  Furthermore, in this invention, you may add a photoinitiator, a polymerization inhibitor, etc. to the said reactive liquid crystal as needed. For example, when polymerizing a polymerizable liquid crystal material by electron beam irradiation, a photopolymerization initiator may not be necessary, but in the case of polymerization by, for example, ultraviolet irradiation, usually photopolymerization is started. This is because the agent is used for promoting the polymerization.

  Examples of the photopolymerization initiator that can be used in the present invention include benzyl (also referred to as bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoylbenzoic acid, benzoylmethyl benzoate, and 4-benzoyl-4′-methyldiphenyl. Sulfide, benzylmethyl ketal, dimethylaminomethylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3′-dimethyl-4-methoxybenzophenone, methylobenzoylformate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-chloro-4- And propoxythioxanthone. In addition to the photopolymerization initiator, it is also possible to add a sensitizer as long as the object of the present invention is not impaired.

  The amount of the photopolymerization initiator added is generally 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. It can be added to the liquid crystal.

  The thickness of the reactive liquid crystal layer is appropriately adjusted according to the target anisotropy, and can be set, for example, within a range of 1 nm to 1000 nm, and preferably within a range of 3 nm to 100 nm. This is because if the reactive liquid crystal layer is too thick, anisotropy more than necessary occurs, and if the reactive liquid crystal layer is too thin, the predetermined anisotropy may not be obtained.

  The reactive liquid crystal layer may be formed by applying a reactive liquid crystal layer forming coating liquid containing a reactive liquid crystal on the alignment film, performing an alignment treatment, and fixing the alignment state of the reactive liquid crystal. it can. Further, the reactive liquid crystal layer may be formed by forming a dry film or the like in advance and laminating it on the alignment film, instead of applying the coating liquid for forming the reactive liquid crystal layer. From the viewpoint of simplicity of the manufacturing process, it is possible to prepare a reactive liquid crystal layer-forming coating solution by dissolving reactive liquid crystal in a solvent, apply this onto the alignment film, and use a method of removing the solvent. preferable.

  The solvent used in the coating liquid for forming the reactive liquid crystal layer is not particularly limited as long as it can dissolve the reactive liquid crystal and the like and does not inhibit the alignment ability of the alignment film. For example, hydrocarbons such as benzene, toluene, xylene, n-butylbenzene, diethylbenzene and tetralin; ethers such as methoxybenzene, 1,2-dimethoxybenzene and diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2 Ketones such as 1,4-pentanedione; esters such as ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone; 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl Amide solvents such as acetamide; t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethyleneglycol 1 or 2 types of alcohols such as phenol and hexylene glycol; phenols such as phenol and parachlorophenol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and ethylene glycol monomethyl ether acetate; is there.

  Further, if only a single kind of solvent is used, the solubility of the reactive liquid crystal or the like may be insufficient or the alignment film may be eroded. In this case, this inconvenience can be avoided by using a mixture of two or more solvents. Among the above-mentioned solvents, hydrocarbons and glycol monoether acetate solvents are preferable as the sole solvent, and a mixed system of ethers or ketones and glycol solvent is preferable as the mixed solvent. It is.

  The concentration of the coating liquid for forming the reactive liquid crystal layer depends on the solubility of the reactive liquid crystal and the thickness of the reactive liquid crystal layer, but cannot be defined unconditionally, but is usually 0.1 to 40% by weight, preferably It is adjusted in the range of 1 to 20% by weight. When the concentration of the reactive liquid crystal layer forming coating liquid is lower than the above range, the reactive liquid crystal may be difficult to align, and conversely when the concentration of the reactive liquid crystal layer forming coating liquid is higher than the above range, This is because the viscosity of the coating liquid for forming a reactive liquid crystal layer is increased, so that it may be difficult to form a uniform coating film.

Furthermore, the following compounds can be added to the reactive liquid crystal layer-forming coating solution as long as the object of the present invention is not impaired. Examples of compounds that can be added include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; A polyurethane (meth) acrylate obtained by reacting a compound having two isocyanate groups with each other and then reacting the reaction product with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak Type epoxy resins, polycarboxylic acid polyglycidyl esters, polyol polyglycidyl ethers, aliphatic or cycloaliphatic epoxy resins, amine epoxy resins, triphenolmethane type epoxy resins, dihydroxybenzene type epoxy resins and the like (meth) Acry Photopolymerizable compound in epoxy (meth) acrylate obtained by reacting an acid; photopolymerizable liquid crystal compound having an acryl group and a methacryl group; and the like.
The amount of these compounds added to the reactive liquid crystal is selected within a range that does not impair the object of the present invention. Addition of these compounds improves the curability of the reactive liquid crystal, increases the mechanical strength of the resulting reactive liquid crystal layer, and improves its stability.

  Examples of the application method of the coating liquid for forming the reactive liquid crystal layer include spin coating, roll coating, printing, dip coating, die coating, casting, bar coating, blade coating, and spray coating. Method, gravure coating method, reverse coating method, extrusion coating method and the like.

  In addition, the solvent is removed after the reactive liquid crystal layer forming coating solution is applied, and the removal of the solvent is performed by, for example, removal under reduced pressure or removal by heating, or a combination thereof. .

  In the present invention, the reactive liquid crystal applied as described above is aligned by the alignment film so as to have liquid crystal regularity. That is, a nematic phase is developed in the reactive liquid crystal. This is usually performed by a method such as a method of performing a heat treatment below the NI transition point. Here, the NI transition point indicates the temperature at which the liquid crystal phase transitions to the isotropic phase.

  The reactive liquid crystal has a polymerizable liquid crystal material, and in order to fix the alignment state of such a polymerizable liquid crystal material, a method of irradiating actinic radiation that activates polymerization is used. As used herein, active radiation refers to radiation that has the ability to cause polymerization of a polymerizable liquid crystal material.

  The actinic radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable liquid crystal material, but usually ultraviolet light or visible light is used from the viewpoint of the ease of the apparatus. Irradiation light having a wavelength of 150 to 500 nm, preferably 250 to 450 nm, and more preferably 300 to 400 nm is used.

