JPWO2015016087A1 - Liquid crystal display element and radiation sensitive resin composition - Google Patents

Abstract

A liquid crystal display element having a wall-like electrode and improved display efficiency is provided, and a radiation-sensitive resin composition used for forming the wall-like electrode is provided. The liquid crystal display element (1) has a liquid crystal (4) sandwiched between a first substrate (2) and a second substrate (3), and electrodes (5, 6) are arranged on the first substrate (2). The liquid crystal (4) is driven by the electric field applied between the electrodes (5, 6). The electrodes (5, 6) are wall-shaped having wall-shaped resin portions (9, 10) and conductive portions (11, 12) made of a conductive member provided on the side surfaces of the resin portions (9, 10). The electrode. The wall-shaped resin portions (9, 10) are formed using a radiation-sensitive resin composition containing [A] polymer and [B] photosensitizer.

Description

  The present invention relates to a liquid crystal display element and a radiation sensitive resin composition.

  The liquid crystal display element is configured by sandwiching liquid crystal between a pair of substrates. In a liquid crystal display element, an orientation change is caused in a liquid crystal by applying an electric field between substrates. Then, light is partially transmitted or shielded corresponding to the change in the orientation of the liquid crystal. A liquid crystal display element can display an image using such characteristics. The liquid crystal display element has an advantage that it can be made thinner and lighter than a conventional CRT display device.

  The liquid crystal display elements at the beginning of development were used as display elements for calculators and clocks centered on character displays and the like. After that, the simple matrix method was developed, and the dot matrix display became easy.

  Next, the development of an active matrix liquid crystal display element using TFT (Thin Film Transistor), which is a semiconductor device, has made it possible to achieve good image quality with excellent contrast ratio and response performance. By overcoming problems such as widening the viewing angle, it has also been used for desktop computer monitors. In recent years, a wider viewing angle, faster response of liquid crystal, improved display quality, and the like have been realized, and it has come to be used as a thin television display element.

  On the other hand, liquid crystal display elements are widely used as display elements for portable information devices such as smartphones in response to high definition. Recently, in such portable information devices, further improvement in image quality has been demanded, and improvement in display efficiency such as higher definition and corresponding aperture ratio has been strongly demanded.

  As a technique for improving the display efficiency of the liquid crystal display element, for example, a technique described in Patent Document 1 is known. In the liquid crystal display device described in Patent Document 1, a pair of electrodes is formed at both ends of a pixel region, a video signal is supplied to one electrode (source electrode), and the other electrode (common electrode) serves as a reference. Supply a common signal. Accordingly, the liquid crystal display device described in Patent Document 1 generates an electric field (referred to as a transverse electric field) parallel to the main surface of the liquid crystal display panel, and the liquid crystal is a surface parallel to the main surface of the liquid crystal display panel. It is the structure which drives in the inside.

  In particular, in the liquid crystal display device described in Patent Document 1, the source electrode and the common electrode are formed so as to protrude from the main surface of the first substrate toward the second substrate, and the extending direction thereof is the main surface of the first substrate. It is a wall-like electrode shape formed so as to be perpendicular to. By providing such a wall-like electrode, the liquid crystal display device of Patent Document 1 has the same density of lines of electric force even in a region far from the region close to the first substrate (region close to the second substrate). Like that. And the drive efficiency of a liquid crystal can be improved and display efficiency can be improved.

  Patent Document 2 describes a technique for improving display efficiency by driving a liquid crystal in a plane parallel to the main surface of a liquid crystal display panel, as in Patent Document 1. In the liquid crystal display device described in Patent Document 2, a stepped portion is formed for each region of a large number of pixels. The step portion is an insulating film formed in a convex shape at the boundary portion of the pixel. In the liquid crystal display device described in Patent Document 2, a planar electrode made of a conductive material such as ITO (Indium Tin Oxide) is provided on the side wall surface of the stepped portion to form a wall-shaped electrode. That is, in the liquid crystal display device described in Patent Document 2, the wall-like electrode is configured to have a stacked structure of an insulating film and a conductive film that form a stepped portion.

JP-A-6-214244 JP 2012-220575 A

  As described above, in order to improve the display efficiency of the liquid crystal display element, a technique using a wall-like electrode (hereinafter also simply referred to as a wall-like electrode) as described in Patent Document 1 is effective. And when improvement of productivity of a liquid crystal display element is considered, as described in Patent Document 2, it is preferable that the wall-like electrode has a laminated structure including an insulating film and a conductive film.

  In that case, in the liquid crystal display element, an insulating film patterned in a convex shape is formed on one of the substrates sandwiching the liquid crystal, and then a patterned conductive film is provided on the side wall surface of the insulating film to form a wall shape. A method of forming an electrode is effective.

