JP2009036861A - Liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal display element capable of polarity inversion driving using a ferroelectric liquid crystal exhibiting monostability and exhibiting half V-shaped switching characteristics.
The present invention provides a first alignment treatment substrate having a first substrate, a first electrode layer, and a first alignment layer made of a rubbing film, and a second substrate, a second electrode layer, and a first alignment. A liquid crystal display element in which a ferroelectric liquid crystal is sandwiched between a second alignment treatment substrate having a pattern and a second alignment layer comprising a second alignment pattern, wherein the ferroelectric liquid crystal exhibits monostability. The first alignment pattern is a pattern made of a photo-alignment film containing a photoisomerizable material, and the second alignment pattern is an alignment for a reactive liquid crystal. Provided is a liquid crystal display element characterized by being a pattern composed of a film and a reactive liquid crystal layer, or a pattern composed of a photo-alignment film containing a photodimerization type material.
[Selection] Figure 5

Description

  The present invention relates to a liquid crystal display element using monostable ferroelectric liquid crystal having spontaneous polarization.

  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 crystals proposed by Clark and Lagerwol are widely known as bistable ones having two stable states when no voltage is applied (FIG. 25, upper), but for switching in two states, bright and dark. Although it has limited memory characteristics, it has a problem that gradation display cannot be performed.

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. 25). As the liquid crystal exhibiting monostability, a ferroelectric liquid crystal that changes phase with a cholesteric (Ch) phase-chiral smectic C (SmC ^* ) phase and does not pass through a smectic A (SmA) phase is generally used (the upper part of FIG. 19). ).

  However, ferroelectric liquid crystals are difficult to align because they have higher molecular ordering than nematic liquid crystals. In particular, a ferroelectric liquid crystal that does not pass through the SmA phase generates two regions having different layer normal directions (hereinafter referred to as “double domain”). Such a double domain becomes a serious problem because black-and-white inversion is displayed during driving.

  As a method for improving the double domain, an electric field applied slow cooling method is known in which a liquid crystal cell is heated to a temperature equal to or higher than the Ch phase and gradually cooled while a DC voltage is applied (Non-Patent Document 2). In addition, as a method for mono-stabilizing ferroelectric liquid crystal, it is stabilized by mixing ultraviolet light curable liquid crystalline monomer with ferroelectric liquid crystal and applying UV light in a state of applying voltage to make it polymerized. There is a polymer stabilization method.

  Moreover, as a method for forming a monodomain, a method of aligning ferroelectric liquid crystal by performing rubbing treatment on one of upper and lower alignment films and applying photoalignment treatment on the other is disclosed (see Patent Document 1). . Furthermore, as a method for monostabilizing the ferroelectric liquid crystal, a method is disclosed in which photo-alignment films are used as upper and lower alignment films, and materials having different compositions are used for these photo-alignment films (Patent Document 2, Patent). Reference 3 and Patent Document 4). Furthermore, as a method for monostabilizing the ferroelectric liquid crystal, a reactive liquid crystal layer is formed by applying and aligning a reactive liquid crystal on one of the upper and lower alignment films, and fixing it. A method of using a liquid crystal layer as an alignment film is disclosed (see Patent Document 5).

  Furthermore, although it does not show monostability, as a method of improving the alignment defect of the ferroelectric liquid crystal, after applying a photo-alignment treatment to the upper and lower alignment films, a nematic liquid crystal is applied on each alignment film. A method of aligning ferroelectric liquid crystal by forming a nematic liquid crystal layer by aligning and fixing, and causing the nematic liquid crystal layer to act as an alignment film is disclosed (see Patent Document 6).

  In general, in a liquid crystal display element, burn-in occurs when a direct current is applied for a long time. Therefore, in order to prevent this burn-in, polarity inversion driving that reverses the polarity of voltage at a constant period is adopted. The polarity inversion driving includes line inversion driving for inverting the polarity for each line in the vertical or horizontal direction and dot inversion driving for inverting the polarity for each dot (one pixel).

  As shown in the lower part of FIG. 25, the ferroelectric liquid crystal exhibiting monostability has a half-V shaped switching (hereinafter referred to as “half-V-shaped”) in which liquid crystal molecules operate only when a positive or negative voltage is applied. It is called “switching”.) Some of them show characteristics, and others show V shaped switching (hereinafter referred to as “V-shaped switching”) characteristics in which liquid crystal molecules operate when either positive or negative voltage is applied. is there. In particular, the ferroelectric liquid crystal exhibiting a half V-shaped switching characteristic has an advantage that the opening time as a black and white shutter can be made sufficiently long.

  As shown in FIG. 2, the ferroelectric liquid crystal exhibiting half V-shaped switching characteristics includes a liquid crystal molecule that operates when a negative voltage is applied (FIG. 2A), and a positive voltage. Some liquid crystal molecules operate when applied (FIG. 2B).

JP 2003-5223 A JP 2005-208353 A JP 2005-234549 A JP 2005-234550 A JP 2005-258428 A JP 2002-532755 A NONAKA, T., LI, J., OGAWA, A., HORNUNG, B., SCHMIDT, W., WINGEN, R., and DUBAL, H., 1999, Liq. Cryst., 26, 1599. PATEL, J., and GOODBY, J. W., 1986, J. Appl. Phys., 59, 2355.

  In order to drive the liquid crystal display element using the ferroelectric liquid crystal exhibiting the half V-shaped switching characteristic by the above polarity inversion driving, when a negative voltage is applied for each line, each dot, or the like. It is necessary to alternately arrange a ferroelectric liquid crystal in which liquid crystal molecules operate and a ferroelectric liquid crystal in which liquid crystal molecules operate when a positive voltage is applied.

  However, since the ferroelectric liquid crystal is difficult to align as described above, no attempt has been made to drive a liquid crystal display element using the ferroelectric liquid crystal by the polarity inversion driving described above.

  The present invention has been made in view of such various points, and provides a liquid crystal display element capable of polarity inversion driving using a ferroelectric liquid crystal exhibiting monostability and exhibiting half V-shaped switching characteristics. The main purpose.

  In order to achieve the above object, the present invention provides a first base material, a first electrode layer formed on the first base material, and a first rubbing film formed on the first electrode layer. A first alignment treatment substrate having an alignment layer; a second substrate; a second electrode layer formed on the second substrate; and a first alignment pattern formed on the second electrode layer. A second alignment processing substrate having a second alignment layer having a second alignment pattern is disposed so that the first alignment layer and the second alignment layer face each other, and the first alignment layer and the second alignment layer are arranged. A liquid crystal display element in which a ferroelectric liquid crystal is sandwiched between the ferroelectric liquid crystal, the ferroelectric liquid crystal exhibiting monostability and half V-shaped switching characteristics, and the first alignment pattern. Is a photoisomerization type that imparts anisotropy to the alignment layer by causing a photoisomerization reaction. The second alignment pattern is formed on the reactive liquid crystal alignment film and the reactive liquid crystal alignment film, and the reactive liquid crystal is immobilized on the reactive liquid crystal. A liquid crystal display characterized in that it is either a pattern composed of a liquid crystal layer or a pattern composed of a photo-alignment film containing a photo-dimerization-type material that imparts anisotropy to the alignment film by causing a photo-dimerization reaction An element is provided.

According to the present invention, the first alignment layer, the first alignment pattern of the second alignment layer, and the second alignment pattern of the second alignment layer are combined in a predetermined combination, thereby allowing ferroelectricity to occur by polar surface interaction. It is possible to control the direction of spontaneous polarization of the liquid crystal. As a result, the direction of spontaneous polarization of the ferroelectric liquid crystal can be reversed for each region where the first alignment pattern or the second alignment pattern of the second alignment layer is provided, and polarity inversion driving is possible. Further, since the direction of spontaneous polarization of the ferroelectric liquid crystal can be controlled, the mono-domain alignment of the ferroelectric liquid crystal is performed in each region where the first alignment pattern or the second alignment pattern of the second alignment layer is provided. It is possible to obtain
Moreover, according to this invention, it is possible to suppress effectively generation | occurrence | production of a zigzag defect and a hairpin defect by using a rubbing film | membrane for a 1st orientation layer.

  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 second electrode layer and the second alignment layer, and on the wettability changing layer surface, A wettability change pattern including a liquid repellent region and a lyophilic region may be formed, and the second alignment layer may be formed only on the lyophilic region. This is because the first alignment pattern and the second alignment pattern can be easily and accurately formed using the wettability change pattern formed on the wettability changing layer surface.

  In the above case, a pattern-shaped light-shielding portion is formed between the second base material and the wettability changing layer, and the liquid-repellent region is disposed in a region where the light-shielding portion is provided. preferable. This is because light leakage due to disordered alignment of the ferroelectric liquid crystal in the liquid repellent region can be prevented.

  In the present invention, an insulating portion is formed between the first alignment pattern and the second alignment pattern, the surface of the insulating portion is a liquid repellent region, and the layer surface in the opening of the insulating portion is a lyophilic region. The second alignment layer may be formed only on the lyophilic region. As in the case described above, the first alignment pattern and the second alignment pattern are changed using the difference in wettability between the lyophobic region on the surface of the insulating portion and the lyophilic region on the surface of the layer in the opening of the insulating portion. This is because it can be easily formed with high accuracy.

  In the above case, the insulating part is preferably a light shielding part. This is because light leakage due to disordered alignment of the ferroelectric liquid crystal in the liquid repellent region can be prevented.

  In the present invention, a partition wall may be formed between the first alignment pattern and the second alignment pattern. Similarly, in this case, since the partition walls are formed, the first alignment pattern and the second alignment pattern can be easily formed with high accuracy.

  The present invention also provides a first base material, a first electrode layer formed on the first base material, and a first orientation pattern and a second orientation pattern formed on the first electrode layer. A first alignment treatment substrate having an alignment layer; a second substrate; a second electrode layer formed on the second substrate; and a first alignment pattern formed on the second electrode layer. A second alignment treatment substrate having a second alignment layer composed of a second alignment pattern, the first alignment pattern of the first alignment layer and the second alignment pattern of the second alignment layer are opposed to each other, and the first alignment layer A liquid crystal display element in which the second alignment pattern and the first alignment pattern of the second alignment layer are opposed to each other, and a ferroelectric liquid crystal is sandwiched between the first alignment layer and the second alignment layer. The ferroelectric liquid crystal exhibits monostability and is half V-shaped. The first alignment pattern is a pattern made of a rubbing film, and the second alignment pattern is formed on the reactive liquid crystal alignment film and the reactive liquid crystal alignment film. A pattern composed of a reactive liquid crystal layer formed by immobilizing a crystalline liquid crystal, a pattern composed of a photo-alignment film containing a photodimerization-type material that gives anisotropy to the alignment film by causing a photodimerization reaction, or photoisomerism Provided is a liquid crystal display element characterized in that it is any one of a pattern made of a photo-alignment film containing a photoisomerizable material that imparts anisotropy to the alignment film by causing an oxidization reaction.

According to the present invention, the direction of the spontaneous polarization of the ferroelectric liquid crystal can be controlled by the polar surface interaction by setting the first alignment pattern and the second alignment pattern in a predetermined combination. As a result, the direction of spontaneous polarization of the ferroelectric liquid crystal can be reversed for each region where the first alignment pattern or the second alignment pattern of the first alignment layer is provided, and polarity inversion driving is possible. In addition, since the direction of spontaneous polarization of the ferroelectric liquid crystal can be controlled, the monodomain alignment of the ferroelectric liquid crystal is performed in each region where the first alignment pattern or the second alignment pattern of the first alignment layer is provided. It is possible to obtain
Further, according to the present invention, it is possible to effectively suppress the occurrence of zigzag defects and hairpin defects by using a rubbing film for the first alignment pattern.

  In the said invention, wettability changes by the effect | action of the photocatalyst accompanying energy irradiation between the said 1st electrode layer and the said 1st orientation layer, and between the said 2nd electrode layer and the said 2nd orientation layer. A wettability change layer is formed, and a wettability change pattern including a liquid repellent region and a lyophilic region is formed on the surface of the wettability change layer. The first alignment layer and the wettability change layer are formed only on the lyophilic region. The second alignment layer may be formed. This is because the first alignment pattern and the second alignment pattern can be easily and accurately formed using the wettability change pattern formed on the wettability changing layer surface.

  In the above case, at least one of the first substrate and the wettability changing layer of the first alignment processing substrate and the second substrate and the wettability changing layer of the second alignment processing substrate. It is preferable that a pattern-shaped light-shielding portion is formed on the liquid-repellent region and the liquid-repellent region is disposed in the region where the light-shielding portion is provided. This is because light leakage due to disordered alignment of the ferroelectric liquid crystal in the liquid repellent region can be prevented.

  In the present invention, insulating portions are respectively formed between the first alignment pattern and the second alignment pattern of the first alignment layer and between the first alignment pattern and the second alignment pattern of the second alignment layer. The surface of the insulating part is a liquid repellent area, the surface of the layer in the opening of the insulating part is a lyophilic area, and the first alignment layer and the second alignment layer are formed only on the lyophilic area. It may be. As in the case described above, the first alignment pattern and the second alignment pattern are changed using the difference in wettability between the lyophobic region on the surface of the insulating portion and the lyophilic region on the surface of the layer in the opening of the insulating portion. This is because it can be easily formed with high accuracy.

  In the above case, it is preferable that at least one of the insulating portion formed on the first alignment processing substrate and the insulating portion formed on the second alignment processing substrate is a light shielding portion. This is because light leakage due to disordered alignment of the ferroelectric liquid crystal in the liquid repellent region can be prevented.

  In the present invention, a partition is formed between the first alignment pattern and the second alignment pattern of the first alignment layer or between the first alignment pattern and the second alignment pattern of the second alignment layer. May be. Similarly, in this case, since the partition walls are formed, the first alignment pattern and the second alignment pattern can be easily formed with high accuracy.

  Furthermore, in the present invention, it is preferable that the rubbing film contains polyimide.

  In the present invention, the combination of the predetermined alignment films with the ferroelectric liquid crystal sandwiched therebetween has an effect that the direction of spontaneous polarization of the ferroelectric liquid crystal can be controlled by the polar surface interaction. As a result, the direction of spontaneous polarization of the ferroelectric liquid crystal can be reversed for each region in which the first alignment pattern or the second alignment pattern is provided, and polarity inversion driving is possible. In addition, the use of a rubbing film for the alignment film on one side has an effect that the generation of zigzag defects and hairpin defects can be effectively suppressed.

  In order to investigate the direction of spontaneous polarization of the ferroelectric liquid crystal, the inventors conducted the following experiment.

First, a liquid crystal display element in which a ferroelectric liquid crystal was sandwiched between a rubbing film and a photo-alignment film containing a photodimerization type material was produced.
On the glass substrate on which the ITO electrode was formed, polyimide (manufactured by Nissan Chemical Industries, trade name: SE-7492) was printed and rubbed to form an alignment film. Further, a 2% by mass cyclopentanone solution of a photodimerization type material (Rolic technologies, trade name: ROP103) was spin-coated on a glass substrate on which an ITO electrode was formed, and dried at 130 ° C. for 15 minutes. Then, alignment treatment was performed by irradiating with linearly polarized ultraviolet rays of about 100 mJ / cm ² .

One substrate was sprayed with 1.5 μm bead spacers, and a sealant was applied to the other substrate with a seal dispenser. Next, both substrates were made to face each other so that their alignment treatment directions were parallel, and thermocompression bonding was performed to produce an empty liquid crystal cell.
Next, a ferroelectric liquid crystal (trade name: R2301, manufactured by AZ Electronic Materials) is used to attach a ferroelectric liquid crystal to the upper portion of the injection port, and an oven is used to obtain an N-phase-isotropic phase transition temperature of 10 Injection was performed at a temperature higher by 20 ° C to 20 ° C, and the temperature was slowly returned to room temperature.

  When a voltage was applied so that the electrode on the photo-alignment film side containing the photodimerization type material became a negative electrode, the molecular direction of the ferroelectric liquid crystal changed about twice the tilt angle. About 85% of the ferroelectric liquid crystal molecules were changed in molecular direction by about twice the tilt angle.

  In addition, by changing the types and combinations of polyimide and photodimerization material, a liquid crystal display element in which a ferroelectric liquid crystal is sandwiched between a rubbing film and a photoalignment film containing the photodimerization material, as described above. As a result, the same results as described above were obtained.

Next, a liquid crystal display element in which ferroelectric liquid crystal was sandwiched between the rubbing film and the reactive liquid crystal layer was produced.
On the glass substrate on which the ITO electrode was formed, polyimide (manufactured by Nissan Chemical Industries, trade name: SE-7492) was printed and rubbed to form an alignment film. In addition, a solution of photoisomerizable material (manufactured by DIC, trade name: LIA01) is spin-coated on a glass substrate on which an ITO electrode is formed, dried at 100 ° C. for 1 minute, and then subjected to linearly polarized ultraviolet rays. Irradiation was performed at 1000 mJ / cm ² to perform alignment treatment. Then, a 2% by mass cyclopentanone solution of reactive liquid crystal containing acrylate monomer (Rolic technologies, trade name: ROF-5101) was spin-coated on the photo-alignment film and dried at 55 ° C. for 3 minutes. After that, non-polarized ultraviolet rays were exposed to 1000 mJ / cm ² at 55 ° C.
Thereafter, a liquid crystal display element was produced in the same manner as described above.