  In the present invention, a method of irradiating ultraviolet rays with active radiation to a polymerizable liquid crystal material in which the photopolymerization initiator generates radicals with ultraviolet rays and the polymerizable liquid crystal material undergoes radical polymerization is a preferable method. . This is because the method using ultraviolet rays as actinic radiation is an already established technique, and therefore it can be easily applied to the present invention including the photopolymerization initiator to be used.

  As a light source of this irradiation light, a low pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), a high pressure discharge lamp (high pressure mercury lamp, metal halide lamp), a short arc discharge lamp (super high pressure mercury lamp, xenon lamp, mercury xenon). Lamp). In particular, the use of metal halide lamps, xenon lamps, high-pressure mercury lamps, etc. is recommended. The irradiation intensity is appropriately adjusted according to the composition of the reactive liquid crystal and the amount of photopolymerization initiator.

  Such irradiation with active radiation may be performed under a temperature condition in which the polymerizable liquid crystal material becomes a liquid crystal phase, or may be performed at a temperature lower than the temperature at which the liquid crystal phase is formed. This is because the alignment state of the polymerizable liquid crystal material once in the liquid crystal phase is not disturbed suddenly even if the temperature is lowered thereafter.

  Further, as a method for fixing the alignment state of the polymerizable liquid crystal material, in addition to the method of irradiating the active radiation, a method of polymerizing the polymerizable liquid crystal material by heating can be used. As the reactive liquid crystal used in this case, it is preferable that the polymerizable liquid crystal monomer contained in the reactive liquid crystal is thermally polymerized below the NI transition point of the reactive liquid crystal.

10. Application The alignment substrate for ferroelectric liquid crystal of the present invention can be applied to, for example, an active matrix liquid crystal display element using TFTs. In this case, the alignment substrate for ferroelectric liquid crystal may be a TFT substrate or a common electrode substrate.

B. Next, the liquid crystal display element of the present invention will be described.
The liquid crystal display element of the present invention includes the above-described alignment substrate for ferroelectric liquid crystal, the second base material, the second electrode layer formed on the second base material, and the second electrode layer. The counter substrate having the formed second alignment film is disposed so that the alignment film of the alignment substrate for ferroelectric liquid crystal and the second alignment film of the counter substrate face each other, and the alignment film and the second It is characterized in that a ferroelectric liquid crystal is sandwiched between alignment films.

The liquid crystal display element of the present invention will be described with reference to the drawings.
FIG. 16 is a cross-sectional view showing an example of the liquid crystal display element of the present invention. In the liquid crystal display element 30 illustrated in FIG. 16, the alignment substrate 1 for ferroelectric liquid crystal and the counter substrate 41 are opposed to each other, and the alignment film 6 and the counter substrate 41 of the alignment substrate 1 for ferroelectric liquid crystal are opposed to each other. A ferroelectric liquid crystal is sandwiched between the second alignment film 46 and a liquid crystal layer 31 is formed. In the alignment substrate 1 for ferroelectric liquid crystal, the electrode layer 3 is formed on the substrate 2, the wettability changing layer 4 is formed on the electrode layer 3, and the lyophilic region 5a is formed on the surface of the wettability changing layer 4. In addition, a wettability change pattern in which the liquid repellent regions 5b are alternately arranged in a stripe shape is formed, and the alignment film 6 is formed on the lyophilic region 5a. The counter substrate 41 is obtained by sequentially forming the second electrode layer 43 and the second alignment film 46 on the second base material 42. Between the liquid-repellent region 5b of the alignment substrate 1 for ferroelectric liquid crystal and the alignment film 46 of the counter substrate 41 is not filled with ferroelectric liquid crystal and is in a vacuum state or nitrogen. An inert gas such as a gas or air is filled to form a decompression portion 32.

  In the liquid crystal display element illustrated in FIG. 16, for example, a sealing material is applied to the periphery of a ferroelectric liquid crystal alignment treatment substrate, and the ferroelectric liquid crystal becomes isotropic in the ferroelectric liquid crystal alignment treatment substrate. The liquid crystal is heated to a temperature, and the ferroelectric liquid crystal is heated to become an isotropic liquid, and the ferroelectric liquid crystal is dropped in the state of the isotropic liquid on the alignment film of the heated alignment substrate for the ferroelectric liquid crystal. The alignment substrate for ferroelectric liquid crystal onto which the ferroelectric liquid crystal is dropped and the counter substrate are made to face each other, the pressure between the two substrates is reduced, the two substrates are stacked under reduced pressure, and the two substrates are bonded via a sealing material Then, it can be produced by orienting the ferroelectric liquid crystal sealed by gradually cooling to room temperature.

  When the liquid crystal dropping method as described above is used as a manufacturing method of the liquid crystal display element of the present invention, the ferroelectric is formed on the alignment film 6 and the liquid repellent region 5b of the alignment substrate 1 for ferroelectric liquid crystal exemplified in FIG. Liquid crystal is dropped. At this time, since the liquid repellent region 5 b is a region having a relatively high contact angle with the liquid, the ferroelectric liquid crystal hardly flows into the liquid repellent region 5 b and flows on the alignment film 6. For this reason, after bonding both substrates under reduced pressure, the substrate is sandwiched between the liquid repellent region 5b of the alignment substrate 1 for ferroelectric liquid crystal and the alignment film 46 of the counter substrate 41 as illustrated in FIG. The space thus formed becomes the decompression portion 32 without being filled with the ferroelectric liquid crystal.

  The liquid crystal display element illustrated in FIG. 16 is, for example, a liquid crystal cell is prepared in advance using a ferroelectric liquid crystal alignment treatment substrate and a counter substrate, and the ferroelectric liquid crystal is heated to form an isotropic liquid. Using the capillary effect, ferroelectric liquid crystal is injected into the liquid crystal cell in the form of an isotropic liquid, the liquid crystal cell is sealed with an adhesive, and the liquid crystal cell is cooled to room temperature and sealed. It can be produced by orientation.

  When the above-described vacuum injection method is used as a method for manufacturing a liquid crystal display element of the present invention, in the liquid crystal display element illustrated in FIG. 16, a space between the alignment film 6 and the second alignment film 46, and The ferroelectric liquid crystal is injected into the space between the liquid repellent region 5 b and the second alignment film 46. At this time, since the liquid repellent region 5b is a region having a relatively high contact angle with the liquid, the ferroelectric liquid crystal flows into the space sandwiched between the liquid repellent region 5b and the second alignment film. It is difficult to flow into the space between the alignment film 6 and the second alignment film 46. Therefore, the space between the liquid repellent region 5b and the second alignment film is not filled with the ferroelectric liquid crystal but is in a vacuum state or filled with an inert gas such as nitrogen gas or air. Thus, the decompression portion 32 is obtained. If this space is not in a vacuum, it is preferably filled with an inert gas.