  The formed wall electrode is for improving display efficiency so as to be effective for high-definition display using a plurality of pixels, and is formed uniformly and simply between the plurality of pixels. Is required. That is, the wall electrode is required to be formed with high uniformity and high productivity. Therefore, the convex insulating film constituting the wall electrode is preferably patterned with high uniformity and formed with high productivity.

  Therefore, there is a demand for a technique for patterning a convex insulating film with high uniformity and high sensitivity to form a wall electrode with high efficiency. There is a need to provide a liquid crystal display element having wall-like electrodes and improved display efficiency.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a liquid crystal display element having a wall-like electrode and improved display efficiency.

  Moreover, the objective of this invention is providing the radiation sensitive resin composition used for formation of the wall-shaped electrode of a liquid crystal display element.

  Other objects and advantages of the present invention will become apparent from the following description.

According to a first aspect of the present invention, a liquid crystal is sandwiched between a first substrate and a second substrate which are arranged to face each other.
A pair of electrodes are arranged on the surface of the first substrate facing the second substrate,
A liquid crystal display element that drives liquid crystal by an electric field applied between a pair of electrodes,
At least one of the pair of electrodes is provided in a region including a wall-shaped resin portion projecting from the surface of the first substrate toward the second substrate side and at least a part of the side surface of the resin portion. A wall-like electrode having a conductive portion made of a conductive member,
The wall-shaped resin part
The present invention relates to a liquid crystal display element formed by using a radiation sensitive resin composition containing [A] a polymer and [B] a photosensitizer.

  In the first aspect of the present invention, the electric field applied between the pair of electrodes preferably has a component parallel to a surface of the first substrate facing the second substrate.

In the first aspect of the present invention, each of the pair of electrodes is a wall electrode,
The conductive portions of the pair of wall electrodes are preferably configured to have portions facing each other.

  In the first aspect of the present invention, it is preferable that [B] the photosensitizer contains at least one selected from a photoradical polymerization initiator and a photoacid generator.

  In the first aspect of the present invention, the wall-shaped resin portion preferably has a forward tapered shape in cross section.

  In the first aspect of the present invention, it is preferable to have an alignment film formed using a photoalignment agent.

The second aspect of the present invention is:
[A] polymer,
[B-1] Radiation sensitive resin composition containing a radical photopolymerization initiator and [C] a polymerizable compound, the wall-shaped resin of the wall-shaped electrode of the liquid crystal display element of the first aspect of the present invention It is related with the radiation sensitive resin composition characterized by being used for formation of a part.

The third aspect of the present invention is:
A radiation-sensitive resin composition comprising [A] a polymer and [B-2] a photoacid generator, wherein the wall-shaped resin portion of the wall-shaped electrode of the liquid crystal display element of the first aspect of the present invention It is related with the radiation sensitive resin composition characterized by being used for formation.

  According to the first aspect of the present invention, a liquid crystal display element having a wall-like electrode and improved display efficiency can be obtained.

  According to the 2nd aspect of this invention, the radiation sensitive resin composition used for formation of the wall-shaped electrode of a liquid crystal display element is obtained.

  According to the 3rd aspect of this invention, the radiation sensitive resin composition used for formation of the wall-shaped electrode of a liquid crystal display element is obtained.

It is sectional drawing which shows typically the pixel structure in the 1st example of the liquid crystal display element of embodiment of this invention. It is a top view which shows typically the pixel structure in the 1st example of the liquid crystal display element of embodiment of this invention. It is sectional drawing which shows typically the pixel structure at the time of the electric field application in the 1st example of the liquid crystal display element of embodiment of this invention. It is a top view which shows typically the pixel structure at the time of the electric field application in the 1st example of the liquid crystal display element of embodiment of this invention. It is a top view which shows typically another example of the wall-shaped electrode of the liquid crystal display element of embodiment of this invention. It is sectional drawing which shows typically the pixel structure in the 2nd example of the liquid crystal display element of embodiment of this invention. It is sectional drawing which shows typically the pixel structure in the 3rd example of the liquid crystal display element of embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

<Liquid crystal display element>
FIG. 1 is a cross-sectional view schematically showing a pixel structure in a first example of a liquid crystal display element of an embodiment of the present invention.

  A liquid crystal display element 1 which is a first example of an embodiment of the present invention sandwiches a liquid crystal 4 between a first substrate 2 and a second substrate 3 which are arranged to face each other. This is a liquid crystal display element in which a pair of electrodes 5 and 6 are disposed on the surface facing the substrate 3 and the liquid crystal 4 is driven by an electric field applied between the pair of electrodes 5 and 6.