  When a voltage was applied so that the electrode on the reactive liquid crystal layer side became a negative electrode, the molecular direction of the ferroelectric liquid crystal changed about twice the tilt angle. About 88% of the ferroelectric liquid crystal molecules were changed in molecular direction by about twice the tilt angle.

  In addition, by changing the type and combination of polyimide and reactive liquid crystal, a liquid crystal display element in which a ferroelectric liquid crystal was sandwiched between a rubbing film and a reactive liquid crystal layer was produced in the same manner as described above. Results were obtained.

Next, a liquid crystal display element in which a ferroelectric liquid crystal was sandwiched between a rubbing film and a photo-alignment film containing a photoisomerizable material was produced.
On the glass substrate on which the ITO electrode was formed, polyimide (manufactured by Nissan Chemical Industries, trade name: SE-7492) was printed and rubbed to form an alignment film. Also, a photoisomerizable material (trade name: LIA01, manufactured by Dainippon Ink Co., Ltd.) is spin-coated on a glass substrate on which an ITO electrode is formed, dried at 100 ° C. for 3 minutes, and then subjected to linearly polarized ultraviolet rays of about 1000 mJ. / Cm < ² > was irradiated and alignment treatment was performed.
Thereafter, a liquid crystal display element was produced in the same manner as described above.

  When a voltage was applied so that the electrode on the rubbing film side became a negative electrode, the molecular direction of the ferroelectric liquid crystal changed about twice the tilt angle. About 70% of the ferroelectric liquid crystal molecules changed in molecular direction about twice the tilt angle.

  In addition, a liquid crystal display in which a ferroelectric liquid crystal is sandwiched between a rubbing film and a photo-alignment film containing a photoisomerizable material in the same manner as described above by changing the type and combination of polyimide and the photoisomerizable material. When the device was fabricated, the same result as above was obtained.

  From the results of the above-described experiment, the positive electrode of the spontaneous polarization of the ferroelectric liquid crystal faces the rubbing film side in the rubbing film and the photo-alignment film or reactive liquid crystal layer containing the photodimerization-type material in the state where no voltage is applied. The rubbing film and the photo-alignment film containing the photoisomerizable material tend to have the spontaneous polarization positive electrode of the ferroelectric liquid crystal facing the photo-alignment film side containing the photoisomerization-type material. I got the knowledge. This is considered to be due to the influence of the polar surface interaction, which is the interaction between the ferroelectric liquid crystal and the surface of each layer.

Hereinafter, the liquid crystal display element of the present invention will be described in detail.
The liquid crystal display element of the present invention can be divided into two embodiments according to the configuration of the first alignment layer of the first alignment processing substrate. In the first embodiment, the first alignment layer of the first alignment substrate is formed on the entire surface of the first base material. In the second embodiment, the first alignment layer of the first alignment substrate is the first substrate. It is formed in a pattern on the material and is composed of a first alignment pattern and a second alignment pattern. Hereinafter, the liquid crystal display element of each embodiment will be described in detail.

I. First Embodiment First, a first embodiment of the liquid crystal display element of the present invention will be described.
The liquid crystal display element of this embodiment includes a first substrate, a first electrode layer formed on the first substrate, a first alignment layer formed on the first electrode layer and made of a rubbing film, A first alignment treatment substrate, a second substrate, a second electrode layer formed on the second substrate, and a first alignment pattern and a second alignment formed on the second electrode layer. A second alignment treatment substrate having a second alignment layer made of a pattern is disposed so that the first alignment layer and the second alignment layer are opposed to each other, and the first alignment layer and the second alignment layer are disposed between the first alignment layer and the second alignment layer. A liquid crystal display element having a ferroelectric liquid crystal sandwiched therebetween, wherein the ferroelectric liquid crystal exhibits monostability and half V-shaped switching characteristics, and the first alignment pattern is a light Includes photoisomerizable materials that impart anisotropy to alignment films by causing isomerization reactions. The second alignment pattern is formed on the reactive liquid crystal alignment film, and the reactive liquid crystal layer is formed by immobilizing the reactive liquid crystal. Or a pattern made of a photo-alignment film containing a photo-dimerization material that imparts anisotropy to the alignment film by causing a photo-dimerization reaction.

  “Showing monostability” means a state in which the state of the ferroelectric liquid crystal when no voltage is applied is stabilized in one state. In the ferroelectric liquid crystal, as illustrated in FIG. 1, the liquid crystal molecules LC are inclined from the layer normal z, and rotate along a cone ridge having a bottom surface perpendicular to the layer normal z. In such a cone, the tilt angle of the liquid crystal molecules LC with respect to the layer normal z is referred to as a tilt angle θ. Thus, the liquid crystal molecules LC can operate on the cone between two states inclined by a tilt angle ± θ with respect to the layer normal z. More specifically, the expression of “monostable” means a state in which the liquid crystal molecules LC are stabilized in any one state on the cone when no voltage is applied.

  The “half V-shaped switching characteristic” refers to an electro-optical characteristic in which the light transmittance with respect to an applied voltage is asymmetric. Specifically, the liquid crystal molecules operate only when a positive or negative voltage as shown in FIG. 2 is applied.

The liquid crystal display element of this embodiment will be described with reference to the drawings.
3 and 4 are cross-sectional views showing an example of the liquid crystal display element of this embodiment.

  In the liquid crystal display element 1 illustrated in FIG. 3, a first alignment treatment substrate 5 in which a first alignment layer 4 including a first electrode layer 3 and a rubbing film is formed on a first substrate 2, and a second substrate The second alignment treatment substrate 15 on which the second electrode layer 13 and the second alignment layer 14 are formed is opposed to each other, and the first alignment layer 4 of the first alignment treatment substrate 5 and the second alignment treatment substrate 15 are opposed to each other. A ferroelectric liquid crystal is interposed between the second alignment layer 14 and the liquid crystal layer 10. The second alignment layer 14 includes a first alignment pattern 14a and a second alignment pattern 14b, and a partition wall 16 is formed between the first alignment pattern 14a and the second alignment pattern 14b. The first alignment pattern 14a is a pattern made of a photo-alignment film containing a photoisomerizable material, and the second alignment pattern 14b is a pattern made of a photo-alignment film containing a photodimerization type material.

  In the liquid crystal display element 1 illustrated in FIG. 4, the first alignment pattern 14a is a pattern made of a photo-alignment film containing a photoisomerizable material, and the second alignment pattern 14b is a reactive liquid crystal alignment. It is a pattern comprising a film 17 and a reactive liquid crystal layer 18 formed on the reactive liquid crystal alignment film 17. Other structures are the same as those of the liquid crystal display element shown in FIG.

Since the ferroelectric liquid crystal has spontaneous polarization, the direction of spontaneous polarization is determined by the polarity effect as the interaction between the ferroelectric liquid crystal and the first alignment layer surface and the second alignment layer surface.
In this embodiment, the ferroelectric liquid crystal is sandwiched between the first alignment layer and the first alignment pattern and the second alignment pattern of the second alignment layer.

  In the example shown in FIG. 3, the first alignment layer 4 is made of a rubbing film, the first alignment pattern 14a of the second alignment layer is a pattern made of a photo-alignment film containing a photoisomerizable material, and the second alignment layer Since the second alignment pattern 14b of the layer is a pattern made of a photo-alignment film containing a photodimerization-type material, the first alignment pattern and the second alignment layer of the first alignment layer and the second alignment layer are selected according to the respective constituent materials. The second alignment pattern of the alignment layer may have different polarities. Accordingly, the polar surface interaction between the ferroelectric liquid crystal and the first alignment layer, the polar surface interaction between the ferroelectric liquid crystal and the first alignment pattern of the second alignment layer, and the ferroelectric liquid crystal and the second alignment. The polar surface interactions with the second alignment pattern of the layers are different from each other.

  As described above, the photo-alignment film containing the photodimerization type material tends to have a relatively positive polarity compared to the rubbing film, and the rubbing film is more in comparison with the photo-alignment film containing the photoisomerization type material. Therefore, it is considered that the positive polarity tends to be relatively strong. Therefore, when no voltage is applied, the first alignment layer (rubbing film) and the first alignment pattern of the second alignment layer (photo-alignment film containing a photoisomerizable material) are positive in the rubbing film side. It is assumed that the photo-alignment film side containing the chemical conversion material is negative. Therefore, the spontaneous polarization positive electrode can be directed to the first alignment pattern (photo-alignment film containing photoisomerizable material) side of the second alignment layer. On the other hand, in a state where no voltage is applied, the first alignment layer (rubbing film) and the second alignment pattern of the second alignment layer (photo-alignment film containing a photodimerization-type material) have a photoalignment containing a photodimerization-type material. It is assumed that the film side is positive and the rubbing film side is negative. Therefore, the positive electrode of spontaneous polarization can be directed to the first alignment layer (rubbing film) side.

  In the example shown in FIG. 4, the first alignment layer 4 is made of a rubbing film, and the first alignment pattern 14a of the second alignment layer is a pattern made of a photo-alignment film containing a photoisomerizable material. Since the second alignment pattern 14b of the two alignment layer is a pattern including the alignment film 17 for reactive liquid crystal and the reactive liquid crystal layer 18, the first alignment layer and the second alignment layer in accordance with the respective constituent materials. The first alignment pattern and the second alignment pattern of the second alignment layer may have different polarities. Accordingly, the polar surface interaction between the ferroelectric liquid crystal and the first alignment layer, the polar surface interaction between the ferroelectric liquid crystal and the first alignment pattern of the second alignment layer, and the ferroelectric liquid crystal and the second alignment. The polar surface interactions with the second alignment pattern of the layers are different from each other.

  As described above, the reactive liquid crystal layer tends to have a relatively positive polarity compared to the rubbing film, and the rubbing film is relatively positive compared to the photo-alignment film containing the photoisomerizable material. It is thought that there is a strong tendency. Therefore, when no voltage is applied, the first alignment layer (rubbing film) and the first alignment pattern of the second alignment layer (photo-alignment film containing a photoisomerizable material) are positive in the rubbing film side. It is assumed that the photo-alignment film side containing the chemical conversion material is negative. Therefore, the spontaneous polarization positive electrode can be directed to the first alignment pattern (photo-alignment film containing photoisomerizable material) side of the second alignment layer. On the other hand, when no voltage is applied, the reactive liquid crystal layer side is positive in the first alignment layer (rubbing film) and the second alignment pattern of the second alignment layer (reactive liquid crystal alignment film and reactive liquid crystal layer). It is assumed that the rubbing film side is negative. Therefore, the positive electrode of spontaneous polarization can be directed to the first alignment layer (rubbing film) side.

  That is, as illustrated in FIG. 5, in the region 21 in which the first alignment pattern 14 a of the second alignment layer is provided, the positive polarity (+) of the spontaneous polarization Ps of the liquid crystal molecules LC is used as the first alignment of the second alignment layer. It can be directed to the pattern 14a side. On the other hand, in the region 22 where the second alignment pattern 14b of the second alignment layer is provided, the positive electrode (+) of the spontaneous polarization Ps of the liquid crystal molecules LC can be directed to the first alignment layer 4 side.

  Thus, in consideration of the surface polarity of the first alignment layer, the first alignment pattern of the second alignment layer, and the second alignment pattern of the second alignment layer, the first alignment pattern of the first alignment layer and the second alignment layer. The direction of spontaneous polarization can be controlled by combining the second alignment pattern of the second alignment layer with a predetermined combination. As a result, the direction of spontaneous polarization can be reversed for each region of the second alignment layer where the first alignment pattern or the second alignment pattern is provided, and polarity inversion driving is possible.

  Moreover, in the ferroelectric liquid crystal, the direction of the liquid crystal molecules, the direction of spontaneous polarization, and the direction of the layer normal are in a predetermined relationship, so the layer normal depends on the direction of the liquid crystal molecules and the direction of spontaneous polarization. The direction is determined. For example, as shown in FIGS. 6A and 6B, the direction of the layer normal z differs depending on the direction of the spontaneous polarization Ps. In FIG. 6A, the spontaneous polarization Ps of the liquid crystal molecules LC is directed from the front to the back of the page (indicated by a cross in FIG. 6A), and in FIG. 6B, the spontaneous polarization of the liquid crystal molecules LC is performed. The polarization Ps is directed toward the back of the paper (the mark ● in FIG. 6B).

  In this embodiment, as described above, the direction of the spontaneous polarization is changed by combining the first alignment layer, the first alignment pattern of the second alignment layer, and the second alignment pattern of the second alignment layer in a predetermined combination. Can be controlled. In the example shown in FIG. 5, in each of the regions 21 and 22, as illustrated in FIG. 7, the monodomain orientation can be obtained by aligning the direction of the spontaneous polarization Ps in a certain direction.

FIG. 7 is a diagram showing an example of the alignment state of the ferroelectric liquid crystal, and shows the alignment state of the ferroelectric liquid crystal when FIG. 5 is viewed from above. 7 are the same as those in FIG. 6.
In general, in a liquid crystal display element using ferroelectric liquid crystal, two alignment layers facing each other are arranged so that their alignment processing directions are parallel to each other. When no voltage is applied, the ferroelectric liquid crystal is aligned along the alignment treatment direction of the first alignment layer and the second alignment layer.
As illustrated in FIG. 7, in the state where no voltage is applied, the liquid crystal molecules LC are aligned along the alignment treatment direction d of the first alignment layer and the second alignment layer, and are in a uniform alignment state. In the region 21 where the first alignment pattern of the second alignment layer is provided and the region 22 where the second alignment pattern of the second alignment layer is provided, the direction of the spontaneous polarization Ps is reversed, and the layer Although the direction of the normal line z is different, in each of the regions 21 and 22, since the directions of the spontaneous polarization Ps are aligned in a certain direction, a monodomain orientation can be obtained. By aligning the direction of spontaneous polarization in each region in a certain direction, the occurrence of alignment defects can be suppressed in each region, and the alignment of the ferroelectric liquid crystal can be made monodomain.

In general, a ferroelectric liquid crystal having a phase sequence passing through an SmA phase has a chevron structure in which the distance between smectic layers is reduced in the process of phase change and the smectic layer is bent to compensate for the volume change. Depending on the bending direction, domains having different major axis directions of liquid crystal molecules are formed, and alignment defects called zigzag defects or hairpin defects are likely to occur at the boundary surface. In order to prevent the occurrence of zigzag defects and hairpin defects, it is effective to increase the pretilt angle.
With the rubbing film, a relatively high pretilt angle can be realized. Therefore, by using a rubbing film for the first alignment layer, it is possible to effectively suppress the occurrence of zigzag defects and hairpin defects.

  Hereinafter, each structure in the liquid crystal display element of this embodiment is demonstrated.

1. First alignment processing substrate The first alignment processing substrate in the present embodiment includes a first base material, a first electrode layer formed on the first base material, and a rubbing film formed on the first electrode layer. And a first alignment layer.
Hereinafter, each structure in a 1st orientation processing board | substrate is demonstrated.

(1) 1st orientation layer The 1st orientation layer in this embodiment is formed on the 1st electrode layer, and consists of a rubbing film.

  The material used for the rubbing film is not particularly limited as long as it can impart anisotropy to the alignment film by rubbing treatment. For example, polyimide, polyamide, polyamideimide, polyetherimide, polyvinyl Examples thereof include alcohol and polyurethane. These may be used alone or in combination of two or more.

  Especially, it is preferable that a rubbing film | membrane contains a polyimide, and it is especially preferable to contain the polyimide which carried out the dehydration ring closure (imidation) of the polyamic acid.

A polyamic acid can be synthesized by reacting a diamine compound with an acid dianhydride.
Examples of the diamine compound used when synthesizing the polyamic acid include alicyclic diamines, carbocyclic aromatic diamines, heterocyclic diamines, aliphatic diamines, and aromatic diamines.

  Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexane, and isophorone diamine. Etc.

  Examples of the carbocyclic aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminotoluenes (specifically 2,4-diaminotoluene), 1,4-diamino- 2-methoxybenzene, diaminoxylenes (specifically 1,3-diamino-2,4-dimethylbenzene), 1,3-diamino-4-chlorobenzene, 1,4-diamino-2,5-dichlorobenzene 1,4-diamino-4-isopropylbenzene, 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylmethane, 2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4'-diaminodiphenyl ether, 4,4'-diphenylthioether, 4,4'-diaminodiphenyl sulfone, , 3'-diaminodiphenylsulfone, 4,4'-diaminobenzoic acid phenyl ester, 4,4'-diaminobenzophenone, 4,4'-diaminobenzyl, bis (4-aminophenyl) phosphine oxide, bis (3-amino Phenyl) sulfone, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) cyclohexylphosphine oxide, N, N-bis (4-aminophenyl) -N-phenylamine, N, N-bis (4 -Aminephenyl) -N-methylamine, 4,4'-diaminodiphenylurea, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, diaminofluorenes (specifically, 2 , 6-Diaminofluorene), bis (4-aminophenyl) diethyl Lan, bis (4-aminophenyl) dimethylsilane, 3,4'-diaminodiphenyl ether, benzidine, 2,2'-dimethylbenzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [ 4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4- Examples thereof include bis (4-aminophenoxy) benzene and 1,3-bis (4-aminophenoxy) benzene.