  According to the present invention, since the alignment substrate for ferroelectric liquid crystal described above is used, the partition wall is formed by utilizing the difference in wettability between the alignment film formed on the lyophilic region and the liquid repellent region. The ferroelectric liquid crystal can be sealed in the linear space without providing it. Thereby, for example, by aligning the alignment treatment direction of the alignment film and the longitudinal direction of the stripe-shaped liquid repellent region at a predetermined angle, the alignment property of the ferroelectric liquid crystal can be improved, and the alignment defects can be improved. It is possible to suppress the occurrence.

For example, as shown in FIG. 17, when the ferroelectric liquid crystal 33 is sealed by the liquid crystal dropping method as described above, the ferroelectric liquid crystal 33 is continuously applied along the longitudinal direction of the stripe-shaped alignment film 6. In the case of dripping, the alignment property of the ferroelectric liquid crystal can be improved by making the alignment treatment direction d of the alignment film 6 and the longitudinal direction n of the striped liquid repellent region 5b substantially perpendicular. This is because it is assumed that when the ferroelectric liquid crystal 33 is continuously dropped along the longitudinal direction of the stripe-shaped alignment film 6, the ferroelectric liquid crystal 33 flows in the width direction p of the stripe-shaped alignment film 6. .
For example, although not shown, when the ferroelectric liquid crystal is sealed by the vacuum injection method as described above, the alignment treatment direction of the alignment film and the longitudinal direction of the stripe-shaped liquid repellent region are substantially parallel. Thus, the orientation of the ferroelectric liquid crystal can be improved. This is because the ferroelectric liquid crystal is assumed to be injected along the longitudinal direction of the stripe-shaped alignment film.

  Further, as described above, since it is not necessary to provide a partition wall, the liquid crystal display element of the present invention is suitable as a small display.

  In the present invention, a reduced pressure portion is provided between the alignment substrate for ferroelectric liquid crystal and the counter substrate, corresponding to the liquid repellent area of the alignment substrate for ferroelectric liquid crystal, It is possible to follow the expansion / contraction of the ferroelectric liquid crystal accompanying the change. Thereby, the cell gap can be kept constant, and the occurrence of display unevenness can be suppressed.

  In addition, due to the difference in pressure between the reduced pressure portion in the reduced pressure state and the outside of the liquid crystal display element that is at atmospheric pressure, a uniform pressure is always applied from the outside between the alignment substrate for the ferroelectric liquid crystal and the counter substrate. Therefore, the adhesion strength between the alignment substrate for ferroelectric liquid crystal and the counter substrate can be increased.

  Note that the alignment substrate for ferroelectric liquid crystal is the same as that described in the section “A. Alignment processing substrate for ferroelectric liquid crystal”, and therefore the description thereof is omitted here. Hereinafter, another configuration of the liquid crystal display element of the present invention will be described.

1. Liquid Crystal Layer The liquid crystal layer in the present invention is configured by sandwiching a ferroelectric liquid crystal between the alignment film of the alignment substrate for ferroelectric liquid crystal and the second alignment film of the counter substrate.

The ferroelectric liquid crystal used in the present invention is not particularly limited as long as it exhibits a chiral smectic C (SmC ^* ) phase. As the phase series of the ferroelectric liquid crystal, for example, a phase change between a nematic (N) phase, a cholesteric (Ch) phase, a chiral smectic C (SmC ^* ) phase, and a nematic (N) phase-chiral smectic in the temperature lowering process. Phase change with C (SmC ^* ) phase, Nematic (N) phase-Smectic A (SmA) phase-Chiral smectic C (SmC ^* ) phase, Nematic (N) phase-Cholesteric (Ch) phase -Smectic A (SmA) phase-What changes phase with chiral smectic C (SmC ^* ) phase.

  Among these, it is preferable that the ferroelectric liquid crystal is monostable. This is because gradation display is possible by using a ferroelectric liquid crystal exhibiting monostability.

  “Showing monostability” means a state in which the state of the ferroelectric liquid crystal when no voltage is applied is stabilized in one state. As illustrated in FIG. 18, the ferroelectric liquid crystal rotates along a cone ridge line in which the liquid crystal molecules 35 are inclined from the layer normal line z and have a bottom surface perpendicular to the layer normal line z. In such a cone, the tilt angle of the liquid crystal molecules 35 with respect to the layer normal z is referred to as a tilt angle θ. Thus, the liquid crystal molecules 35 can operate on the cone between two states inclined by a tilt angle ± θ with respect to the layer normal z. Specifically, the expression of monostability means a state in which the liquid crystal molecules 35 are stabilized in any one state on the cone when no voltage is applied.

Among those exhibiting monostability, liquid crystal molecules operate only when a positive or negative voltage is applied as shown in the lower left of FIG. 19, for example, referred to as HV-shaped switching. ) Those exhibiting characteristics are particularly preferred. When the ferroelectric liquid crystal exhibiting such HV-shaped switching characteristics is used, the opening time as a black and white shutter can be made sufficiently long, whereby each color that can be temporally switched can be displayed brighter. This is because a bright color display liquid crystal display element can be realized.
The “HV-shaped switching characteristic” refers to an electro-optical characteristic in which the light transmittance with respect to an applied voltage is asymmetric.

  Such a ferroelectric liquid crystal can be variously selected from generally known liquid crystal materials according to required characteristics.

In particular, a liquid crystal material that exhibits an SmC ^* phase from the Ch phase without passing through the SmA phase is suitable as a material that exhibits HV-shaped switching characteristics. Specifically, “R2301” manufactured by AZ Electronic Materials may be mentioned.

In addition, as the liquid crystal material that passes through the SmA phase, a material that expresses the SmC ^* phase from the Ch phase through the SmA phase is preferable because of a wide range of material selection. In this case, a single liquid crystal material exhibiting an SmC ^* phase can be used, but a non-chiral liquid crystal (hereinafter sometimes referred to as a host liquid crystal) having a low viscosity and easily exhibiting an SmC phase is used. By adding a small amount of an optically active substance that does not show large spontaneous polarization and an appropriate helical pitch, the liquid crystal material showing the phase sequence as described above has low viscosity and can realize faster response. preferable.

The host liquid crystal is preferably a material exhibiting an SmC phase in a wide temperature range, and can be used without particular limitation as long as it is generally known as a host liquid crystal of a ferroelectric liquid crystal. For example, the general formula:
^{Ra-Q 1 -X 1 - (} Q 2 -Y 1) m -Q 3 -Rb
(In the formula, Ra and Rb are each a linear or branched alkyl group, alkoxy group, alkoxycarbonyl group, alkanoyloxy group or alkoxycarbonyloxy group, and Q ¹ , Q ² and Q ³ are each 1 , 4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, 1,3-dioxane-2,5 -Diyl group, and these groups may have a substituent such as a halogen atom, a hydroxyl group, and a cyano group, and X ¹ and Y ¹ are each —COO—, —OCO—, —CH ₂ O— , —OCH ₂ —, —CH ₂ CH ₂ —, —C≡C—, or a single bond, and m is 0 or 1.). As the host liquid crystal, the above compounds can be used alone or in combination of two or more.

The optically active substance added to the host liquid crystal is not particularly limited as long as it is a material having a large spontaneous polarization and the ability to induce an appropriate helical pitch, and is generally added to a liquid crystal composition exhibiting an SmC phase. Any known material can be used. In particular, a material that can induce large spontaneous polarization with a small addition amount is preferable. Examples of such an optically active substance include the following general formula:
^{Rc-Q 1 -Za-Q 2} -Zb-Q 3 -Zc-Rd
(In the formula, Q ¹ , Q ² and Q ³ represent the same meaning as in the above general formula, and Za and Zb represent —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ CH _{2, respectively.} -, -C≡C-, -CH = N-, -N = N-, -N (→ O) = N-, -C (= O) S- or a single bond, and Rc is an asymmetric carbon atom. A linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkanoyloxy group or an alkoxycarbonyloxy group, which may have Rd is a linear or branched alkyl group having an asymmetric carbon atom An alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkanoyloxy group or an alkoxycarbonyloxy group, wherein Rc and Rd may be substituted with a halogen atom, a cyano group or a hydroxyl group). can do. As the optically active substance, the above compounds may be used alone or in combination of two or more.

  Specific examples of the ferroelectric liquid crystal passing through the SmA phase include “FELIXM4851-100” manufactured by AZ Electronic Materials.

  The liquid crystal layer in the present invention may contain other compounds in addition to the above ferroelectric liquid crystal. As other compounds, those having an arbitrary function can be used depending on the function required for the liquid crystal display element of the present invention. Examples of other compounds that can be suitably used include a polymer of a polymerizable monomer. This is because when the polymer of the polymerizable monomer is contained in the liquid crystal layer, the alignment of the ferroelectric liquid crystal is so-called “polymer stabilization” and excellent alignment stability is obtained.

  The polymerizable monomer is not particularly limited as long as it is a compound that generates a polymer by a polymerization reaction. Examples of the polymerizable monomer include a thermosetting resin monomer that causes a polymerization reaction by heat treatment, and an actinic radiation curable resin monomer that causes a polymerization reaction by irradiation with actinic radiation. Among these, it is preferable to use an actinic radiation curable resin monomer. When a thermosetting resin monomer is used, it is necessary to perform a heating process in order to cause a polymerization reaction. Therefore, the regular arrangement of the ferroelectric liquid crystal is impaired by such a heating process, There is a risk of inducing a phase transition. On the other hand, when the actinic radiation curable resin monomer is used, there is no such fear, and the alignment of the ferroelectric liquid crystal is hardly harmed by the polymerization reaction.

  Examples of the actinic radiation curable resin monomer include an electron beam curable resin monomer that undergoes a polymerization reaction upon irradiation with an electron beam, and a photocurable resin monomer that undergoes a polymerization reaction upon irradiation with light. Among these, it is preferable to use a photocurable resin monomer. It is because a manufacturing process can be simplified by using a photocurable resin monomer.

  The photocurable resin monomer is not particularly limited as long as it causes a polymerization reaction when irradiated with light having a wavelength in the range of 150 nm to 500 nm. Among them, it is preferable to use an ultraviolet curable resin monomer that generates a polymerization reaction when irradiated with light having a wavelength in the range of 250 nm to 450 nm, particularly in the range of 300 nm to 400 nm. This is because it has advantages in terms of the ease of the irradiation apparatus.

  The polymerizable functional group possessed by the ultraviolet curable resin monomer is not particularly limited as long as it causes a polymerization reaction upon irradiation with ultraviolet rays in the above wavelength region. In particular, it is preferable to use an ultraviolet curable resin monomer having an acrylate group.

  Further, the UV curable resin monomer may be a monofunctional monomer having one polymerizable functional group in one molecule, or a polyfunctional having two or more polymerizable functional groups in one molecule. It may be a monomer. Among these, it is preferable to use a polyfunctional monomer. By using a polyfunctional monomer, a stronger polymer network can be formed in the liquid crystal layer, so that the intermolecular force and the polymer network at the alignment film interface can be strengthened. Thereby, disorder of the alignment of the ferroelectric liquid crystal due to the temperature change of the liquid crystal layer can be suppressed.

  Among the polyfunctional monomers, bifunctional monomers having a polymerizable functional group at both ends of the molecule are preferably used. By having polymerizable functional groups at both ends of the molecule, it is possible to form a polymer network in which the distance between the polymers is wide, and the driving voltage of the ferroelectric liquid crystal is reduced due to the liquid crystal layer containing a polymer of a polymerizable monomer. It is because it can prevent.

  Of the ultraviolet curable resin monomers, it is preferable to use an ultraviolet curable liquid crystal monomer that exhibits liquid crystallinity. The reason why such an ultraviolet curable liquid crystal monomer is preferable is as follows. That is, since the ultraviolet curable liquid crystal monomer exhibits liquid crystallinity, it can be regularly arranged by the alignment regulating force of the alignment film. For this reason, the ultraviolet curable liquid crystal monomer can be fixed while maintaining the regular alignment state by causing a polymerization reaction after the ultraviolet light curable liquid crystal monomer is regularly arranged. The presence of the polymer having such a regular alignment state in the liquid crystal layer can improve the alignment stability of the ferroelectric liquid crystal, and can obtain excellent heat resistance and impact resistance. .