  Examples of the heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-s-triazine, 2,5-diaminodibenzofuran, 2,7-diaminocarbazole, 3, Examples include 6-diaminocarbazole, 3,7-diaminophenothiazine, 2,5-diamino-1,3,4-thiadiazole, 2,4-diamino-6-phenyl-s-triazine.

  Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,5-diamino-2,4-dimethylheptane, 1,7- Examples include diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.

  Examples of the aromatic diamine include those having a long-chain alkyl or perfluoro group represented by the structure of the following formula.

Here, in the above formula, R ²¹ represents a monovalent organic group containing a long-chain alkyl group, a long-chain alkyl group or a perfluoroalkyl group having 5 or more carbon atoms, preferably 5 to 20 carbon atoms.

  Examples of the acid dianhydride used as a raw material when synthesizing a polyamic acid include aromatic acid dianhydrides and alicyclic acid dianhydrides.

  Examples of aromatic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid. Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid A dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride etc. are mentioned.

  Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4 , 5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy- Examples include 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, and the like.

  These acid dianhydrides may be used alone or in combination of two or more. From the viewpoint of polymer transparency, it is preferable to use an alicyclic acid dianhydride.

  The polyamic acid is a mixture of the above diamine compound and acid dianhydride in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 80 ° C., for 30 minutes to 24 hours, preferably 1 hour. It can synthesize | combine by making it react for 10 hours.

  As a method of obtaining a polyimide film using polyamic acid, after polyamic acid is formed, all or part of the ring is dehydrated (imidized) by heating or a catalyst, or all polyamic acid is heated or by a catalyst. Alternatively, a method of forming a film after forming a soluble polyimide after partially dehydrating and ring-closing (imidizing) to form a soluble polyimide can be mentioned. Especially, since the soluble polyimide obtained by imidizing polyamic acid is excellent in storage stability, the method of forming a film of soluble polyimide is preferable.

  Examples of a method for performing an imidization reaction for converting a polyamic acid into a soluble polyimide include thermal imidation in which a polyamic acid solution is heated as it is, and chemical imidation in which a catalyst is added to the polyamic acid solution to perform imidization. . Among these, the chemical imidation in which the imidization reaction proceeds at a relatively low temperature is preferable because the molecular weight of the resulting soluble polyimide is less likely to decrease.

  In the chemical imidization reaction, polyamic acid in an organic solvent is 0.5 to 30 mol times, preferably 1 to 20 mol times the base catalyst of the amic acid group, and 0.5 to 50 mol times of the amic acid group. The reaction is preferably performed in the presence of 1 to 30 moles of acid anhydride at a temperature of -20 ° C to 250 ° C, preferably 0 ° C to 200 ° C for 1 hour to 100 hours. This is because when the amount of the base catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and when the amount is too large, it is difficult to completely remove the reaction after completion of the reaction.

Examples of the base catalyst used in the chemical imidation reaction include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has a basicity suitable for advancing the reaction.
Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among these, use of acetic anhydride is preferable because purification after completion of the reaction becomes easy.

  As an organic solvent for performing the imidization reaction, a solvent used at the time of polyamic acid synthesis can be used.

  The imidization rate by chemical imidation can be controlled by adjusting the amount of catalyst and the reaction temperature. Among these, the imidation ratio is preferably 0.1% to 99%, more preferably 5% to 90%, and further preferably 30% to 70% of the number of moles of all polyamic acids. This is because if the imidization rate is too low, the storage stability is deteriorated, and if it is too high, the solubility is poor and may be precipitated.

  As the material for the rubbing film, “SE-5291”, “SE-7992”, and “SE-7492” manufactured by Nissan Chemical Industries, Ltd. are preferably used.

  As a rubbing treatment method, it is possible to use a method of applying anisotropy to the alignment film by applying and curing the above-mentioned material on the first electrode layer and rubbing the obtained film with a rubbing cloth in a certain direction. it can.

  Examples of the method for applying the material include a roll coating method, a rod bar coating method, a slot die coating method, a wire bar coating method, an ink jet method, a flexographic printing method, and a screen printing method.

  Further, the thickness of the rubbing film is set to about 1 nm to 1000 nm, and preferably in the range of 50 nm to 100 nm.

  As the rubbing cloth, for example, a cloth made of a fiber such as nylon resin, vinyl resin, rayon, or cotton can be used. For example, by rotating a drum wound with such a rubbing cloth and bringing it into contact with the surface of the film using the above material, fine grooves are formed in one direction on the film surface, and the alignment film has anisotropy. Is granted.

(2) 1st electrode layer The 1st electrode layer in this embodiment will not be specifically limited if it is generally used as an electrode of a liquid crystal display element. The first electrode layer may be transparent or opaque and is appropriately selected according to the image display surface. When the first alignment processing substrate side is an image display surface, the first electrode layer is preferably transparent and is preferably composed of a transparent conductor. Preferred examples of the transparent conductor material include indium oxide, tin oxide, indium tin oxide (ITO), and the like.

  When the liquid crystal display element of the present invention is driven by an active matrix method using TFTs, for example, when the first alignment processing substrate is a TFT substrate, the first electrode layer is a pixel electrode. On the other hand, when the first alignment processing substrate is a common electrode substrate, the first electrode layer is a common electrode.

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

(3) 1st base material The 1st base material in this embodiment will not be specifically limited if generally used as a base material of a liquid crystal display element, Transparent or opaque may be sufficient as it. . As a 1st base material, a glass plate, a plastic plate, etc. are mentioned preferably, for example.

2. Second alignment processing substrate The second alignment processing substrate in the present embodiment is formed on the second base material, the second electrode layer formed on the second base material, the second electrode layer, and the first base material. A second alignment layer comprising an alignment pattern and a second alignment pattern.
The second base material and the second electrode layer are the same as the first base material and the first electrode layer of the first alignment processing substrate, respectively, and thus the description thereof is omitted here. Hereinafter, another configuration of the second alignment processing substrate will be described.

(1) Second alignment layer The second alignment layer in the present embodiment is formed on the second electrode layer, and includes a first alignment pattern and a second alignment pattern. This first alignment pattern is a pattern made of a photo-alignment film containing a photoisomerizable material. Further, the second alignment pattern is a pattern composed of a reactive liquid crystal alignment film and a reactive liquid crystal layer formed on the reactive liquid crystal alignment film, or a photo alignment film containing a photodimerization type material. Is one of the following patterns.
Hereinafter, other configurations of the first alignment pattern, the second alignment pattern, and the second alignment layer will be described.

(I) 1st orientation pattern The 1st orientation pattern which comprises a 2nd orientation layer is a pattern which consists of a photo-alignment film containing a photoisomerization type material. A photo-alignment film containing a photoisomerizable material irradiates the substrate with the photoisomerizable material irradiated with light with controlled polarization to cause anisotropy to the film obtained by causing a photoisomerization reaction. By doing so, the liquid crystal molecules on the film are aligned. Since the photo-alignment process is a non-contact alignment process, it is useful in that there is no generation of static electricity or dust and quantitative alignment control is possible.

  The photoisomerization type material is a material that imparts anisotropy to the photo-alignment film by causing a photoisomerization reaction as described above, and is not 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 isomers of either the cis form or the trans form are increased by light irradiation, whereby anisotropy can be imparted to the 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 spacer 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 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 (1).

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) to (5).

  Examples of the polymerizable monomer having the azobenzene skeleton as a side chain include compounds represented by the following formula (6).

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 (7) to (10).

  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 polymerization inhibitor is preferably in the range of 0.001% by mass to 20% by mass, and in the range of 0.1% by mass to 5% by mass 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.

  The wavelength region of the light that causes the photoisomerization reaction of the photoisomerizable material 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. .

  In order to form a photo-alignment film containing a photoisomerizable material, first, a photoalignment film-forming coating solution obtained by diluting the photoisomerizable material with an organic solvent is applied and dried. In this case, the content of the photodimerization reactive compound in the coating liquid for forming a photoalignment film is preferably in the range of 0.05% by mass to 10% by mass, and 0.2% by mass to 2% by mass. % Is more preferable. 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.

  Examples of the application method of the coating liquid for forming a photo-alignment film include spin coating, roll coating, rod bar coating, spray coating, air knife coating, slot die coating, wire bar coating, ink jet, and flexographic 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 region of the light to be irradiated may be appropriately selected according to the photoisomerization type material to be used, but is preferably in the range of the ultraviolet region, that is, in the range of 100 nm to 400 nm, more preferably 250 nm It is in the range of 380 nm. The polarization direction is not particularly limited as long as it can cause the photoisomerization reaction.

  Furthermore, when a polymerizable monomer is used as a photoisomerization type material among photoisomerization reactive compounds, it is polymerized by heating after photoalignment treatment and applied to the photoalignment film. Anisotropy can be stabilized.

(Ii) Second alignment pattern The second alignment pattern constituting the second alignment layer is a pattern comprising a reactive liquid crystal alignment film and a reactive liquid crystal layer formed on the reactive liquid crystal alignment film, or , Any of a pattern made of a photo-alignment film containing a photodimerization type material. Hereinafter, a pattern composed of a photo-alignment film containing a photodimerization type material and a pattern composed of a reactive liquid crystal alignment film and a reactive liquid crystal layer will be described.

(Pattern consisting of photo-alignment film containing photo-dimerization type material)
A photo-alignment film containing a photo-dimerization type material is obtained by irradiating a substrate coated with the photo-dimerization-type material with light having a controlled polarization, and causing anisotropy to the film obtained by causing a photo-dimerization reaction. The liquid crystal molecules on the film are aligned. Since the photo-alignment process is a non-contact alignment process, it is useful in that there is no generation of static electricity or dust and quantitative alignment control is possible. In addition, the photodimerization type material has the advantages of high exposure sensitivity and a wide range of material selection.

  The photodimerization type material is a material that imparts anisotropy to the photoalignment film by causing a photodimerization reaction. The photodimerization reaction is a reaction in which reaction sites aligned in the polarization direction by light irradiation undergo radical polymerization and two molecules are polymerized. This reaction stabilizes the alignment in the polarization direction and is anisotropic to the photo-alignment film. It is possible to impart sex.

  The photodimerization type material is not particularly limited as long as it is a material that can impart anisotropy to the photo-alignment film by a photodimerization reaction, but has a radical polymerizable functional group and is polarized. It is preferable to include a photodimerization reactive compound having dichroism with different absorption depending on the 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.

  An example of the dimerization reactive polymer is a compound represented by the following formula (11).

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 spacer units.

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 (12) to (15).

  More specific examples of the dimerization reactive polymer include compounds (16) to (19) represented by the following formulae.

  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 photodimerization-type material 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 mass to 20% by mass, and in the range of 0.1% by mass to 5% by mass 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 light dimerization type material include “ROP102” and “ROP103” manufactured by Rolic technologies.

  The wavelength region of light that causes the photodimerization reaction of the photodimerization material 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.

  Note that the method for forming the photo-alignment film containing the photodimerization-type material is the same as the method for forming the photo-alignment film containing the photoisomerization-type material, and the description thereof is omitted here.

(Pattern consisting of an alignment film for reactive liquid crystal and a reactive liquid crystal layer)
The second alignment pattern may be composed of an alignment film for reactive liquid crystal and a reactive liquid crystal layer. The reactive liquid crystal is aligned by the alignment film for reactive liquid crystal. 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 is preferably one that 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.

  Examples of the monoacrylate monomer include compounds represented by the following formulas (20) and (21).

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. Furthermore, the acryloyloxy group at the end of the molecular chain and A or D may be bonded via a spacer such as an alkylene group having 3 to 6 carbon atoms.

  Examples of the diacrylate monomer include compounds represented by the following formulas (22) and (23).

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 (22), X is preferably alkyloxycarbonyl having 1 to 20 carbon atoms, methyl or chlorine, and especially alkyloxycarbonyl having 1 to 20 carbon atoms, particularly CH ₃ (CH ₂ ) ₄ OCO. It is preferable that

  Examples of the diacrylate monomer include a compound represented by the following formula (24).

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 (24) include a compound represented by the following formula (25).

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.

  Among these, compounds represented by the above formulas (22) and (24) are preferably used. Specific examples of the compound represented by the above formula (24) 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.

  Of 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, 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. As a photoinitiator, the photoinitiator as described in Unexamined-Japanese-Patent No. 2005-258428 can be used, for example. Moreover, it is also possible to add a sensitizer other than a photoinitiator in the range which does not impair the objective of this invention.

  The amount of the photopolymerization initiator added is generally 0.01 to 20% by mass, preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass. 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 is formed by applying a reactive liquid crystal layer forming coating liquid containing reactive liquid crystal on the alignment film for reactive liquid crystal, performing an alignment treatment, and fixing the alignment state of the reactive liquid crystal. Can be formed. Alternatively, a reactive liquid crystal layer may be formed by forming a dry film or the like in advance and laminating it on the reactive liquid crystal alignment film, instead of applying a reactive liquid crystal layer forming coating solution. Good. From the viewpoint of the simplicity of the manufacturing process, a method of preparing a reactive liquid crystal layer forming coating solution by dissolving a reactive liquid crystal in a solvent, applying the solution on a reactive liquid crystal alignment film, and removing the solvent Is preferably used.

  The solvent used in the reactive liquid crystal layer forming coating solution 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 reactive liquid crystal alignment film. is not. As such a solvent, for example, a solvent described in Japanese Patent Application Laid-Open No. 2005-258428 can be used. A solvent may be used independently and may use 2 or more types together.

  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 reactive liquid crystal 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 and thus cannot be defined unconditionally, but is usually 0.1 to 40% by mass, preferably It adjusts in the range of 1-20 mass%. 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 reactive liquid crystal layer forming coating solution may be added with a compound as described in, for example, Japanese Patent Application Laid-Open No. 2005-258428, within a range not impairing the object of the present invention. 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, ink jet method, flexographic printing method, screen printing 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 for reactive liquid crystal 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 the light source of this irradiation light, low pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high pressure discharge lamp (high pressure mercury lamp, metal halide lamp), 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 actinic radiation may be performed under a temperature condition where the polymerizable liquid crystal material becomes a liquid crystal phase, or may be performed at a temperature lower than a temperature where the polymerizable liquid crystal material becomes a liquid crystal phase. 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.

  The alignment film for reactive liquid crystal is not particularly limited. For example, a rubbing film, a photo-alignment film containing a photoisomerizable material, a photo-alignment film containing a photodimerization material, or the like can be used. .

  The alignment film for reactive liquid crystal may be the same as or different from the photo-alignment film containing the photoisomerizable material constituting the first alignment pattern. When the alignment film for reactive liquid crystal is the same as the photo-alignment film containing the photoisomerizable material constituting the first alignment pattern, as illustrated in FIG. 8, the alignment film 17 for reactive liquid crystal and the first alignment film The alignment pattern 14a may be formed continuously, and as illustrated in FIG. 4, the reactive liquid crystal alignment film 17 and the first alignment pattern 14a may be formed apart from each other. On the other hand, when the alignment film for the reactive liquid crystal is different from the photo alignment film containing the photoisomerizable material constituting the first alignment pattern, the alignment film for the reactive liquid crystal and the first alignment pattern are usually formed separately. Is done.

(Iii) First alignment pattern and second alignment pattern The shape of the first alignment pattern and the second alignment pattern in the present invention may be a pattern shape generally applied to polarity inversion driving, for example, a line shape , Dot shape and the like.

  The formation method of the first alignment pattern and the second alignment pattern is not particularly limited as long as a desired pattern can be obtained. Among them, a wettability change pattern composed of a liquid repellent region and a lyophilic region as described later, or a liquid repellent region on the surface of the insulating portion and a lyophilic region on the surface of the layer in the opening of the insulating portion. A method of forming the first alignment pattern and the second alignment pattern by using a difference in wettability or by using a partition wall is preferably used.

The second alignment pattern includes a reactive liquid crystal alignment film and a reactive liquid crystal layer, and the reactive liquid crystal alignment film contains a photoisomerizable material that forms the first alignment pattern. If it is the same as the photo-alignment film, a photo-alignment film containing a photoisomerizable material is formed on the entire surface of the second substrate, and a reactive liquid crystal layer-forming coating solution is applied to the entire surface of the photo-alignment film. The obtained film is subjected to pattern exposure to partially cure the reactive liquid crystal, and then developed with an organic solvent, whereby the first alignment pattern and the second alignment pattern can be formed. In this case, as illustrated in FIG. 8, the first alignment pattern 14a is a pattern made of a photo-alignment film containing a photoisomerizable material, and the second alignment pattern 14b is a photo-alignment containing a photoisomerizable material. A second alignment-treated substrate 15, which is a pattern composed of a film (reactive liquid crystal alignment film 17) and a reactive liquid crystal layer 18, in which a first alignment pattern and a reactive liquid crystal alignment film are continuously formed. Obtainable.
In order to partially cure the reactive liquid crystal by pattern exposure, the method of irradiating actinic radiation described in the above-mentioned reactive liquid crystal layer may be used. Fixation of the alignment state of the polymerizable liquid crystal material and pattern exposure can be performed simultaneously. Moreover, as a developing method, the method of immersing the film | membrane after pattern exposure in MEK etc. can be used, for example. After development, washing with IPA, water or the like is preferable.