  The liquid crystal phase exhibited by the ultraviolet curable liquid crystal monomer is not particularly limited, and examples thereof include an N phase, an SmA phase, and an SmC phase.

  Examples of the ultraviolet curable liquid crystal monomer used in the present invention include compounds represented by the following formulas (4), (5) and (7).

In the above formulas (4) and (5), A, B, D, E and F represent benzene, cyclohexane or pyrimidine, and these may have a substituent such as halogen. A and B, or D and E may be bonded via a bonding group such as an acetylene group, a methylene group, or an ester group. M ¹ and M ² may be any of a hydrogen atom, an alkyl group having 3 to 9 carbon atoms, an alkoxycarbonyl group having 3 to 9 carbon atoms, or a cyano group. Further, the acryloyloxy group at the end of the molecular chain and A or D may be bonded via a bonding group such as an alkylene group having 3 to 6 carbon atoms.

  In the above formula (7), Y is hydrogen, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, alkyloxy having 1 to 20 carbons, alkyloxycarbonyl having 1 to 20 carbons, formyl Represents alkylcarbonyl having 1 to 20 carbon atoms, alkylcarbonyloxy having 1 to 20 carbon atoms, halogen, cyano or nitro.

  Among the above, the compounds represented by the following formulas can be exemplified as those suitably used.

  The polymer of the polymerizable monomer may be a polymer of a single polymerizable monomer or a polymer of two or more different polymerizable monomers. In the case of using a polymer of two or more different polymerizable monomers, for example, a polymer of an ultraviolet curable liquid crystal monomer represented by the above formula and another ultraviolet curable resin monomer can be exemplified.

  When an ultraviolet curable liquid crystal monomer is used as the polymerizable monomer, the polymer of the polymerizable monomer is a main chain liquid crystal type polymer in which the main chain exhibits liquid crystallinity by having an atomic group exhibiting liquid crystallinity in the main chain. It may be a side chain liquid crystal polymer in which the side chain exhibits liquid crystallinity by having an atomic group exhibiting liquid crystallinity in the side chain. Especially, it is preferable that the polymer of a polymerizable monomer is a side chain liquid crystal type polymer. This is because the presence of the atomic group exhibiting liquid crystallinity in the side chain increases the degree of freedom of the atomic group, and therefore the atomic group exhibiting liquid crystallinity is easily aligned in the liquid crystal layer. Further, as a result, the alignment stability of the ferroelectric liquid crystal can be improved.

  The amount of the polymerized polymerizable monomer in the liquid crystal layer is not particularly limited as long as it is within a range in which the alignment stability of the ferroelectric liquid crystal can be set to a desired level, but is 0.5% by mass to 30% by mass. Within the range, more preferably within the range of 1% by mass to 20% by mass, and even more preferably within the range of 1% by mass to 10% by mass. This is because if the amount of the polymerized monomer is larger than the above range, the driving voltage of the ferroelectric liquid crystal may increase or the response speed may decrease. Further, when the amount of the polymerizable monomer polymer is less than the above range, the alignment stability of the ferroelectric liquid crystal becomes insufficient, and the heat resistance and impact resistance may be lowered.

  The abundance of the polymerizable monomer polymer in the liquid crystal layer is obtained by washing the monomolecular liquid crystal in the liquid crystal layer with a solvent and then weighing the weight of the remaining polymerizable monomer polymer with an electronic balance. It can be calculated from the remaining amount and the total mass of the liquid crystal layer.

  As a method of encapsulating the ferroelectric liquid crystal, a general encapsulating method can be used, and for example, either a vacuum injection method or a liquid crystal dropping method can be applied.

  In the case of the vacuum injection method, for example, a liquid crystal cell is prepared in advance using an alignment treatment substrate for a ferroelectric liquid crystal and a counter substrate, and the ferroelectric liquid crystal is heated to obtain an isotropic liquid, which utilizes the capillary effect. Then, the liquid crystal layer can be formed by injecting the ferroelectric liquid crystal into the liquid crystal cell in an isotropic liquid state and sealing with an adhesive. Thereafter, the encapsulated ferroelectric liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

  In the case of the liquid crystal dropping method, for example, a sealing material is applied to the periphery of the alignment substrate for ferroelectric liquid crystal, the alignment substrate for ferroelectric liquid crystal is heated, and the ferroelectric liquid crystal is heated. A ferroelectric liquid crystal is dropped in the state of an isotropic liquid on a heated alignment substrate for a ferroelectric liquid crystal, and the ferroelectric liquid crystal alignment processing substrate on which the ferroelectric liquid crystal is dropped The liquid crystal layer can be formed by making the substrates face each other, stacking them under reduced pressure, and bonding them with a sealant. Thereafter, the encapsulated ferroelectric liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

  In the case of the liquid crystal dropping method, the method for dropping the ferroelectric liquid crystal is not particularly limited as long as a predetermined amount that can be sealed can be dropped. For example, a method of dropping intermittently or a method of dropping continuously may be used. Specifically, the dropping method of the ferroelectric liquid crystal includes an ink jet method, a dispenser method, and the like.

  The thickness of the liquid crystal layer composed of ferroelectric liquid crystal is preferably in the range of 1.2 μm to 3.0 μm, more preferably 1.3 μm to 2.5 μm, still more preferably 1.4 μm to 2. It is in the range of 0 μm. This is because if the thickness of the liquid crystal layer is too thin, the contrast may be lowered. Conversely, if the thickness of the liquid crystal layer is too thick, the ferroelectric liquid crystal may be difficult to align.

  The thickness of the liquid crystal layer can be adjusted by a spacer such as a bead or a column spacer. This spacer is preferably formed on the liquid repellent region. That is, the spacer is preferably formed in the non-display area. In general, ferroelectric liquid crystal alignment defects are likely to occur in the vicinity of the spacer. However, since the spacer is formed in the non-display region, the influence on the image display due to the alignment defect in the vicinity of the spacer can be reduced. is there.

2. The counter substrate used in the present invention has a second base material, a second electrode layer formed on the second base material, and a second alignment film formed on the second electrode layer. is there.

  In the present invention, it is preferable that the alignment film of the alignment substrate for ferroelectric liquid crystal and the second alignment film of the counter substrate are made of materials having different compositions. This is because the occurrence of orientation defects such as zigzag defects, hairpin defects, and double domains can be suppressed. In particular, the occurrence of double domains can be effectively suppressed, and monodomain orientation can be obtained. The reason why a good alignment state can be obtained by making the constituent materials of the alignment film and the second alignment film different is not clear, but is thought to be due to the difference in the interaction between each of the alignment films and the ferroelectric liquid crystal. It is done. In addition, since the ferroelectric liquid crystal can be aligned by the alignment regulating force of the alignment film and the second alignment film, alignment disorder due to temperature rise above the phase transition point hardly occurs, and excellent alignment stability is obtained. Can do.

  In order to make the composition of the constituent materials of the alignment film and the second alignment film different, for example, one of the alignment film and the second alignment film may be a photo-alignment film and the other may be a rubbing alignment film. Also, both the alignment film and the second alignment film are used as the rubbing alignment film, and the constituent materials of the rubbing alignment film are different, or both are used as the photo-alignment film, and the constituent materials of the photo-alignment film are different. By making it, the composition of the constituent material of the alignment film can be made different.

  Further, when both the alignment film and the second alignment film are photo-alignment films, for example, by using a photoisomerization type material for one photo-alignment film and using a photo-reactive type material for the other photo-alignment film The composition of the constituent material of the photo-alignment film can be made different.

  Further, when both the alignment film and the second alignment film are photo-alignment films using a photoisomerization type material, cis-trans isomerization is selected from the above-mentioned photoisomerization-reactive compounds according to required characteristics. The composition of the constituent material of the photo-alignment film can be made different by selecting various reactive skeletons and substituents. Furthermore, the composition can be changed by changing the amount of the additive described above.

  Similarly, when both the alignment film and the second alignment film are photo-alignment films using photoreactive materials, various photo-dimerization reactive compounds such as the photo-dimerization-reactive polymer described above can be selected. The composition of the constituent material of the alignment film can be different. Furthermore, the composition can be changed by changing the amount of the additive described above.

  Further, a reactive liquid crystal layer is formed on one of the alignment film and the second alignment film, or a reactive liquid crystal layer is formed on both the alignment film and the second alignment film, and each reaction is performed. By making the composition of the constituent material of the conductive liquid crystal layer different, the composition of the constituent material of the member formed on the outermost surface of each substrate can be made different from that of the ferroelectric liquid crystal.

  The second alignment film used in the present invention may be formed on the entire surface of the second substrate, or may be formed in a pattern on the second substrate. It is preferable. In this case, the counter substrate is also preferably the above-mentioned alignment processing substrate for ferroelectric liquid crystal.

  FIG. 3 shows an example in which the counter substrate is a ferroelectric liquid crystal alignment treatment substrate. In the liquid crystal display element 30 illustrated in FIG. 3, two alignment substrates 1 and 1 ′ for ferroelectric liquid crystal face each other, and each of these alignment substrates 1 and 1 ′ for ferroelectric liquid crystal is opposed. A ferroelectric liquid crystal is sandwiched between the alignment films 6 and 6 ′ to form a liquid crystal layer 31. The alignment substrates 1 and 1 ′ for ferroelectric liquid crystal have electrode layers 3, 3 ′ and wettability changing layers 4, 4 ′ formed on the substrates 2, 2 ′, respectively. A wettability change pattern in which stripe-like lyophilic regions 5a and 5a 'and lyophobic regions 5b and 5b' are alternately arranged is formed on the surface of 4 ', and is oriented on the lyophilic regions 5a and 5a'. Films 6 and 6 'are formed. The two alignment processing substrates 1 and 1 'for ferroelectric liquid crystal face the respective alignment films 6 and 6', that is, the respective lyophilic regions 5a and 5a ', and the respective liquid repellent regions 5b and 5b. It is arranged so that ′ faces each other. Further, the liquid-repellent regions 5b and 5b ′ are not filled with the ferroelectric liquid crystal and are in a vacuum state, or filled with an inert gas such as nitrogen gas or air, and the decompression portion 32. It has become.

  Thus, when the counter substrate is a ferroelectric liquid crystal alignment treatment substrate, the alignment films of each ferroelectric liquid crystal alignment treatment substrate face each other, and the liquid repellent regions of each ferroelectric liquid crystal alignment treatment substrate face each other. Both substrates are arranged so that they face each other.

  The second substrate, the second electrode layer, and the second alignment film are the same as the substrate, electrode layer, and alignment film described in “A. Alignment processing substrate for ferroelectric liquid crystal”, respectively. The alignment substrate for dielectric liquid crystal is the same as that described above in “A. Alignment processing substrate for ferroelectric liquid crystal”, and the description thereof is omitted here.

3. Polarizing plate In the present invention, polarizing plates may be provided on the outer sides of the alignment substrate for ferroelectric liquid crystal and the counter substrate, respectively. Thereby, the incident light becomes linearly polarized light, and only light polarized in the alignment direction of the liquid crystal molecules can be transmitted. Usually, each polarizing plate is arranged with the polarization axis twisted by 90 °. As a result, the direction of the optical axis of the liquid crystal molecules and the magnitude of the birefringence of the liquid crystal molecules in the non-voltage applied state and the voltage applied state are controlled, and a bright state and a dark state are created by using the liquid crystal molecules as a monochrome shutter. Can do. For example, in the state where no voltage is applied, the ferroelectric liquid crystal is arranged by aligning the polarization axis of the polarizing plate on the alignment substrate for the ferroelectric liquid crystal with the alignment direction of the liquid crystal molecules (the alignment processing direction of the alignment film). The polarized light transmitted through the polarizing plate on the alignment processing substrate side cannot be rotated by 90 °, and is blocked by the polarizing plate on the counter substrate side to be in a dark state. On the other hand, in the voltage application state, the orientation direction of the liquid crystal molecules has an angle θ (preferably θ = 45 °) with respect to the polarization axis of each polarizing plate. The polarized light is transmitted through the polarizing plate on the counter substrate side and becomes a bright state. As described above, the liquid crystal display element of the present invention uses the ferroelectric liquid crystal as a black and white shutter, and thus has an advantage that the response speed can be increased. Then, gradation display is possible by controlling the amount of transmitted light by the applied voltage.