(2) Wettability changing layer In the second alignment treatment substrate of the present embodiment, as illustrated in FIG. 9, the photocatalyst action accompanying energy irradiation is provided between the second electrode layer 13 and the second alignment layer 14. The wettability changing layer 25 whose wettability changes due to the wettability changing layer 25 may be formed, and a wettability changing pattern including the lyophilic region 26a and the liquid repellent region 26b may be formed on the surface of the wettability changing layer 25. In this case, the second alignment layer 14 (the first alignment pattern 14a and the second alignment pattern 14b) is formed only on the lyophilic region 26a. By forming the wettability changing layer, the first alignment pattern and the second alignment pattern can be easily and accurately formed using the wettability changing pattern formed on the surface of the wettability changing layer.

  The wettability changing layer 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 second alignment treatment substrate is not affected by the photocatalyst over time.

In this embodiment, as illustrated in FIG. 10, a wettability changing layer 25 formed on the second electrode layer 13 and a photocatalyst-containing layer substrate 51 having a base 52 and a photocatalyst processing layer 53 are separated from each other by a predetermined gap. And irradiating with energy 56 through the photomask 55 (FIG. 10A) to change the wettability of the energy irradiated portion of the wettability changing layer 25 surface to form the lyophilic region 26a. Thus, a wettability change pattern composed of the lyophilic region 26a and the liquid repellent region 26b can be formed (FIG. 10B). Then, a first alignment pattern forming coating solution is applied to a predetermined portion of the lyophilic region 26a by an ink jet method or the like to form the first alignment pattern 14a, and then to the other portion of the lyophilic region 26a. A second alignment pattern forming coating solution is applied by an ink jet method or the like to form the second alignment pattern 14b (FIG. 10C).
Hereinafter, the wettability changing layer, the photocatalyst processing layer substrate, the wettability changing pattern forming method, and the wettability changing pattern 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.

The photocatalyst used in the present invention is 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 represented by the above 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 mass, preferably within a range of 20 to 50% by mass. 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 part 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 where 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.
In addition, as a method of irradiating energy in a pattern shape, in addition to a method of irradiating a pattern through a photomask using these light sources, a method of irradiating a pattern in a pattern shape 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 spacer described above, 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.

(Wettability change pattern)
The wettability change pattern in this embodiment is formed on the surface of the wettability change layer, and consists of a lyophilic region that is an energy irradiated portion and a liquid repellent region that is an unirradiated portion.
In this embodiment, the lyophilic region is an energy irradiation portion, and is a region that has changed in a direction in which the contact angle with the liquid decreases due to energy irradiation. Further, the liquid repellent region is a non-energy-irradiated portion and refers to a region having a larger contact angle with respect to the liquid than the lyophilic region.

  In the liquid repellent region, the contact angle to a liquid having a surface tension equivalent to the surface tension of the alignment layer forming coating solution is preferably 60 ° or more, more preferably 80 ° or more. This is because if the contact angle with the liquid in the liquid repellent region is too low, the alignment layer 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 the alignment layer is preferably 30 ° or less, more preferably 10 ° or less, and still more preferably. 5 ° or less. If the contact angle with the liquid in the lyophilic region is too high, the coating liquid for forming the alignment layer is difficult to spread and the second alignment layer (the first alignment pattern and the second alignment pattern) may be lost. Because there is.

  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.

(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, the wettability changing layer 25 formed on the second electrode layer 13 is irradiated with energy 56 through the photomask 55 (FIG. 11A), and the wettability changing layer 25 is wetted. By changing the wettability of the energy irradiated portion on the surface of the property change layer 25 to form the lyophilic region 26a, a wettability change pattern including the lyophilic region 26a and the lyophobic region 26b can be formed. (FIG. 11 (b)). Then, a first alignment pattern forming coating solution is applied to a predetermined portion of the lyophilic region 26a by an ink jet method or the like to form the first alignment pattern 14a, and then to the other portion of the lyophilic region 26a. A second alignment pattern forming coating solution is applied by an ink jet method or the like to form the second alignment pattern 14b (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. Further, 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 second alignment layer are directly formed. Since it can be made not to contact, it can suppress that the 2nd alignment layer receives the influence of a photocatalyst with 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 5-60 mass%, Preferably it exists in the range of 20-40 mass%.

  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.
Also, the wettability change pattern is the same as that described in the first aspect, and the description thereof is omitted here.

(Iii) Light-shielding part In this embodiment, when the wettability changing layer is formed, the light-shielding part 27 is formed in a pattern on the second substrate 12 as illustrated in FIG. The liquid repellent area 26 b of the change layer 25 is preferably disposed on the light shielding portion 27. Since the second alignment layer is not formed in the liquid repellent region, the ferroelectric liquid crystal is difficult to align, and thus light leakage may occur. However, by arranging the liquid repellent region on the light shielding portion, This is because leakage can be prevented.
Although not shown, in the first alignment substrate, the light shielding portion may be formed in a pattern on the first base material, and the liquid repellent region of the wettability changing layer may be disposed on the light shielding portion. .

The light shielding portion is usually formed in a pattern corresponding to the wettability change pattern.
Examples of the material for forming the light shielding part include a resin composition containing a black colorant such as carbon black, or a metal or metal oxide such as chromium.

  Examples of the method for forming the light-shielding portion include a photolithography method and a printing method when using a resin composition. When using a metal or a metal oxide, for example, an evaporation method, an ion plating method, a sputtering method, an electric fieldless method, or the like. The plating method etc. are mentioned.

(3) Insulating portion In the second alignment processing substrate of the present embodiment, as illustrated in FIG. 13, an insulating portion 28 is formed between the first alignment pattern 14a and the second alignment pattern 14b, so that insulation is achieved. The surface of the portion 28 may be the liquid repellent region 26b, and the layer surface in the opening of the insulating portion 28 (the surface of the second electrode layer 13) may be the lyophilic region 26a. In this case, the second alignment layer 14 (the first alignment pattern 14a and the second alignment pattern 14b) is formed only on the lyophilic region 26a. Since the insulating portion is formed and the surface of the insulating portion is a liquid repellent region, the first alignment pattern and the second alignment pattern can be easily formed with high accuracy.

  By subjecting the surface of the insulating portion to a liquid repellent treatment, the surface of the insulating portion can be made a liquid repellent region, and the layer surface in the opening of the insulating portion can be made a lyophilic region.

  The liquid repellent treatment method is particularly limited as long as the contact angle with the liquid on the surface of the insulating portion can be made relatively higher than the contact angle with the liquid on the surface of the layer in the opening of the insulating portion. It is not a thing. Generally, glass or the like is used for the base material, and metal or metal oxide is used for the electrode layer. Therefore, an organic material is used for the insulating portion, and a plasma using a fluorine compound as an introduction gas for the insulating portion. The method of irradiating is preferably used. In plasma irradiation using a fluorine compound as an introduction gas, a fluorine compound can be introduced only into an organic substance, so that fluorine can be selectively introduced into an insulating part containing an organic material, and the surface of the insulating part is liquid repellent. Because it can be.

  For example, as shown in FIG. 14, the insulating portion 28 formed between the first alignment pattern 14a and the second alignment pattern 14b is irradiated with plasma 57 using a fluorine compound as an introduction gas (FIG. 14 (a)). By making the plasma-irradiated portion on the surface of the insulating portion 28 lyophobic, the surface of the insulating portion 28 is lyophobic region 26 b and the surface of the layer in the opening of the insulating portion 28 (second electrode layer 13 surface) is a lyophilic region. 26a (FIG. 14B). Then, a first alignment pattern forming coating solution is applied to a predetermined portion of the lyophilic region 26a by an ink jet method or the like to form the first alignment pattern 14a, and then to the other portion of the lyophilic region 26a. A second alignment pattern forming coating solution is applied by an inkjet method or the like to form a second alignment pattern 14b (FIG. 14C).

Examples of the fluorine compound used as the introduced 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 etc. are mentioned.

  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 it is a method capable of irradiating plasma using a fluorine compound as an introduction gas and making the surface of the insulating portion 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. In this case, the distance between the irradiated plasma electrode and the insulating portion 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 insulating part is an X-ray photoelectron spectrometer (XPS: ESCALAB) used in X-ray photoelectron spectroscopy (also called 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 insulating part. At this time, the proportion of fluorine introduced into the insulating portion is preferably 10% or more of all elements detected from the surface of the insulating portion.

In addition, the insulating portion has a contact angle with a liquid having a surface tension equivalent to the surface tension of the coating liquid for forming the alignment layer that is 1 ° or more higher than the contact angle with the liquid of the insulating portion before the liquid repellent treatment. It is preferable to irradiate with plasma. In particular, the insulating portion is preferably irradiated with plasma so that the contact angle with the liquid is 5 ° or more, especially 10 ° or more, and more preferably 30 ° or more. This is because, when the contact angle of the insulating part after the liquid repellent treatment with the liquid is small, the alignment layer forming coating liquid may adhere to the liquid repellent region.
In addition, about the measuring method of a contact angle with a liquid, it is the same as that of what was described in the term of the said wettability change layer.

  The pattern shape of the insulating portion is appropriately selected according to the shapes of the first alignment pattern and the second alignment pattern, and examples thereof include a line shape and a matrix shape. In addition, the pitch, width, etc. of the insulating portions are appropriately adjusted according to the pitch, width, etc. of the first alignment pattern and the second alignment pattern.

  The material for forming the insulating portion is not particularly limited as long as it is an insulating material. However, in the case of irradiating plasma using the above fluorine compound as an introduction gas, it may be an organic material having an insulating property. preferable. Examples of the organic material having insulating properties include resins, and among these, photosensitive resins are 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 insulating part is preferably a light shielding part. Since the second alignment layer is not formed in the liquid repellent region, the orientation of the ferroelectric liquid crystal may be disturbed. However, since the surface of the insulating portion, which is a light shielding portion, is a liquid repellent region, it is ferroelectric. This is because light leakage due to liquid crystal alignment disorder can be prevented.

  When the insulating part is a light-shielding part, as a forming material of the insulating part, for example, a photosensitive resin composition containing a black colorant such as carbon black or titanium black can be used.

  Although the thickness of an insulating part is not specifically limited, When an insulating part is a light shielding part, it is preferable that it is about 1.5 micrometers-2.0 micrometers from a viewpoint of a light shielding function.

  In addition, the method for forming the insulating portion is not particularly limited as long as the insulating portion 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.

(4) Partition Wall In the second alignment treatment substrate of this embodiment, as illustrated in FIG. 15, the partition wall 16 may be formed so as to partition the first alignment pattern 14a and the second alignment pattern 14b. This is because the first alignment pattern and the second alignment pattern can be easily formed with high accuracy by forming the partition walls.

  The pattern shape of the partition is appropriately selected according to the shapes of the first alignment pattern and the second alignment pattern, and examples thereof include a line shape and a matrix shape. In addition, the pitch and width of the partition walls are appropriately adjusted according to the pitch and width of the first alignment pattern and the second alignment pattern. Further, the height of the partition wall is usually set to be approximately the same as the thickness of the liquid crystal layer.

  The material for forming the partition is not particularly limited as long as it is a material generally used as a partition for a liquid crystal display element. Specific examples include resins, and among these, photosensitive resins are 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 partition wall of a liquid crystal display element.

  Further, the method for forming the partition wall is not particularly limited as long as the partition wall 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.

(5) Colored layer In this embodiment, the colored layer may be formed between the 2nd base material and the 2nd electrode layer. In the first alignment treatment substrate, a colored layer may be formed between the first base material and the first electrode layer. That is, a colored layer may be formed on either the first alignment treatment substrate or the second alignment treatment substrate. When a colored layer is formed, color display can be realized by the colored layer.

  The colored layer 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.

3. Liquid Crystal Layer The liquid crystal layer in this embodiment is configured by sandwiching a ferroelectric liquid crystal between the first alignment layer of the first alignment processing substrate and the second alignment layer of the second alignment processing substrate. The ferroelectric liquid crystal used in the present invention is not particularly limited as long as it exhibits monostability and exhibits half V-shaped switching characteristics. Using a ferroelectric liquid crystal exhibiting a half V-shaped switching characteristic, it is possible to take a sufficiently long opening time as a black and white shutter, whereby each color that can be temporally switched can be displayed brighter, and a bright color A liquid crystal display element for display can be realized.

  In this embodiment, the ferroelectric liquid crystal is a ferroelectric liquid crystal when a voltage is applied so that the second electrode layer becomes a negative electrode in the region where the first alignment pattern of the second alignment layer is provided. The first electrode layer is formed in a region where the molecular direction of the first alignment layer is changed approximately twice the tilt angle of the ferroelectric liquid crystal parallel to the first alignment processing substrate surface and the second alignment pattern of the second alignment layer is provided. When a voltage is applied so as to be a negative electrode, the molecular direction of the ferroelectric liquid crystal changes approximately twice the tilt angle of the ferroelectric liquid crystal in parallel to the first alignment treatment substrate surface. preferable.

FIG. 16 shows an example of the alignment state of the ferroelectric liquid crystal sandwiched between the first alignment layer and the first alignment pattern of the second alignment layer.
As described above, in the state where no voltage is applied, as illustrated in FIG. 16A, the positive polarity (+) of the spontaneous polarization Ps of the liquid crystal molecules LC becomes the first alignment pattern of the second alignment layer by the polar surface interaction. It tends to face the 14a side (the photo-alignment film side containing the photoisomerizable material). Then, as illustrated in FIG. 16B, when a voltage is applied so that the first electrode layer 3 is a positive electrode (+) and the second electrode layer 13 is a negative electrode (−), it is influenced by the polarity of the applied voltage. The spontaneous polarization Ps of the liquid crystal molecules LC is directed to the first alignment layer 4 side. Next, when a voltage is applied so that the first electrode layer 3 is a negative electrode (−) and the second electrode layer 13 is a positive electrode (+), as illustrated in FIG. 16A due to the influence of the polarity of the applied voltage. The spontaneous polarization Ps of the liquid crystal molecules LC is directed to the first alignment pattern 14a side of the second alignment layer. In this case, the direction of spontaneous polarization is the same as that in the state where no voltage is applied.

  On the other hand, the orientation state of the ferroelectric liquid crystal sandwiched between the first orientation layer and the second orientation pattern of the second orientation layer is not shown, but as described above, in the voltage-free state, the polar surface Due to the interaction, the positive electrode of the spontaneous polarization of the liquid crystal molecules tends to face the first alignment layer side (rubbing film side). When a voltage is applied so that the first electrode layer is a positive electrode and the second electrode layer is a negative electrode, the spontaneous polarization of the liquid crystal molecules faces the second alignment pattern side of the second alignment layer due to the influence of the polarity of the applied voltage. It becomes like this. Next, when a voltage is applied so that the first electrode layer is a negative electrode and the second electrode layer is a positive electrode, the spontaneous polarization of the liquid crystal molecules comes to the first alignment layer side due to the influence of the polarity of the applied voltage. In this case, the direction of spontaneous polarization is the same as that in the state where no voltage is applied.

  The direction of spontaneous polarization is such a direction because the direction of spontaneous polarization is the direction in which the polarization of the ferroelectric liquid crystal and the polarization of the alignment film or the polarity of the voltage are electrically balanced. This is because the state becomes stable.

  In the region where the first alignment pattern of the second alignment layer is provided, the negative electrode applied to the second electrode layer from the state where no voltage is applied or the state where a positive voltage is applied to the second electrode layer (FIG. 16A). When a negative voltage application state (FIG. 16B) is established, the repulsion between the negative polarity of the applied voltage and the negative polarity of the spontaneous polarization of the liquid crystal molecules causes the liquid crystal molecules LC to have an angle as illustrated in FIG. Rotate about 2θ. That is, when a voltage is applied so that the second electrode layer is a negative electrode, the molecular direction of the ferroelectric liquid crystal is approximately parallel to the first alignment processing substrate surface and is approximately equal to the tilt angle θ of the ferroelectric liquid crystal. It changes twice.

  On the other hand, in the region where the second alignment pattern of the second alignment layer is provided, although not shown in the figure, the negative polarity to the first electrode layer from the voltage non-application state or the positive voltage application state to the first electrode layer. When the voltage is applied, the repulsion between the negative polarity of the applied voltage and the negative polarity of the spontaneous polarization of the liquid crystal molecules causes the liquid crystal molecules LC to rotate by an angle of about 2θ, as illustrated in FIG. That is, when a voltage is applied so that the first electrode layer is a negative electrode, the molecular direction of the ferroelectric liquid crystal is parallel to the first alignment substrate surface, and the tilt angle θ of the ferroelectric liquid crystal is about It changes twice.

  In the region where the first alignment pattern of the second alignment layer is provided, when a voltage is applied so that the second electrode layer is a negative electrode, the molecular direction of the ferroelectric liquid crystal changes about twice the tilt angle. Is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and most preferably 95% or more. In addition, in the region where the second alignment pattern of the second alignment layer is provided, when a voltage is applied so that the first electrode layer becomes a negative electrode, the molecular direction of the ferroelectric liquid crystal changes approximately twice the tilt angle. 70% or more is preferably present, more preferably 80% or more, still more preferably 90% or more, and most preferably 95% or more. This is because a good contrast ratio can be obtained within the above range.

In addition, said ratio can be measured as follows.
First, on the outside of the first alignment treatment substrate and the second alignment treatment substrate, the polarizing plate is crossed Nicol, and the polarization axis of one polarizing plate and the alignment direction of the liquid crystal molecules of the liquid crystal layer are parallel to each other. Deploy. When no voltage is applied, the linearly polarized light transmitted through one polarizing plate and the alignment direction of the liquid crystal molecules coincide with each other. Therefore, the refractive index anisotropy of the liquid crystal molecules is not expressed, and the linearly polarized light transmitted through the other polarizing plate is As it passes through the liquid crystal molecules, it is blocked by the other polarizing plate and becomes dark. On the other hand, in the voltage application state, the liquid crystal molecules move on the cone, and the linearly polarized light transmitted through one polarizing plate and the alignment direction of the liquid crystal molecules have a predetermined angle, and thus transmitted through one polarizing plate. Linearly polarized light becomes elliptically polarized light due to the birefringence of liquid crystal molecules. Of the elliptically polarized light, only the linearly polarized light that matches the polarization axis of the other polarizing plate is transmitted through the other polarizing plate and becomes a bright state.

  For this reason, in a region where the first alignment pattern of the second alignment layer is provided, when a voltage is applied so that the second electrode layer is a negative electrode, the molecular direction of the ferroelectric liquid crystal is about twice the tilt angle. A bright state is obtained when it changes. On the other hand, when a voltage is applied so that the second electrode layer is a negative electrode, for example, when a portion of the ferroelectric liquid crystal whose molecular direction does not change partially exists, a dark state is partially obtained. Therefore, from the white / black area ratio of black and white (bright and dark) display obtained when the voltage is applied, the molecular direction of the ferroelectric liquid crystal when the voltage is applied so that the second electrode layer is a negative electrode is about 2 tilt angles. The ratio of what doubles can be calculated.

  Similarly, in a region where the second alignment pattern of the second alignment layer is provided, when a voltage is applied so that the first electrode layer becomes a negative electrode, the molecular direction of the ferroelectric liquid crystal is about twice the tilt angle. A bright state is obtained when it changes. On the other hand, when a voltage is applied so that the first electrode layer is a negative electrode, for example, when a portion of the ferroelectric liquid crystal whose molecular direction does not change partially exists, a dark state is partially obtained. Therefore, from the white / black area ratio of black and white (bright / dark) display obtained when the voltage is applied, the molecular direction of the ferroelectric liquid crystal is about 2 of the tilt angle when the voltage is applied so that the first electrode layer is a negative electrode. The ratio of what doubles can be calculated.

  In the region where the first alignment pattern of the second alignment layer is provided, “when the voltage is applied so that the second electrode layer becomes a negative electrode, the molecular direction of the ferroelectric liquid crystal is the first alignment processing substrate. “It changes about twice the tilt angle θ of the ferroelectric liquid crystal with respect to the surface” means that the liquid crystal molecules are stabilized in one state on the cone when no voltage is applied, and the second electrode layer becomes a negative electrode. When a voltage is applied to the liquid crystal molecule, the liquid crystal molecule is tilted from the mono-stabilized state to one side on the cone, and when the voltage is applied so that the second electrode layer becomes the positive electrode, the liquid crystal molecule is in the mono-stabilized state. Or when the voltage is applied so that the second electrode layer becomes a negative electrode, when the voltage is applied so that the second electrode layer becomes a negative electrode from the mono-stabilized state. The inclination angle from the mono-stabilized state of the liquid crystal molecules is such that the second electrode layer becomes the positive electrode. When a voltage is applied to refers to larger than the inclination angle of the monostable state of the liquid crystal molecules.

  FIG. 18 is a schematic diagram illustrating an example of the alignment state of a ferroelectric liquid crystal exhibiting monostability. 18A shows a case where no voltage is applied, FIG. 18B shows a case where a voltage is applied so that the second electrode layer becomes a negative electrode, and FIG. 18C shows a case where the second electrode layer becomes a positive electrode. A case where a voltage is applied is shown. When no voltage is applied, the liquid crystal molecules LC are stabilized in one state on the cone (FIG. 18A). When a voltage is applied so that the second electrode layer is a negative electrode, the liquid crystal molecules LC are tilted from the stabilized state (broken line) to one side (FIG. 18B). In addition, when a voltage is applied so that the second electrode layer becomes a positive electrode, the liquid crystal molecules LC are in a state where a voltage is applied so that the second electrode layer becomes a negative electrode from a stabilized state (broken line). It tilts to the opposite side (FIG. 18 (c)). At this time, the inclination angle δ when the voltage is applied so that the second electrode layer becomes the negative electrode is larger than the inclination angle ω when the voltage is applied so that the second electrode layer becomes the positive electrode. In FIG. 18, d indicates the orientation processing direction, and z indicates the layer normal.

  When a voltage is applied so that the second electrode layer is a negative electrode, the liquid crystal molecules are tilted from the mono-stabilized state to one side on the cone at an angle corresponding to the magnitude of the applied voltage. In the ferroelectric liquid crystal, as illustrated in FIG. 18A, the position A (the direction of the liquid crystal molecules LC), the position B (the alignment treatment direction d), and the position C do not necessarily match. Absent. Therefore, as illustrated in FIG. 18B, the maximum tilt angle δ when a voltage is applied so that the second electrode layer is a negative electrode is about twice the tilt angle θ (angle 2θ).

  For example, as shown in FIG. 17, the direction of the liquid crystal molecules LC changes approximately twice the tilt angle θ (angle 2θ) in parallel to the first alignment processing substrate surface. About 2 times change means the case of 2θ-2θ-5 ° change.

  The angle at which the molecular direction of the ferroelectric liquid crystal changes in parallel to the first alignment processing substrate surface can be measured as follows. First, a polarizing microscope and a liquid crystal display element in which polarizing plates are arranged in crossed Nicols are arranged so that the polarization axis of one polarizing plate and the alignment direction of liquid crystal molecules in the liquid crystal layer are parallel, and this position is used as a reference. . When a voltage is applied, the liquid crystal molecules come to have a predetermined angle with the polarization axis, so that the polarized light transmitted through one polarizing plate is transmitted through the other polarizing plate to be in a bright state. With this voltage applied, the liquid crystal display element is rotated to a dark state. And the angle which rotated the liquid crystal display element at this time is measured. The angle by which the liquid crystal display element is rotated is an angle at which the molecular direction of the ferroelectric liquid crystal changes in parallel to the first alignment processing substrate surface.

  As described above, when a voltage is applied so that the second electrode layer becomes a negative electrode in the region where the first alignment pattern of the second alignment layer is provided, the liquid crystal molecules correspond to the magnitude of the applied voltage. Since the angle is inclined from the mono-stabilized state to one side on the cone, when the liquid crystal display element is actually driven, when the voltage is applied so that the second electrode layer becomes the negative electrode, the liquid crystal molecules The direction does not change about twice the tilt angle.

  In the region where the second alignment pattern of the second alignment layer is provided, “when the voltage is applied so that the first electrode layer is a negative electrode, the molecular direction of the ferroelectric liquid crystal is the first alignment processing substrate. Regarding “changes about twice the tilt angle θ of the ferroelectric liquid crystal with respect to the surface”, in the region where the first alignment pattern of the second alignment layer is provided, “the second electrode layer becomes a negative electrode” Thus, when the voltage is applied, the molecular direction of the ferroelectric liquid crystal changes about twice the tilt angle θ of the ferroelectric liquid crystal with respect to the first alignment treatment substrate surface. The description here is omitted.

The phase series of the ferroelectric liquid crystal is not particularly limited as long as it exhibits a chiral smectic C (SmC ^* ) phase. For example, the phase sequence changes from a nematic (N) phase to a cholesteric (Ch) phase to a chiral smectic C (SmC ^* ) phase or from a nematic (N) phase to a chiral smectic 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-chiral smectic Examples thereof include those that change phase with the C (SmC ^* ) phase. In particular, a material that changes from the Ch phase to the SmC ^* phase without passing through the SmA phase is suitable for exhibiting a half V-shaped switching characteristic.

  In general, a ferroelectric liquid crystal having a phase sequence passing through an SmA phase as illustrated in the lower part of FIG. 19 has a smectic layer in order to compensate for the volume change because the layer spacing of the smectic layer is reduced during the phase change process. A domain having a bent chevron structure and different major axis directions of the liquid crystal molecules is formed depending on the bending direction, and alignment defects called zigzag defects and hairpin defects are likely to occur at the interface. In general, a ferroelectric liquid crystal having a phase series that does not pass through the SmA phase as exemplified in the upper part of FIG. 19 is likely to generate two regions (double domains) having different layer normal directions. In this embodiment, the first alignment layer, the first alignment pattern of the second alignment layer, and the second alignment pattern of the second alignment layer are combined in a predetermined combination to cause such an alignment defect. Therefore, the alignment of the ferroelectric liquid crystal can be monostabilized.

Such a ferroelectric liquid crystal can be variously selected from generally known liquid crystal materials according to required characteristics. As described above, a liquid crystal material that exhibits an SmC ^* phase from the Ch phase without passing through the SmA phase is particularly suitable as a material that exhibits a half V-shaped switching characteristic. 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.

  In addition to the ferroelectric liquid crystal, the liquid crystal layer may contain a compound having any function depending on the function required for the liquid crystal display element. Examples of such a compound include a polymerized polymerizable monomer. By containing such a polymerizable monomer polymer in the liquid crystal layer, the alignment of the liquid crystal material is so-called “polymer stabilization”, and a liquid crystal display device excellent in alignment stability can be obtained.

  The polymerizable monomer used in the polymerized polymer of the polymerizable monomer is not particularly limited as long as it is a compound that generates a polymer by a polymerization reaction, and a thermosetting resin monomer that generates a polymerization reaction by heat treatment, and actinic radiation. An actinic radiation curable resin monomer that undergoes a polymerization reaction upon irradiation of can be exemplified. 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, so that the intermolecular force and the polymer network at the alignment film interface can be strengthened. Thereby, the disorder of the alignment of the ferroelectric liquid crystal due to the temperature change 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 a polymerizable functional group at both ends of the molecule, it is possible to form a polymer network with a wide interval between polymers, and to prevent a decrease in driving voltage of the ferroelectric liquid crystal due to the inclusion of a polymer of a polymerizable monomer. Because.

  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. By the presence of the polymer having such a regular alignment state, the alignment stability of the ferroelectric liquid crystal can be improved, and excellent heat resistance and impact resistance can be obtained.

  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 (20), (21), and (23).

In the above formulas (20) and (21), 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 (23), 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, It represents formyl, alkylcarbonyl having 1 to 20 carbons, alkylcarbonyloxy having 1 to 20 carbons, halogen, cyano or nitro.

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

  Moreover, the said polymerizable monomer may be used independently and may be used in combination of 2 or more type. When two or more different polymerizable monomers are used, for example, an ultraviolet curable liquid crystal monomer represented by the above formula and another ultraviolet curable resin monomer can be used.

  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 an atomic group exhibiting liquid crystallinity in the side chain increases the degree of freedom of the atomic group, so that the atomic group exhibiting liquid crystallinity is easily aligned. Further, as a result, the alignment stability of the ferroelectric liquid crystal can be improved.

The amount of the polymerized monomer in the liquid crystal layer is not particularly limited as long as the alignment stability of the ferroelectric liquid crystal is within a desired range, but usually 0.5% by mass in the liquid crystal layer. It is preferably within the range of ˜30% by mass, 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 it exceeds the above range, the drive voltage may increase or the response speed may decrease. Further, if the amount is less than the above range, the alignment stability of the ferroelectric liquid crystal becomes insufficient, and the heat resistance and impact resistance of the liquid crystal display element may be impaired.
Here, the abundance of the polymerizable monomer polymer in the liquid crystal layer is determined by measuring the weight of the remaining polymerizable monomer polymer with an electronic balance after washing the monomolecular liquid crystal in the liquid crystal layer with a solvent. It can be calculated from the obtained remaining amount and the total mass of the liquid crystal layer.

  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.

  As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used. For example, a vacuum injection method, a liquid crystal dropping method, or the like can be used.

  In the vacuum injection method, an isotropic liquid is formed by heating a ferroelectric liquid crystal into a liquid crystal cell prepared using a first alignment treatment substrate and a second alignment treatment substrate in advance, and is injected using the capillary effect. The liquid crystal layer can be formed by sealing with an adhesive. At this time, the thickness of the liquid crystal layer can be adjusted by a spacer such as a bead.

  In the liquid crystal dropping method, a ferroelectric liquid crystal is discharged in the state of an isotropic liquid onto the second alignment layer of the second alignment processing substrate by an ink jet method. Further, a sealant is applied around the first alignment processing substrate. Next, the first alignment treatment substrate and the second alignment treatment substrate are heated to a temperature at which the ferroelectric liquid crystal exhibits a nematic phase or an isotropic phase, and the alignment treatment directions of the first alignment layer and the second alignment layer are substantially parallel. They are made to face each other, overlapped under reduced pressure, and bonded through a sealant. Thereby, a liquid crystal layer can be formed.

4). Polarizing plate In this embodiment, polarizing plates may be provided outside the first alignment treatment substrate and the second alignment treatment 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 first alignment treatment substrate is disposed by aligning the polarization axis of the polarizing plate on the first alignment treatment substrate side with the alignment direction of the liquid crystal molecules (the alignment treatment direction of the first alignment layer). The polarized light transmitted through the polarizing plate on the side cannot be rotated by 90 °, and is blocked by the polarizing plate on the second alignment processing substrate side, and becomes dark. 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 second alignment treatment 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 this embodiment is not particularly limited as long as it transmits only a specific direction among the wave of light, and a polarizing plate generally used as a polarizing plate of a liquid crystal display element should be used. Can do.

5). Method for Driving Liquid Crystal Display Element The liquid crystal display element of this embodiment can use the high-speed response of the ferroelectric liquid crystal, so that one pixel is time-divided and high-speed response is obtained in order to obtain good video display characteristics. It is suitable to drive by a field sequential color method that particularly requires the above.
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 this embodiment 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. Further, gradation control is possible by voltage modulation.

  In the case of an active matrix system using TFTs, either the first alignment treatment substrate or the second alignment treatment 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. As illustrated in FIG. 20, the liquid crystal display element 1 includes a common electrode substrate (first alignment treatment substrate 5) in which a common electrode (first electrode layer 3) is formed on a first base 2, and a second substrate. The TFT elements 61 are arranged in a matrix on the material 12 and have a TFT substrate (second alignment treatment substrate 15) on which the gate electrode 62x, the source electrode 62y, and the pixel electrode 63 are formed. The gate electrode 62x and the source electrode 62y are arranged vertically and horizontally, respectively, and by applying a signal to the gate electrode 62x and the source electrode 62y, the TFT element 61 can be operated to drive the ferroelectric liquid crystal. A portion where the gate electrode 62x and the source electrode 62y intersect with each other is insulated by an insulating layer (not shown), and can operate independently of signals from the gate electrode 62x and the source electrode 62y. A portion surrounded by the gate electrode 62x and the source electrode 62y is a pixel which is a minimum unit for driving the liquid crystal display element, and at least one TFT element 61 and a pixel electrode 63 are formed in each pixel. Then, by sequentially applying a signal voltage to the gate electrode and the source electrode, the TFT element of each pixel can be operated. In FIG. 20, the liquid crystal layer, the first alignment layer, and the second alignment layer are omitted.

  Further, the liquid crystal display element of this embodiment can be driven by a segment system.

6). Manufacturing method of liquid crystal display element The liquid crystal display element of this embodiment can be manufactured by the method generally used as a manufacturing method of a liquid crystal display element. For example, a vacuum injection method, a liquid crystal dropping method, or the like can be used.
Hereinafter, as an example of a method for manufacturing a liquid crystal display element of the present embodiment, a method for manufacturing an active matrix liquid crystal display element using a TFT element will be described.

In the vacuum injection method, first, a gate electrode and a source electrode are formed in a matrix on a first substrate, and a TFT element and a pixel electrode are further installed. Next, polyimide is printed on the gate electrode, the source electrode, the TFT element, and the pixel electrode, and a rubbing process is performed to form a rubbing film. The substrate thus obtained is referred to as a first alignment processing substrate.
Next, a transparent conductive film is formed on the second substrate by a vacuum deposition method to form a common electrode on the entire surface. Next, partition walls are formed in a pattern on the common electrode layer by photolithography. Next, a photoisomerizable material is applied to a predetermined region defined by the partition walls by an ink jet method, and a photoalignment treatment is performed to form a photoalignment film containing the photoisomerizable material in a pattern. Next, a photodimerization material is applied to a predetermined region defined by the partition walls by an ink jet method, and a photoalignment treatment is performed to form a photoalignment film containing the photodimerization material in a pattern. Thereby, the 2nd alignment layer which has the 1st alignment pattern which consists of a photo-alignment film containing a photoisomerization-type material, and the 2nd alignment pattern which consists of a photo-alignment film containing a photodimerization-type material is obtained. The substrate thus obtained is referred to as a second alignment processing substrate.
Next, a sealant is applied around one of the substrates, and the first alignment treatment substrate and the second alignment treatment substrate are opposed so that the alignment treatment directions of the first alignment layer and the second alignment layer are substantially parallel, Bonding and thermocompression bonding. Then, the ferroelectric liquid crystal is injected in an isotropic liquid state using the capillary effect from the injection port, and the injection port is sealed with an ultraviolet curable resin or the like. Thereafter, the ferroelectric liquid crystal is aligned by slow cooling.