  The polarizing plate used in the present invention is not particularly limited as long as it transmits only a specific direction in the wave of light, and a polarizing plate generally used as a polarizing plate of a liquid crystal display element may be used. it can.

4). Driving method of liquid crystal display element The liquid crystal display element of the present invention can use the high-speed response of ferroelectric liquid crystal, so that one pixel is time-divided and high-speed response is obtained in order to obtain good video display characteristics. In particular, driving by the required field sequential color method is suitable.
Further, the driving method of the liquid crystal display element of the present invention is not limited to the field sequential method, and color display may be performed by a color filter method.

  The liquid crystal display element of the present invention is preferably driven by an active matrix method using TFTs since the ferroelectric liquid crystal exhibits monostability. This is because by adopting an active matrix system using a TFT element, a target pixel can be reliably turned on and off, so that a high-quality display is possible. Furthermore, gradation control is possible by voltage modulation.

  In the case of the active matrix system using TFTs, either the alignment substrate for ferroelectric liquid crystal or the counter substrate may be a TFT substrate or a common electrode substrate.

  FIG. 20 is a perspective view showing an example of an active matrix type liquid crystal display element using TFTs. A liquid crystal display element 30 illustrated in FIG. 20 includes a ferroelectric liquid crystal alignment processing substrate 1 (common electrode substrate) and a counter substrate 41 (TFT substrate). The alignment substrate 1 (common electrode substrate) for ferroelectric liquid crystal has an electrode layer 3 (common electrode) formed on a base material 2, a wettability changing layer (not shown), and stripes on the wettability changing layer surface. The wettability change pattern in which the lyophilic regions and the liquid repellent regions are alternately arranged is formed, and the alignment film 6 is formed on the lyophilic region. The counter substrate 41 (TFT substrate) includes a pixel electrode (second electrode layer) 43, a gate electrode 44a, a source electrode 44b, and a TFT 45 formed on a second base material 42. An alignment film is formed. The gate electrode 44a and the source electrode 44b are arranged vertically and horizontally, respectively, and by applying a signal to the gate electrode 44a and the source electrode 44b, the TFT 45 can be operated to drive the ferroelectric liquid crystal. A portion where the gate electrode 44a and the source electrode 44b intersect with each other is insulated by an insulating layer (not shown), and the signal of the gate electrode 44a and the signal of the source electrode 44b can operate independently. A portion surrounded by the gate electrode 44a and the source electrode 44b is a pixel which is a minimum unit for driving the liquid crystal display element of the present invention. Each pixel includes at least one TFT 45 and a pixel electrode (second electrode layer). 43 is formed. Then, by sequentially applying a signal voltage to the gate electrode and the source electrode, the TFT of each pixel can be operated. In FIG. 20, the liquid crystal layer, the wettability changing layer, the wettability changing pattern, and the second alignment film are omitted.

  The liquid crystal display element of the present invention can also be driven by a segment system.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[Example]
First, 3 g of isopropyl alcohol, 0.4 g of organosiloxane (manufactured by Toshiba Silicone, TSL8113), 0.3 g of fluoroalkoxysilane MF-160E (manufactured by Tochem Products), and photocatalyst inorganic coating agent ST-K01 (Ishihara Sangyo Co., Ltd.) 2 g) and a solution was prepared. Next, two glass substrates on which ITO electrodes were formed were thoroughly washed, and the above solution was applied to the entire surface of these glass substrates. The obtained coating film was dried and subjected to hydrolysis and polycondensation reaction to form a transparent wettability variable layer having a thickness of 0.1 μm in which the photocatalyst was firmly fixed in the organopolysiloxane.

Next, using a predetermined photomask, the wettability changing layer was irradiated with ultraviolet rays in a stripe pattern so that the pattern of the light irradiation portion was L (line) / S (space) = 1500 μm / 10 μm. Ultraviolet irradiation was performed for 3 minutes at an illuminance of 23.6 mW / cm ² using a UV exposure machine MA-1200DUV manufactured by Dainippon Screen Co., Ltd. A liquid repellent region was formed in a predetermined region of the wettability changing layer by irradiation with ultraviolet rays.

Next, a 2% by mass cyclopentanone solution of a photodimerization reaction type photo-alignment film material (trade name: ROP-102, manufactured by Roric Technology Co., Ltd.) is spin-coated on the wettability changing layer, and is maintained at 130 ° C. for 10 minutes. After drying, linearly polarized ultraviolet rays were irradiated at about 100 mJ / cm ² to perform an alignment treatment, and a photo-alignment film was formed. Further, on one substrate, a polymerizable liquid crystal (trade name: ROF-5101, manufactured by Rorlic Technology) is further laminated on the photo-alignment film by a spin coat method, and unpolarized light is 1 J / cm in a nitrogen atmosphere. ^Two reactive liquid crystal layers were formed by irradiation. Then, 1.5 μm bead spacers were dispersed on the reactive liquid crystal layer.

A hot plate placed in a vacuum chamber is heated to 100 ° C., one substrate is placed on the hot plate, and a ferroelectric liquid crystal (trade name: R2301, AZ) is formed using an inkjet head heated to 100 ° C. Electronic Materials) was applied. Next, the other substrate was adsorbed by an adsorption plate, and the two substrates were opposed to each other so that their alignment processing directions were parallel to each other. Then, the substrates were brought into close contact with each other in a state where evacuation was performed so that the inside of the vacuum chamber became 10 Torr, and after applying a certain pressure, the inside of the vacuum chamber was returned to normal pressure. Thereafter, the ferroelectric liquid crystal was gradually cooled to room temperature to produce a liquid crystal display element.
As a result, it was possible to produce a panel having no display unevenness without cell gap change due to expansion or contraction due to temperature change of the ferroelectric liquid crystal.