In the liquid crystal dropping method, first, a gate electrode and a source electrode are formed in a matrix on a first substrate, and a TFT element and a pixel electrode are further installed. Next, polyimide is printed on the gate electrode, the source electrode, the TFT element, and the pixel electrode, and a rubbing process is performed to form a rubbing film. The substrate thus obtained is referred to as a first alignment processing substrate.
Next, a transparent conductive film is formed on the second substrate by a vacuum deposition method to form a common electrode on the entire surface. Next, partition walls are formed in a pattern on the common electrode layer by photolithography. Next, a photoisomerizable material is applied to a predetermined region defined by the partition walls by an ink jet method, and a photoalignment treatment is performed to form a photoalignment film containing the photoisomerizable material in a pattern. Next, a photodimerization material is applied to a predetermined region defined by the partition walls by an ink jet method, and a photoalignment treatment is performed to form a photoalignment film containing the photodimerization material in a pattern. Thereby, the 2nd alignment layer which has the 1st alignment pattern which consists of a photo-alignment film containing a photoisomerization-type material, and the 2nd alignment pattern which consists of a photo-alignment film containing a photodimerization-type material is obtained. The substrate thus obtained is referred to as a second alignment processing substrate.
Next, the first alignment treatment substrate is heated to a temperature at which the ferroelectric liquid crystal becomes isotropic, and the ferroelectric liquid crystal isotropically is formed on the first alignment layer of the first alignment treatment substrate using an ink jet apparatus. Apply in a liquid state. Next, the first alignment treatment substrate and the second alignment treatment substrate are opposed to each other so that the alignment treatment directions of the first alignment layer and the second alignment layer are substantially parallel, and are superposed under reduced pressure, via a sealing agent. Adhere.
Thereafter, the encapsulated ferroelectric liquid crystal is aligned by slowly cooling the liquid crystal cell to room temperature.

When aligning the ferroelectric liquid crystal, if a polymerizable monomer is added to the ferroelectric liquid crystal, the ferroelectric liquid crystal is aligned and then the polymerizable monomer is polymerized. The polymerization method of the polymerizable monomer is appropriately selected according to the type of the polymerizable monomer. For example, when an ultraviolet curable resin monomer is used as the polymerizable monomer, the polymerizable monomer can be polymerized by ultraviolet irradiation. .
Further, when polymerizing the polymerizable monomer, a voltage may or may not be applied to the liquid crystal layer composed of the ferroelectric liquid crystal, but no voltage is applied to the liquid crystal layer. It is preferable to polymerize a polymerizable monomer.

II. Second Embodiment Next, a second embodiment of the liquid crystal display element of the present invention will be described.
The liquid crystal display element of this embodiment includes a first substrate, a first electrode layer formed on the first substrate, and a first alignment pattern and a second alignment pattern formed on the first electrode layer. A first alignment treatment substrate having a first alignment layer, a second substrate, a second electrode layer formed on the second substrate, a second electrode layer formed on the second electrode layer, A second alignment treatment substrate having a first alignment pattern and a second alignment layer comprising a second alignment pattern, the first alignment pattern of the first alignment layer and the second alignment pattern of the second alignment layer are opposed to each other, and The second alignment pattern of the first alignment layer and the first alignment pattern of the second alignment layer are arranged to face each other, and a ferroelectric liquid crystal is sandwiched between the first alignment layer and the second alignment layer. A liquid crystal display element, wherein the ferroelectric liquid crystal exhibits monostability and The first alignment pattern is a pattern made of a rubbing film, and the second alignment pattern is formed on the reactive liquid crystal alignment film and the reactive liquid crystal alignment film. A pattern formed from a reactive liquid crystal layer formed by fixing a reactive liquid crystal, a pattern formed from a photo-alignment film containing a photo-dimerization type material that imparts anisotropy to the alignment film by causing a photo-dimerization reaction, Alternatively, the pattern is any one of patterns made of a photo-alignment film containing a photo-isomerization material that imparts anisotropy to the alignment film by causing a photoisomerization reaction.

The liquid crystal display element of this embodiment will be described with reference to the drawings.
21 and 22 are cross-sectional views showing an example of the liquid crystal display element of this embodiment.

  In the liquid crystal display element 1 illustrated in FIG. 21, the first alignment treatment substrate 5 in which the first electrode layer 3 and the first alignment layer 4 are formed on the first base material 2, and the second alignment material 12 on the first base material 12. The second alignment treatment substrate 15 on which the two-electrode layer 13 and the second alignment layer 14 are formed is opposed to the first alignment layer 4 of the first alignment treatment substrate 5 and the second alignment treatment substrate 15 of the second alignment treatment substrate 15. A ferroelectric liquid crystal is sandwiched between the layer 14 and the liquid crystal layer 10 is formed. The first alignment layer 4 includes a first alignment pattern 4a and a second alignment pattern 4b, and an insulating portion 28 is formed between the first alignment pattern 4a and the second alignment pattern 4b. The second alignment layer 14 includes a first alignment pattern 14a and a second alignment pattern 14b, and an insulating portion 28 is also formed between the first alignment pattern 14a and the second alignment pattern 14b. The first alignment patterns 4a and 14a are patterns made of a rubbing film, and the second alignment patterns 4b and 14b are patterns made of a photo-alignment film containing a photoisomerizable material or light containing a photodimerization-type material. It is a pattern made of an alignment film. Further, the first alignment pattern 4 a of the first alignment layer 4 and the second alignment pattern 14 b of the second alignment layer 14 face each other, and the second alignment pattern 4 b of the first alignment layer 4 and the first alignment layer 14 of the second alignment layer 14 are first. The alignment pattern 14a faces the alignment pattern 14a.

  In the liquid crystal display element 1 illustrated in FIG. 22, the first alignment patterns 4a and 14a are patterns made of a rubbing film, and the second alignment patterns 4b and 14b are the alignment film 17 for reactive liquid crystal and the reactive liquid crystal layer. 18 is a pattern. In the first alignment treatment substrate 5, the partition wall 16 is formed on the first electrode layer 3, and the first alignment pattern 4 a and the reactive liquid crystal alignment film 17 are continuously formed on the partition wall 16, so that the reactive liquid crystal substrate is used. A reactive liquid crystal layer 18 is formed on the alignment film 17. In the second alignment treatment substrate 15, the first alignment pattern 14 a and the reactive liquid crystal alignment film 17 are continuously formed on the second electrode layer 13, and the reactive liquid crystal layer is formed on the reactive liquid crystal alignment film 17. 18 is formed. Other structures are the same as those of the liquid crystal display element shown in FIG.

Since the ferroelectric liquid crystal has spontaneous polarization, the direction of spontaneous polarization is determined by the polarity effect as the interaction between the ferroelectric liquid crystal and the first alignment layer surface and the second alignment layer surface.
In this embodiment, the ferroelectric liquid crystal is sandwiched between the first alignment pattern and the second alignment pattern of the first alignment layer and the first alignment pattern and the second alignment pattern of the second alignment layer. .

In the example shown in FIG. 21, the first alignment pattern of the first alignment layer and the first alignment pattern of the second alignment layer are patterns made of a rubbing film, and the second alignment pattern of the first alignment layer and the second alignment layer The second alignment pattern is a pattern made of a photo-alignment film containing a photoisomerizable material or a pattern made of a photo-alignment film containing a photodimerization-type material. The first alignment pattern and the second alignment pattern can have different polarities.
In the example shown in FIG. 22, the first alignment pattern of the first alignment layer and the first alignment pattern of the second alignment layer are patterns made of a rubbing film, and the second alignment pattern and the second alignment layer of the first alignment layer are the same. Since the second alignment pattern of the alignment layer is a pattern comprising an alignment film for reactive liquid crystal and a reactive liquid crystal layer, the first alignment pattern and the second alignment pattern have different polarities depending on the respective constituent materials. Can be.
As a result, the polar surface interaction between the ferroelectric liquid crystal and the first alignment pattern and the polar surface interaction between the ferroelectric liquid crystal and the second alignment pattern are different.

As described above, it is considered that the photo-alignment film and the reactive liquid crystal layer containing the photodimerization type material tend to have a relatively strong positive polarity as compared with the rubbing film. Therefore, when the second alignment pattern is a pattern made of a photo-alignment film containing a photo-dimerization-type material, the first alignment pattern (rubbing film) and the second alignment pattern (the photo-dimerization-type material) are applied in the absence of voltage. It is assumed that the photo-alignment film side containing the photodimerization-type material is positive and the rubbing film side is negative. Further, when the second alignment pattern is a pattern composed of an alignment film for reactive liquid crystal and a reactive liquid crystal layer, the first alignment pattern (rubbing film) and the second alignment pattern (reaction) are applied in the absence of voltage. With respect to the alignment film for reactive liquid crystal and the reactive liquid crystal layer), it is assumed that the reactive liquid crystal layer side is positive and the rubbing film side is negative. Therefore, in these cases, the positive electrode of spontaneous polarization can be directed to the first alignment pattern (rubbing film) side.
That is, as illustrated in FIG. 23, in the region 23 where the first alignment pattern 4a of the first alignment layer is provided, the positive polarity (+) of the spontaneous polarization Ps of the liquid crystal molecules LC is set to the first alignment of the first alignment layer. It can be directed to the pattern 4a side. On the other hand, in the region 24 where the second alignment pattern 4b of the first alignment layer is provided, the positive electrode (+) of the spontaneous polarization Ps of the liquid crystal molecules LC can be directed to the first alignment pattern 14a side of the second alignment layer. it can.

Further, as described above, it is considered that the rubbing film tends to have a relatively strong positive polarity as compared with the photo-alignment film containing the photoisomerizable material. Therefore, when the second alignment pattern is a pattern made of a photo-alignment film containing a photoisomerizable material, the first alignment pattern (rubbing film) and the second alignment pattern (photoisomerization) are applied in the absence of voltage. It is assumed that the rubbing film side is positive and the photo alignment film side containing the photoisomerizable material is negative. Therefore, the positive electrode of spontaneous polarization can be directed to the second alignment pattern (photo-alignment film containing photoisomerizable material) side.
That is, as illustrated in FIG. 24, in the region 23 where the first alignment pattern 4a of the first alignment layer is provided, the positive polarity (+) of the spontaneous polarization Ps of the liquid crystal molecules LC is set to the second alignment of the second alignment layer. It can be directed to the pattern 14b side. On the other hand, in the region 24 where the second alignment pattern 4b of the first alignment layer is provided, the positive electrode (+) of the spontaneous polarization Ps of the liquid crystal molecules LC can be directed to the second alignment pattern 4b side of the first alignment layer. it can.

  Thus, the direction of spontaneous polarization can be controlled by considering the surface polarities of the first alignment pattern and the second alignment pattern, and combining the first alignment pattern and the second alignment pattern in a predetermined combination. As a result, the direction of spontaneous polarization can be reversed for each region of the first alignment layer where the first alignment pattern or the second alignment pattern is provided, and polarity inversion driving is possible.

  Moreover, in the ferroelectric liquid crystal, the direction of the liquid crystal molecules, the direction of spontaneous polarization, and the direction of the layer normal are in a predetermined relationship, so the layer normal depends on the direction of the liquid crystal molecules and the direction of spontaneous polarization. The direction is determined. Therefore, in the regions where the first alignment pattern and the second alignment pattern of the first alignment layer are provided, the occurrence of alignment defects is suppressed by aligning the direction of spontaneous polarization in a certain direction, and monodomain alignment is achieved. Obtainable.

  Furthermore, by using a rubbing film for the first alignment pattern, it is possible to effectively suppress the occurrence of zigzag defects and hairpin defects.

  Hereinafter, each structure in the liquid crystal display element of this embodiment is demonstrated. Since the polarizing plate, the driving method of the liquid crystal display element, and the manufacturing method of the liquid crystal display element are the same as those in the first embodiment, description thereof is omitted here.

1. First alignment treatment substrate The first alignment treatment substrate in the present embodiment is formed on the first base material, the first electrode layer formed on the first base material, the first electrode layer, and the first base material. A first alignment layer comprising an alignment pattern and a second alignment pattern. The first alignment pattern is a pattern made of a rubbing film, the second alignment pattern is a pattern made of a reactive liquid crystal alignment film and a reactive liquid crystal layer, a pattern made of a photo alignment film containing a photodimerization type material, Alternatively, it is one of patterns formed of a photo-alignment film containing a photoisomerizable material.

  The first substrate, the first electrode layer, the rubbing film, the alignment film for reactive liquid crystal, the reactive liquid crystal layer, the photo-alignment film containing the photodimerization type material, the photo-alignment film containing the photoisomerization type material, The shape of the first alignment pattern and the second alignment pattern, and the formation method of the first alignment pattern and the second alignment pattern are the same as those described in the first embodiment. Omitted.

In the first alignment treatment substrate, a wettability changing layer is formed between the first electrode layer and the first alignment layer, and the wettability consisting of a liquid repellent region and a lyophilic region is formed on the surface of the wettability changing layer. A change pattern may be formed. In this case, the first alignment layer is formed only on the lyophilic region.
Since the wettability changing layer is the same as that described in the first embodiment, description thereof is omitted here.

When a wettability changing layer is formed between the first electrode layer and the first alignment layer and between the second electrode layer and the second alignment layer, the first alignment treatment substrate A patterned light shielding portion is formed between at least one of the first base material and the wettability changing layer and at least one of the second base material and the wettability changing layer of the second alignment processing substrate. It is preferable that the liquid-repellent region of the wettability changing layer of the alignment treatment substrate and the second alignment treatment substrate is disposed in the region where the light shielding portion is provided. This is because light leakage due to disordered alignment of the ferroelectric liquid crystal in the liquid repellent region can be prevented.
The light shielding portion may be provided on either the first alignment treatment substrate or the second alignment treatment substrate, or may be provided on both the first alignment treatment substrate and the second alignment treatment substrate.

Further, in the first alignment processing substrate, an insulating portion is formed between the first alignment pattern and the second alignment pattern, the surface of the insulating portion is a liquid repellent region, and the layer surface in the opening of the insulating portion is lyophilic. It may be an area. In this case, the first alignment layer is formed only on the lyophilic region.
In addition, about an insulation part, since it is the same as that of what was described in the said 1st embodiment, description here is abbreviate | omitted.

In the case where insulating portions are formed between the first alignment pattern and the second alignment pattern of the first alignment layer and between the first alignment pattern and the second alignment pattern of the second alignment layer, respectively, the first It is preferable that at least one of the insulating portion of the alignment treatment substrate and the insulation portion of the second alignment treatment substrate is a light shielding portion. This is because, as described above, it is possible to prevent light leakage due to the alignment disorder of the ferroelectric liquid crystal in the liquid repellent region.
The insulating part may be provided on either the first alignment treatment substrate or the second alignment treatment substrate, or may be provided on both the first alignment treatment substrate and the second alignment treatment substrate.

Furthermore, in the 1st orientation processing board | substrate, the partition may be formed between the 1st orientation pattern and the 2nd orientation pattern.
In addition, about a partition, since it is the same as that of what was described in the said 1st embodiment, description here is abbreviate | omitted.
The partition is formed on either the first alignment processing substrate or the second alignment processing substrate.

In the first alignment treatment substrate, a colored layer may be formed between the first base material and the first electrode layer.
In addition, about a colored layer, since it is the same as that of what was described in the said 1st embodiment, description here is abbreviate | omitted.

2. Second alignment processing substrate The second alignment processing substrate in the present embodiment is formed on the second base material, the second electrode layer formed on the second base material, the second electrode layer, and the first base material. A second alignment layer comprising an alignment pattern and a second alignment pattern. The first alignment pattern is a pattern made of a rubbing film, the second alignment pattern is a pattern made of a reactive liquid crystal alignment film and a reactive liquid crystal layer, a pattern made of a photo alignment film containing a photodimerization type material, Alternatively, it is one of patterns formed of a photo-alignment film containing a photoisomerizable material.

  In addition, about each structure of a 2nd orientation processing board | substrate, since it is the same as that of the said 1st orientation processing board | substrate, description here is abbreviate | omitted.

3. Liquid Crystal Layer The liquid crystal layer in this embodiment is configured by sandwiching a ferroelectric liquid crystal between the first alignment layer of the first alignment processing substrate and the second alignment layer of the second alignment processing substrate.

  In this embodiment, when the second alignment pattern is a pattern made of a photo-alignment film containing a photodimerization type material, or a pattern made of a reactive liquid crystal alignment film and a reactive liquid crystal layer, a ferroelectric liquid crystal When the voltage is applied so that the electrode on the second alignment pattern side is a negative electrode, the molecular direction of the ferroelectric liquid crystal is parallel to the first alignment processing substrate surface and is about the tilt angle of the ferroelectric liquid crystal. It is preferable that it changes twice.

  As described above, when no voltage is applied, the positive polarity of spontaneous polarization of liquid crystal molecules tends to face the first alignment pattern side (rubbing film side) due to the polar surface interaction. A voltage is applied so that the electrode on the first alignment pattern side (rubbing film side) is a positive electrode and the electrode on the second alignment pattern side (photo-alignment film or reactive liquid crystal layer side containing the photodimerization type material) is a negative electrode. When applied, the positive polarity of the spontaneous polarization of the liquid crystal molecules comes to face the second alignment pattern side (the photo-alignment film containing the photodimerization type material or the reactive liquid crystal layer side) due to the influence of the polarity of the applied voltage. Next, voltage is applied so that the electrode on the first alignment pattern side (rubbing film side) is the negative electrode and the electrode on the second alignment pattern side (photo alignment film or reactive liquid crystal layer side containing the photodimerization type material) is the positive electrode. When applied, the positive polarity of the spontaneous polarization of the liquid crystal molecules comes to face the first alignment pattern side (rubbing film side) due to the influence of the polarity of the applied voltage. In this case, the direction of spontaneous polarization is the same as that in the state where no voltage is applied.

  When no voltage is applied or when a positive voltage is applied to the electrode on the second alignment pattern side, a negative voltage is applied to the electrode on the second alignment pattern side. Due to the repulsion of the spontaneous polarization of the molecules with the negative polarity, the liquid crystal molecules LC rotate about an angle of about 2θ as illustrated in FIG. That is, when a voltage is applied so that the electrode on the second alignment pattern side is a negative electrode, the tilt direction of the ferroelectric liquid crystal is such that the molecular direction of the ferroelectric liquid crystal is parallel to the first alignment processing substrate surface. It changes about twice as much as θ.

When a voltage is applied so that the electrode on the second alignment pattern side is a negative electrode, it is preferable that there are 70% or more, more preferably 80%, in which the molecular direction of the ferroelectric liquid crystal changes about twice the tilt angle. % Or more, more preferably 90% or more, and most preferably 95% or more.
In addition, about the measuring method of said ratio, since it described in the said 1st embodiment, description here is abbreviate | omitted.

  Further, when the second alignment pattern is a pattern made of a photo-alignment film containing a photodimerization type material, or a pattern made of a reactive liquid crystal alignment film and a reactive liquid crystal layer, the “second alignment pattern side” When the voltage is applied so that the electrode of the first electrode becomes a negative electrode, the molecular direction of the ferroelectric liquid crystal changes about twice the tilt angle θ of the ferroelectric liquid crystal with respect to the first alignment treatment substrate surface. In the first embodiment, in the region where the first alignment pattern of the second alignment layer is provided, “when the voltage is applied so that the second electrode layer becomes a negative electrode, the molecules of the ferroelectric liquid crystal Since the direction can be considered in the same manner as “the direction changes about twice the tilt angle θ of the ferroelectric liquid crystal with respect to the first alignment processing substrate surface”, the description thereof is omitted here.

  On the other hand, in the present embodiment, when the second alignment pattern is a pattern made of a photo-alignment film containing a photoisomerizable material, the ferroelectric liquid crystal has a voltage so that the electrode on the first alignment pattern side becomes a negative electrode. It is preferable that the molecular direction of the ferroelectric liquid crystal changes approximately twice as much as the tilt angle of the ferroelectric liquid crystal in parallel with the first alignment treatment substrate surface.

  As described above, when no voltage is applied, the positive polarity of spontaneous polarization of liquid crystal molecules tends to face the second alignment pattern side (the photo-alignment film-containing photo-alignment film side) due to the polar surface interaction. When a voltage is applied so that the electrode on the first alignment pattern side (rubbing film side) is a negative electrode and the electrode on the second alignment pattern side (photo alignment film side containing the photoisomerizable material) is a positive electrode, Due to the influence of the polarity of the voltage, the positive electrode of the spontaneous polarization of the liquid crystal molecules comes to face the first alignment pattern side (rubbing film side). Next, when a voltage is applied such that the electrode on the first alignment pattern side (rubbing film side) is a positive electrode and the electrode on the second alignment pattern side (photo alignment film side containing the photoisomerizable material) is a negative electrode, Due to the influence of the polarity of the voltage, the positive electrode of the spontaneous polarization of the liquid crystal molecules comes to face the second alignment pattern side (the photo-alignment film side containing the photoisomerizable material). In this case, the direction of spontaneous polarization is the same as that in the state where no voltage is applied.

  When no voltage is applied or when a positive voltage is applied to the first alignment pattern side electrode, a negative voltage is applied to the first alignment pattern side electrode. Due to the repulsion of the spontaneous polarization of the molecules with the negative polarity, the liquid crystal molecules LC rotate about an angle of about 2θ as illustrated in FIG. That is, when a voltage is applied so that the electrode on the first alignment pattern side is a negative electrode, the tilt direction of the ferroelectric liquid crystal is such that the molecular direction of the ferroelectric liquid crystal is parallel to the first alignment processing substrate surface. It changes about twice as much as θ.

When a voltage is applied so that the electrode on the first alignment pattern side is a negative electrode, it is preferable that 70% or more of the ferroelectric liquid crystal molecules change in molecular direction by about twice the tilt angle, more preferably 80%. % Or more, more preferably 90% or more, and most preferably 95% or more.
In addition, about the measuring method of said ratio, since it described in the said 1st embodiment, description here is abbreviate | omitted.

  Further, when the second alignment pattern is a pattern made of a photo-alignment film containing a photoisomerizable material, “when the voltage is applied so that the electrode on the first alignment pattern side becomes a negative electrode, the ferroelectricity Regarding the fact that the molecular direction of the liquid crystal changes about twice the tilt angle θ of the ferroelectric liquid crystal with respect to the surface of the first alignment substrate, in the first embodiment, the first alignment pattern of the second alignment layer is In the region provided, “when the voltage is applied so that the second electrode layer is a negative electrode, the molecular direction of the ferroelectric liquid crystal is tilted with respect to the first alignment substrate surface. Since it may be considered in the same manner as “changes approximately twice θ,” the description thereof is omitted here.

  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 1]
(Production of first alignment processing substrate)
On the alkali-free glass substrate on which the electrodes were formed, polyimide (Nissan Chemical Industry Co., Ltd., trade name: SE-7492) was printed and rubbed to form an alignment film.

(Preparation of second alignment processing substrate)
A solution of photoisomerizable material (manufactured by DIC, trade name: LIA01) is spin-coated at 1500 rpm for 15 seconds on an alkali-free glass substrate on which an electrode is formed, and dried on a hot plate at 100 ° C. for 1 minute. It was. Next, a 5 mass% cyclopentanone solution of a reactive liquid crystal material (Rolic technologies, trade name: ROF5101) is spin-coated on this alignment film for 15 seconds at a rotation speed of 1500 rpm, and 1% on a hot plate at 60 ° C. Let dry for minutes. Subsequently, the reactive liquid crystal material thus obtained was irradiated with about 1000 mJ / cm ^{2 of} ultraviolet rays through a mask in a nitrogen atmosphere to cure the reactive liquid crystal material. Thereafter, the uncured reactive liquid crystal material was washed with MEK for about 2 seconds, and then washed with IPA and water for 30 seconds each. As a result, stripe-shaped reactive liquid crystal layers having a width of 200 μm were formed on the alignment film with an interval of 200 μm. This obtained the 2nd orientation processing board | substrate.

(Production of liquid crystal display element)
One alignment treatment substrate was sprayed with 1.5 μm bead spacers, and a sealant was applied to the other alignment treatment substrate with a seal dispenser. Next, both substrates were made to face each other so that the respective alignment treatment directions were parallel, and thermocompression bonding was performed to produce an empty liquid crystal cell.
Next, a ferroelectric liquid crystal (trade name: R2301, manufactured by AZ Electronic Materials) is used to attach a ferroelectric liquid crystal to the upper portion of the injection port, and an oven is used to obtain an N-phase-isotropic phase transition temperature of 10 Injection was performed at a temperature higher by 20 ° C to 20 ° C, and the temperature was slowly returned to room temperature.

The obtained liquid crystal cell was arranged between two polarizing plates arranged in crossed Nicol so that the alignment treatment direction and the polarizing axis of one polarizing plate coincided. Using a pulse generator, a voltage of ± 5 V rectangle was applied between the electrodes at a frequency of 1 Hz. As a result, only the alignment film and the region where the alignment film and the reactive liquid crystal layer were laminated on the second alignment processing substrate It was observed that light was alternately transmitted through the formed area.
Further, when the optical response was measured when a voltage of ± 5 V was applied using a polarizing microscope and a measuring device comprising a photodiode and a pulse generator, the region side where the alignment film and the reactive liquid crystal layer were laminated It was observed that the transmittance changed when a negative voltage was applied to the electrode. Furthermore, at this time, it was measured that the direction of the liquid crystal molecules changed twice the tilt angle.
Regarding the liquid crystal alignment in this case, no zigzag defect or hairpin defect was observed.

[Comparative Example 1]
In Example 1, a liquid crystal cell was produced in the same manner as in Example 1 except that a photo-alignment film containing a photodimerization type material was used instead of the rubbing film.

The obtained liquid crystal cell was arranged between two polarizing plates arranged in crossed Nicol so that the alignment treatment direction and the polarizing axis of one polarizing plate coincided. When a voltage of ± 5 V rectangle was applied between the electrodes at a frequency of 1 Hz using a pulse generator, the alignment film and the reactive liquid crystal layer of the second alignment processing substrate were laminated as in Example 1. It was observed that light was alternately transmitted through the region and the region where only the alignment film was formed.
Further, when the optical response when a voltage of ± 5 V was applied was measured using a polarizing microscope and a measuring device composed of a photodiode and a pulse generator, the alignment film and the reactive liquid crystal layer were obtained in the same manner as in Example 1. It was observed that the transmittance changed when a negative voltage was applied to the electrode on the side where the layer was laminated. Furthermore, at this time, it was measured that the direction of the liquid crystal molecules changed twice the tilt angle.
However, for the liquid crystal alignment in this case, zigzag defects occurred in the liquid crystal texture, and the contrast was reduced by 103.

[Example 2]
(Production of first alignment processing substrate)
On the alkali-free glass substrate on which the electrodes were formed, polyimide (Nissan Chemical Industry Co., Ltd., trade name: SE-7492) was printed and rubbed to form an alignment film.

(Preparation of second alignment processing substrate)
3 g of isopropyl alcohol, 0.4 g of organosilane (TSL8113, manufactured by Toshiba Silicone), 0.04 g of fluoroalkylsilane (MF-160E, manufactured by Tochem Products), and a photocatalytic inorganic coating agent (ST-K01, manufactured by Ishihara Sangyo Co., Ltd.) ) 1.5 g was mixed and heated at 100 ° C. for 20 minutes with stirring. This solution is applied on a non-alkali glass substrate on which an ITO transparent electrode is formed by spin coating, and the substrate is dried at a temperature of 150 ° C. for 10 minutes to promote hydrolysis and polycondensation reaction. Obtained a 0.2 μm thick wettability changing layer firmly fixed in the organopolysiloxane.

Next, the pattern surface of the negative photomask is placed on this wettability changing layer, and UV exposure is performed from the photomask side with a mercury lamp (wavelength 365 nm) at an illuminance of 300 mW / cm ² for 900 seconds. A sex change pattern was formed. The wettability change pattern was formed by alternately forming stripe-shaped liquid repellent areas having a width of 20 μm and stripe-shaped lyophilic areas having a width of 180 μm.

Next, an odd numbered lyophilic region of the wettability changing layer is a solution of a photoisomerizable material (manufactured by DIC, trade name: LIA01) using an ink jet device (Dimatix, Dimatix SE-128). Was applied in a pattern. This solution spreads only in the lyophilic region and was dried at 100 ° C. for 1 minute to obtain a striped first pattern. Subsequently, alignment treatment was performed by irradiating the first pattern with linearly polarized ultraviolet rays at about 1000 mJ / cm ^{2 so} that the polarization direction was perpendicular to the stripe direction of the pattern. Next, in the even-numbered lyophilic region of the wettability changing layer, a 2% by mass cyclopentanone solution of a photodimerization material (Rolic technologies, trade name: ROP103) is patterned using the above-described inkjet device. And dried at 130 ° C. for 15 minutes to obtain a striped second pattern. This second pattern was subjected to alignment treatment by irradiating linearly polarized ultraviolet rays at about 100 mJ / cm ^{2 so} that the polarization direction coincided with the stripe direction of the pattern. In this way, a first alignment pattern and a second alignment pattern were obtained. This produced the 2nd alignment processing board | substrate.

(Production of liquid crystal display element)
One alignment treatment substrate was sprayed with 1.5 μm bead spacers, and a sealant was applied to the other alignment treatment substrate with a seal dispenser. Next, both substrates were made to face each other so that the respective alignment treatment directions were parallel, and thermocompression bonding was performed to produce an empty liquid crystal cell.
Next, a ferroelectric liquid crystal (trade name: R2301, manufactured by AZ Electronic Materials) is used to attach a ferroelectric liquid crystal to the upper portion of the injection port, and an oven is used to obtain an N-phase-isotropic phase transition temperature of 10 Injection was performed at a temperature higher by 20 ° C to 20 ° C, and the temperature was slowly returned to room temperature.

The obtained liquid crystal cell was arranged between two polarizing plates arranged in crossed Nicol so that the alignment treatment direction and the polarizing axis of one polarizing plate coincided. When a voltage of ± 5 V rectangle is applied between the electrodes at a frequency of 1 Hz using a pulse generator, a region where the first alignment pattern using the photoisomerizable material is formed on the second alignment processing substrate; It was observed that light was alternately transmitted through the region where the second alignment pattern using the photodimerization type material was formed.
Further, when the optical response was measured when a voltage of ± 5 V was applied using a polarizing microscope and a measuring device consisting of a photodiode and a pulse generator, a second alignment pattern using a photodimerization type material was formed. It was observed that the transmittance changed when a negative voltage was applied to the electrode on the region side. Furthermore, at this time, it was measured that the direction of the liquid crystal molecules changed twice the tilt angle.
Regarding the liquid crystal alignment in this case, no zigzag defect or hairpin defect was observed.

[Example 3]
(Preparation of the first alignment processing substrate)
On the alkali-free glass substrate on which the electrodes were formed, polyimide (Nissan Chemical Industry Co., Ltd., trade name: SE-7492) was printed and rubbed to form an alignment film.

(Preparation of second alignment processing substrate)
A mixture having the following composition was heated to 90 ° C. for dissolution, centrifuged at 12000 rpm, and then filtered through a 1 μm glass filter. To the obtained aqueous colored resin solution, 1% by mass of ammonium dichromate was added as a crosslinking agent to prepare a light shielding part forming coating solution.
<Composition of aqueous colored resin solution>
Carbon black (Mitsubishi Chemical Co., Ltd., # 950) 4 parts by weight Polyvinyl alcohol (Nippon Synthetic Chemical Co., Ltd., Gohsenol AH-26) 0.7 parts by weight Ion-exchanged water 95.3 parts by weight

  Using the obtained light shielding part forming coating solution, light shielding parts were formed in a pattern as follows and evaluated. First, the said light shielding part formation coating liquid was apply | coated on the alkali free glass substrate in which the ITO transparent electrode was formed with the spin coater, and it dried at 80 degreeC for 1 minute on the hotplate. When the thickness of the light-shielding film after drying was measured with a stylus type film thickness meter (α-step, manufactured by Tencor), it was 1 μm. Next, this light-shielding film was image-exposed with a mercury lamp through a mask. Subsequently, immersion development was performed in a developer containing a temperature of 25 ° C., a potassium hydroxide with a concentration of 0.05% and a nonionic surfactant with a concentration of 0.1% (Emulgen A-60, manufactured by Kao Corporation). Thereafter, drying is performed at 60 ° C. for 3 minutes, and exposure is performed with a mercury lamp, so that the applied coating liquid for forming the light shielding part is cured, and further, heat treatment is performed at 150 ° C. for 30 minutes to form a light shielding part. did. The light shielding part pattern was a line and space pattern with a light shielding part width of 20 μm and an opening width of 180 μm.

Next, atmospheric pressure plasma was irradiated twice on the substrate on which the light-shielding portion was formed under the following conditions. Thereby, fluorine was introduced into the surface of the light shielding part. The contact angle with the liquid with a surface tension of 40 mN / m on the surface of the light shielding part before irradiation with atmospheric pressure plasma was 20 °, but the contact angle with the liquid with a surface tension of 40 mN / m on the surface of the light shielding part after irradiation with atmospheric pressure plasma. Became 70 °. The contact angle with this liquid was measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., CA-Z type) (30 seconds after dropping a droplet from a microsyringe).
<Atmospheric pressure plasma irradiation conditions>
Introducing gas: CF ₄ ... 12 (l / min); N ₂ ... 20 (l / min)
・ Distance between electrode and substrate: 2 mm
-Power output: 190V-4.8A
・ Conveying speed: 0.5m / min

Next, energy irradiation is performed for 1200 seconds from the glass substrate side with an ultra-high pressure mercury lamp (illuminance 30 mW / cm ² ) on the substrate on which the light-shielding portion irradiated with plasma is formed, and impurities in the opening section partitioned by the light-shielding portion are removed. Removed. Thereby, in the opening part, the contact angle with the liquid of surface tension 40mN / m became 10 degrees or less. The contact angle with the liquid was measured by the method described above.
In this way, the surface of the light shielding portion was defined as a liquid repellent region, and the inside of the opening was defined as a lyophilic region.