[Comparative example]
First, two glass substrates on which ITO electrodes were formed were thoroughly washed.
A transparent resist (trade name: NN780, manufactured by JSR) was spin-coated on one glass substrate, dried under reduced pressure, and prebaked at 90 ° C. for 3 minutes. Subsequently, it exposed to a mask with 100 mJ / cm ² ultraviolet rays, developed with an inorganic alkali solution, and post-baked at 230 ° C. for 30 minutes. Thereby, stripe-shaped partition walls having a stripe-shaped height of 1.5 μm and L / S = 10 μm / 1500 μm were formed.
Next, a 2% by mass cyclopentanone solution of a photodimerization reaction type photo-alignment film material (trade name: ROP-102, manufactured by Rorlic Technology Co., Ltd.) is spin-coated on the substrate on which the partition walls are formed at 130 ° C. After drying for 10 minutes, a linearly polarized ultraviolet ray was irradiated at about 100 mJ / cm ² to perform an alignment treatment to form a photo-alignment film. On this photo-alignment film, a polymerizable liquid crystal (trade name: ROF-5101, manufactured by Rorlic Technology Co., Ltd.) is further laminated by a spin coating method, and irradiated with 1 J / cm ² of non-polarized light in a nitrogen atmosphere. A liquid crystal layer was formed.

Next, a 2% by mass cyclopentanone solution of a photo-dimerization reaction type photo-alignment film material (trade name: ROP-102, manufactured by Rorlic Technology) is spin-coated on the other glass substrate, and 10% at 130 ° C. After drying for a minute, linearly polarized ultraviolet rays were irradiated at about 100 mJ / cm ² to perform alignment treatment to form a photo-alignment film.

A hot plate placed in a vacuum chamber is heated to 100 ° C., one substrate is placed on the hot plate, and a ferroelectric liquid crystal (trade name: R2301, AZ) is formed using an inkjet head heated to 100 ° C. Electronic Materials) was applied. Next, the other substrate was adsorbed by an adsorption plate, and the two substrates were opposed to each other so that their alignment processing directions were parallel to each other. Then, the substrates were brought into close contact with each other in a state where evacuation was performed so that the inside of the vacuum chamber became 10 Torr, and after applying a certain pressure, the inside of the vacuum chamber was returned to normal pressure. Thereafter, the ferroelectric liquid crystal was gradually cooled to room temperature to produce a liquid crystal display element.
As a result, a cell gap change due to expansion and contraction accompanying the temperature change of the ferroelectric liquid crystal occurred in the panel, and display unevenness was confirmed.

It is a schematic plan view which shows an example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is the sectional view on the AA line of FIG. It is a schematic sectional drawing which shows an example of the liquid crystal display element of this invention. It is a schematic plan view which shows the other example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is the BB sectional view taken on the line of FIG. It is a schematic plan view which shows the other example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is CC sectional view taken on the line of FIG. It is a schematic plan view which shows the other example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is a schematic plan view which shows the other example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is process drawing which shows an example of the manufacturing method of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is process drawing which shows the other example of the manufacturing method of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is a schematic plan view which shows the other example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is the DD sectional view taken on the line of FIG. It is process drawing which shows the other example of the manufacturing method of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is a schematic sectional drawing which shows the other example of the alignment processing board | substrate for ferroelectric liquid crystals of this invention. It is a schematic sectional drawing which shows the other example of the liquid crystal display element of this invention. It is a schematic diagram which shows an example of the sealing method of the ferroelectric liquid crystal in the manufacturing method of the liquid crystal display element of this invention. It is a schematic diagram which shows the behavior of a liquid crystal molecule. It is the graph which showed the change of the transmittance | permeability with respect to the applied voltage of a ferroelectric liquid crystal. It is a schematic perspective view which shows the other example of the liquid crystal display element of this invention. It is the figure which showed the difference in orientation by the difference in the phase sequence which a ferroelectric liquid crystal has.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,1 '... Orientation processing board | substrate for ferroelectric liquid crystals 2,2' ... Base material 3,3 '... Electrode layer 4,4' ... Wetting property change layer 5a, 5a '... Lipophilic area | region 5b, 5b' ... Liquid repellent area 6, 6 '... Alignment film 7 ... Resin layer 8 ... Micro lyophilic area 9 ... Reactive liquid crystal layer 13 ... Non-display area 30 ... Liquid crystal display element 31 ... Liquid crystal layer 41 ... Counter substrate 42 ... Second Base material 43 ... Second electrode layer 46 ... Second alignment film

Claims (8)

  A base material, an electrode layer formed on the base material, a wettability change pattern formed on the electrode layer, in which stripe-shaped lyophilic regions and lyophobic regions are alternately arranged, and the parent An alignment treatment substrate for ferroelectric liquid crystal, comprising an alignment film formed on a liquid region.   Between the electrode layer and the alignment film, a wettability changing layer whose wettability is changed by the action of a photocatalyst accompanying energy irradiation is formed, and the wettability changing pattern is formed on the wettability changing layer surface The alignment processing board | substrate for ferroelectric liquid crystals of Claim 1 characterized by these.   A resin layer containing fluorine is formed on the surface between the alignment film patterns on the electrode layer, the resin layer surface is the liquid repellent region, and the electrode layer surface in the opening of the resin layer is the parent layer. 2. The alignment substrate for ferroelectric liquid crystal according to claim 1, which is a liquid region.   4. The alignment substrate for ferroelectric liquid crystal according to claim 1, wherein the liquid repellent region is provided in a non-display region. 5.   5. The lyophilic region is formed with a lyophilic region connecting the lyophilic regions adjacent to each other with the lyophobic region interposed therebetween. An alignment substrate for a ferroelectric liquid crystal according to claim 1.   6. A substrate for aligning a ferroelectric liquid crystal according to claim 1, wherein a reactive liquid crystal layer formed by fixing a reactive liquid crystal is formed on the alignment film. .   7. The alignment substrate for ferroelectric liquid crystal according to claim 1, a second base, a second electrode layer formed on the second base, and the second A counter substrate having a second alignment film formed on the electrode layer, the alignment film of the alignment substrate for ferroelectric liquid crystal and the second alignment film of the counter substrate facing each other, and the alignment film And a ferroelectric liquid crystal sandwiched between the second alignment films.   The counter substrate is the alignment processing substrate for ferroelectric liquid crystal according to any one of claims 1 to 6, wherein the liquid repellent regions of the alignment processing substrates for ferroelectric liquid crystal face each other. The liquid crystal display element according to claim 7.

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