Next, a solution of photoisomerizable material (DIC, trade name: LIA01) is applied in a pattern using an inkjet device (Dimatix SE-128, manufactured by Dimatix) to odd-numbered lyophilic areas. did. This solution spreads only in the lyophilic region and was dried at 100 ° C. for 1 minute to obtain a striped first pattern. Subsequently, alignment treatment was performed by irradiating the first pattern with linearly polarized ultraviolet rays at about 1000 mJ / cm ^{2 so} that the polarization direction was perpendicular to the stripe direction of the pattern. Next, a 2% by mass cyclopentanone solution of a photodimerization type material (Rolic technologies, trade name: ROP103) is applied in a pattern to the even-numbered lyophilic region using the above-described ink jet device. The striped second pattern was obtained by drying at a temperature of 15 ° C. for 15 minutes. This second pattern was subjected to alignment treatment by irradiating linearly polarized ultraviolet rays at about 100 mJ / cm ^{2 so} that the polarization direction coincided with the stripe direction of the pattern. In this way, a first alignment pattern and a second alignment pattern were obtained. This produced the 2nd alignment processing board | substrate.

(Production of liquid crystal display element)
One alignment treatment substrate was sprayed with 1.5 μm bead spacers, and a sealant was applied to the other alignment treatment substrate with a seal dispenser. Next, both substrates were made to face each other so that the respective alignment treatment directions were parallel, and thermocompression bonding was performed to produce an empty liquid crystal cell.
Next, a ferroelectric liquid crystal (trade name: R2301, manufactured by AZ Electronic Materials) is used to attach a ferroelectric liquid crystal to the upper portion of the injection port, and an oven is used to obtain an N-phase-isotropic phase transition temperature of 10 Injection was performed at a temperature higher by 20 ° C to 20 ° C, and the temperature was slowly returned to room temperature.

  The obtained liquid crystal cell was arranged between two polarizing plates arranged in crossed Nicol so that the alignment treatment direction and the polarizing axis of one polarizing plate coincided. When a voltage of ± 5 V rectangle is applied between the electrodes at a frequency of 1 Hz using a pulse generator, a region where the first alignment pattern using the photoisomerizable material is formed on the second alignment processing substrate; It was observed that light was alternately transmitted through the region where the second alignment pattern using the photodimerization type material was formed.

[Example 4]
(Preparation of the first alignment processing substrate)
On the alkali-free glass substrate on which the electrodes were formed, polyimide (Nissan Chemical Industry Co., Ltd., trade name: SE-7492) was printed and rubbed to form an alignment film.

(Preparation of second alignment processing substrate)
A partition wall forming resist solution (manufactured by JSR, trade name: NN780) was spin-coated at a rotation speed of 2000 pm for 15 seconds on an alkali-free glass substrate on which electrodes were formed, and dried on a hot plate at 100 ° C. for 3 minutes. Subsequently, the resist was cured by irradiating with ultraviolet rays through a mask at about 100 mJ / cm ² . Thereafter, the uncured resist was washed with an inorganic alkaline solution for about 30 seconds, and then washed with water for 30 seconds. As a result, stripe-shaped partition walls having a width of 20 μm were formed on the substrate at intervals of a width of 180 μm.

Next, an odd numbered pattern separated by the partition walls is used to form a pattern of a solution of a photoisomerizable material (DIC, trade name: LIA01) using an inkjet device (Dimatix, Dimatix SE-128). It was applied to. This solution spreads only in the pattern and was dried at 100 ° C. for 1 minute to obtain a striped first pattern. Subsequently, alignment treatment was performed by irradiating the first pattern with linearly polarized ultraviolet rays at about 1000 mJ / cm ^{2 so} that the polarization direction was perpendicular to the stripe direction of the pattern. Next, a 2% by mass cyclopentanone solution of a photodimerization material (Rolic technologies, trade name: ROP103) is applied to the even-numbered patterns separated by the partition walls in the form of a pattern using the inkjet device. And dried at 130 ° C. for 15 minutes to obtain a striped second pattern. This second pattern was subjected to alignment treatment by irradiating linearly polarized ultraviolet rays at about 100 mJ / cm ^{2 so} that the polarization direction coincided with the stripe direction of the pattern. In this way, a first alignment pattern and a second alignment pattern were obtained. This produced the 2nd alignment processing board | substrate. This obtained the 2nd orientation processing board | substrate.

(Production of liquid crystal display element)
One alignment treatment substrate was sprayed with 1.5 μm bead spacers, and a sealant was applied to the other alignment treatment substrate with a seal dispenser. Next, both substrates were made to face each other so that the respective alignment treatment directions were parallel, and thermocompression bonding was performed to produce an empty liquid crystal cell.
Next, a ferroelectric liquid crystal (trade name: R2301, manufactured by AZ Electronic Materials) is used to attach a ferroelectric liquid crystal to the upper portion of the injection port, and an oven is used to obtain an N-phase-isotropic phase transition temperature of 10 Injection was performed at a temperature higher by 20 ° C to 20 ° C, and the temperature was slowly returned to room temperature.

  The obtained liquid crystal cell was arranged between two polarizing plates arranged in crossed Nicol so that the alignment treatment direction and the polarizing axis of one polarizing plate coincided. When a voltage of ± 5 V rectangle is applied between the electrodes at a frequency of 1 Hz using a pulse generator, a region where the first alignment pattern using the photoisomerizable material is formed on the second alignment processing substrate; It was observed that light was alternately transmitted through the region where the second alignment pattern using the photodimerization type material was formed.

[Example 5]
(Production of first alignment processing substrate)
3 g of isopropyl alcohol, 0.4 g of organosilane (TSL8113, manufactured by Toshiba Silicone), 0.04 g of fluoroalkylsilane (MF-160E, manufactured by Tochem Products), and a photocatalytic inorganic coating agent (ST-K01, manufactured by Ishihara Sangyo Co., Ltd.) ) 1.5 g was mixed and heated at 100 ° C. for 20 minutes with stirring. This solution is applied on a non-alkali glass substrate on which an ITO transparent electrode is formed by spin coating, and the substrate is dried at a temperature of 150 ° C. for 10 minutes to promote hydrolysis and polycondensation reaction. Obtained a 0.2 μm thick wettability changing layer firmly fixed in the organopolysiloxane.

Next, the pattern surface of the negative photomask is placed on this wettability changing layer, and UV exposure is performed from the photomask side with a mercury lamp (wavelength 365 nm) at an illuminance of 300 mW / cm ² for 900 seconds. A sex change pattern was formed. The wettability change pattern was formed by alternately forming stripe-shaped liquid repellent areas having a width of 20 μm and stripe-shaped lyophilic areas having a width of 180 μm.

Next, a solution of polyimide (Nissan Chemical Industries, trade name: SE-7492) is used in an odd-numbered lyophilic region of the wettability changing layer by using an inkjet device (Dimatix, Dimatix SE-128). Was applied in a pattern. This solution wets and spreads only in the lyophilic region, is dried at 100 ° C. for 15 minutes, and is then fired at 200 ° C. for 30 minutes to obtain a striped first pattern. This substrate was rubbed to obtain a striped first alignment pattern.
Next, on the even-numbered lyophilic region of the wettability changing layer, using the above-described ink jet device, a photoisomerization material (manufactured by DIC, product name: LIA01) solution is applied in a pattern, and at 100 ° C. Dry for 1 minute. Subsequently, this photoisomerizable material was subjected to alignment treatment by irradiating linearly polarized ultraviolet rays at about 1000 mJ / cm ^{2 so} that the polarization direction was perpendicular to the stripe direction of the pattern. Next, a 5% by mass solution of a reactive liquid crystal material (Rolic technologies, trade name: ROF5101) was applied onto the photo-alignment film in a pattern using the inkjet apparatus. The reactive liquid crystal was irradiated with ultraviolet rays of about 1000 mJ / cm ² in a nitrogen atmosphere to cure the reactive liquid crystal material, thereby obtaining a striped second alignment pattern.

(Preparation of second alignment processing substrate)
A second alignment treatment substrate was produced in the same manner as the production of the first alignment treatment substrate.

(Production of liquid crystal display element)
One alignment treatment substrate was sprayed with 1.5 μm bead spacers, and a sealant was applied to the other alignment treatment substrate with a seal dispenser. Next, both substrates are opposed so that the first alignment pattern made of a rubbing film and the second alignment pattern having the reactive liquid crystal layer face each other so that the respective alignment treatment directions are parallel, and thermocompression bonding is performed. An empty liquid crystal cell was prepared.
Next, a ferroelectric liquid crystal (trade name: R2301, manufactured by AZ Electronic Materials) is used to attach a ferroelectric liquid crystal to the upper portion of the injection port, and an oven is used to obtain an N-phase-isotropic phase transition temperature of 10 Injection was performed at a temperature higher by 20 ° C to 20 ° C, and the temperature was slowly returned to room temperature.

The obtained liquid crystal cell was arranged between two polarizing plates arranged in crossed Nicol so that the alignment treatment direction and the polarizing axis of one polarizing plate coincided. When a voltage of ± 5 V rectangle was applied between the electrodes at a frequency of 1 Hz using a pulse generator, it was observed that light was transmitted alternately at odd and even numbers in the lyophilic region.
Further, when the optical response when a voltage of ± 5 V was applied using a polarizing microscope and a measuring device consisting of a photodiode and a pulse generator was measured, a second alignment pattern having a reactive liquid crystal layer was formed. It was observed that the transmittance changed when a negative voltage was applied to the electrode on the side of the region. Furthermore, at this time, it was measured that the direction of the liquid crystal molecules changed twice the tilt angle.

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 sectional drawing which shows an example of the liquid crystal display element 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 orientation state of a ferroelectric liquid crystal. It is explanatory drawing which shows the spontaneous polarization of a ferroelectric liquid crystal. It is a schematic diagram which shows the other example of the orientation state of a ferroelectric liquid crystal. It is a schematic sectional drawing which shows the other example of the liquid crystal display element of this invention. It is a schematic sectional drawing which shows an example of the 2nd orientation processing board | substrate in this invention. It is process drawing which shows an example of the manufacturing method of the 2nd orientation processing board | substrate in this invention. It is process drawing which shows the other example of the manufacturing method of the 2nd orientation processing board | substrate in this invention. It is a schematic sectional drawing which shows the other example of the 2nd orientation processing board | substrate in this invention. It is a schematic sectional drawing which shows the other example of the 2nd orientation processing board | substrate in this invention. It is process drawing which shows the other example of the manufacturing method of the 2nd orientation processing board | substrate in this invention. It is a schematic sectional drawing which shows the other example of the 2nd orientation processing board | substrate in this invention. It is a schematic diagram which shows the other example of the orientation state of a ferroelectric liquid crystal. It is explanatory drawing which shows the spontaneous polarization of a ferroelectric liquid crystal. It is a schematic diagram which shows the other example of the orientation state of a ferroelectric liquid crystal. It is the figure which showed the difference in orientation by the difference in the phase sequence which a ferroelectric liquid crystal has. It is a schematic perspective view which shows an example of the liquid crystal display element 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 sectional drawing which shows the other example of the liquid crystal display element of this invention. It is a schematic diagram which shows the other example of the orientation state of a ferroelectric liquid crystal. It is a schematic diagram which shows the other example of the orientation state of a ferroelectric liquid crystal. It is the graph which showed the change of the transmittance | permeability with respect to the applied voltage of a ferroelectric liquid crystal.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Liquid crystal display element 2 ... 1st base material 3 ... 1st electrode layer 4 ... 1st orientation layer 5 ... 1st orientation processing board | substrate 4a, 14a ... 1st orientation pattern 4b, 14b ... 2nd orientation pattern 10 ... Liquid crystal layer DESCRIPTION OF SYMBOLS 12 ... 2nd base material 13 ... 2nd electrode layer 14 ... 2nd alignment layer 15 ... 2nd alignment processing board 16 ... Partition 17 ... Reactive liquid crystal alignment film 18 ... Reactive liquid crystal layer 25 ... Wetting property change layer 26a ... Lipophilic region 26b ... Liquid repellent region 27 ... Shading part 28 ... Insulating part LC ... Liquid crystal molecule Ps ... Spontaneous polarization

Claims (13)

A first alignment treatment substrate having a first substrate, a first electrode layer formed on the first substrate, and a first alignment layer formed on the first electrode layer and made of a rubbing film; and A second substrate, a second electrode layer formed on the second substrate, and a second alignment layer formed on the second electrode layer and comprising a first alignment pattern and a second alignment pattern. A second alignment treatment substrate having the first alignment layer and the second alignment layer facing each other, and a ferroelectric liquid crystal sandwiched between the first alignment layer and the second alignment layer; A liquid crystal display element,
The ferroelectric liquid crystal exhibits monostability and exhibits half V-shaped switching characteristics,
The first alignment pattern is a pattern composed of a photo-alignment film containing a photoisomerization-type material that imparts anisotropy to the alignment film by causing a photoisomerization reaction, and the second alignment pattern is reactive. A pattern comprising an alignment film for liquid crystal and a reactive liquid crystal layer formed on the alignment film for reactive liquid crystal and immobilizing reactive liquid crystal, or anisotropic to the alignment film by causing a photodimerization reaction A liquid crystal display element, wherein the liquid crystal display element is any one of a pattern made of a photo-alignment film containing a photodimerization-type material that imparts a light.   Between the second electrode layer and the second alignment layer, there is formed a wettability changing layer whose wettability is changed by the action of a photocatalyst accompanying energy irradiation, and a liquid repellent region and a surface of the wettability changing layer are formed. The liquid crystal display element according to claim 1, wherein a wettability change pattern including a lyophilic region is formed, and the second alignment layer is formed only on the lyophilic region.   A patterned light-shielding portion is formed between the second base material and the wettability changing layer, and the liquid-repellent region is disposed in a region where the light-shielding portion is provided. Item 4. A liquid crystal display device according to Item 3.   An insulating part is formed between the first alignment pattern and the second alignment pattern, the surface of the insulating part is a liquid-repellent region, the surface of the layer in the opening of the insulating part is a lyophilic region, The liquid crystal display element according to claim 1, wherein the second alignment layer is formed only on the active region.   The liquid crystal display element according to claim 5, wherein the insulating portion is a light shielding portion.   The liquid crystal display element according to claim 1, wherein a partition wall is formed between the first alignment pattern and the second alignment pattern. A first base material; a first electrode layer formed on the first base material; and a first alignment layer formed on the first electrode layer and including a first alignment pattern and a second alignment pattern. From the first alignment pattern and the second alignment pattern, the first alignment processing substrate, the second substrate, the second electrode layer formed on the second substrate, and the second electrode layer. A second alignment treatment substrate having a second alignment layer, wherein the first alignment pattern of the first alignment layer and the second alignment pattern of the second alignment layer face each other, and the second alignment pattern of the first alignment layer And a liquid crystal display element which is arranged so that the first alignment patterns of the second alignment layer face each other, and a ferroelectric liquid crystal is sandwiched between the first alignment layer and the second alignment layer,
The ferroelectric liquid crystal exhibits monostability and half V-shaped switching characteristics,
The first alignment pattern is a pattern made of a rubbing film,
The second alignment pattern is formed on the reactive liquid crystal alignment film and the reactive liquid crystal alignment layer formed on the reactive liquid crystal alignment film, and generates a photodimerization reaction. Contains a photo-alignment film that contains a photo-dimerization-type material that imparts anisotropy to the alignment film, or a photoisomerization-type material that imparts anisotropy to the alignment film by causing a photoisomerization reaction A liquid crystal display element, wherein the liquid crystal display element is one of a pattern made of a photo-alignment film.   A wettability changing layer in which wettability changes between the first electrode layer and the first alignment layer and between the second electrode layer and the second alignment layer by the action of a photocatalyst accompanying energy irradiation. Are formed on the surface of the wettability changing layer, and a wettability changing pattern including a liquid repellent region and a lyophilic region is formed, and the first alignment layer and the second alignment layer are formed only on the lyophilic region. The liquid crystal display element according to claim 8, wherein a layer is formed.   A pattern is formed between at least one of the first base material and the wettability changing layer of the first alignment processing substrate and between the second base material and the wettability changing layer of the second alignment processing substrate. The liquid crystal display element according to claim 9, wherein a light shielding portion is formed, and the liquid repellent region is disposed in a region where the light shielding portion is provided.   An insulating portion is formed between the first alignment pattern and the second alignment pattern of the first alignment layer, and between the first alignment pattern and the second alignment pattern of the second alignment layer, and the surface of the insulating portion is A liquid repellent region, a layer surface in the opening of the insulating portion is a lyophilic region, and the first alignment layer and the second alignment layer are formed only on the lyophilic region. The liquid crystal display element according to claim 8.   The liquid crystal display element according to claim 11, wherein at least one of an insulating portion formed on the first alignment processing substrate and an insulating portion formed on the second alignment processing substrate is a light shielding portion.   A partition is formed between the first alignment pattern and the second alignment pattern of the first alignment layer or between the first alignment pattern and the second alignment pattern of the second alignment layer. The liquid crystal display element according to claim 8.   The liquid crystal display element according to claim 1, wherein the rubbing film contains polyimide.

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