  The distance between the first substrate 2 and the second substrate 3 is usually 2 μm or more and 20 μm or less, that is, 2 μm to 20 μm, and these are fixed to each other by a sealing material (not shown) provided in the periphery. Yes.

  Examples of the material constituting the first substrate 2 and the second substrate 3 include glass such as soda lime glass and non-alkali glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, Examples thereof include polyamideimide and polyimide. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  An alignment film (not shown) is preferably provided on the opposing surfaces of the first substrate 2 and the second substrate 3. For example, the alignment film can be provided on the surfaces of the first substrate 2 and the second substrate 3 that are in contact with the liquid crystal 4 and the surfaces of the electrodes 5 and 6 that will be described later that are in contact with the liquid crystal 4. The alignment film can be formed using a polymer material such as polyimide, for example. In addition, the alignment film is subjected to alignment treatment such as rubbing treatment or photo-alignment treatment, if necessary, so that the liquid crystal 4 sandwiched between the first substrate 2 and the second substrate 3 is uniformly aligned. Can be realized.

  Each of the pair of electrodes 5 and 6 of the liquid crystal display element 1 includes wall-shaped resin portions 9 and 10 protruding from the surface of the first substrate 2 toward the second substrate 3 side, 10 is a wall-like electrode having film-like conductive portions 11 and 12 made of a conductive member provided on the side surface of the plate. The conductive portions 11 and 12 are provided in regions including at least a part of the side surfaces of the resin portions 9 and 10 facing each other. That is, the conductive portions 11 and 12 of the electrodes 5 and 6 forming the wall electrode are configured to have portions facing each other with the liquid crystal 4 interposed therebetween.

  The conductive portions 11 and 12 of the electrodes 5 and 6 forming the wall-like electrodes can be provided on the entire surfaces of the side surfaces of the resin portions 9 and 10 facing each other, as shown in FIG. The conductive portions of the electrodes 5 and 6 may be provided only on part of the side surfaces of the resin portions 9 and 10 that face each other.

  Similarly, the conductive portions 11 and 12 of the electrodes 5 and 6 are each formed using a conductive member. Examples of the conductive members constituting the conductive portions 11 and 12 include transparent conductive materials such as ITO (Indium Tin Oxide), zinc oxide-based AZO (Aluminum doped Zinc Oxide), and GZO (Gallium doped Zinc Oxide). it can.

  Similarly, the wall-shaped resin portions 9 and 10 of the electrodes 5 and 6 are made of insulating resin. The electrodes 5 and 6 are formed so as to protrude from the surface of the first substrate 2 toward the second substrate 3 according to the structure of the wall-shaped resin portions 9 and 10, and the extending direction thereof is the first. A wall-like electrode is formed so as to be perpendicular to the main surface of the substrate.

  Therefore, the electric field applied between the pair of electrodes 5 and 6 using the conductive portions 11 and 12 of the electrodes 5 and 6 is a component parallel to the surface of the first substrate 2 facing the second substrate 3. Have In the liquid crystal display element 1, the liquid crystal 4 is driven from the initial alignment state by an electric field applied between the pair of electrodes 5 and 6, and the first substrate 2 is in a plane facing the second substrate 3. Change orientation.

  By providing such wall-shaped electrodes 5 and 6, the liquid crystal display element 1 can generate electric lines of force even in a region far from the region close to the first substrate 2 (region close to the second substrate 3). Thus, the driving efficiency of the liquid crystal 4 can be improved and the display efficiency can be improved.

  Hereinafter, the driving of the liquid crystal 4 in the liquid crystal display element 1 will be described in more detail with reference to FIGS.

  FIG. 2 is a plan view schematically showing a pixel structure in the first example of the liquid crystal display element of the embodiment of the present invention.

  As shown in FIG. 2, the liquid crystal display element 1 which is the first example of the liquid crystal display element of the embodiment of the present invention is illustrated in a rod shape that constitutes the liquid crystal 4 by the action of the alignment film (not shown) described above. The liquid crystal molecules 7 are uniformly aligned. That is, in the liquid crystal 4, in the initial alignment state when no voltage is applied between the electrodes 5 and 6, the liquid crystal molecules 7 illustrated in a rod shape with respect to the longitudinal direction of the electrodes 5 and 6 shown in FIG. Are uniformly oriented to form an angle of More specifically, the above-described electric field formation direction formed between the electrodes 5 and 6 when a voltage is applied between the electrodes 5 and 6 (in FIG. 2, the electric field direction is indicated by an arrow. The same applies to FIG. 4), and the liquid crystal 4 is uniformly aligned so that the angle formed by the major axis (optical axis) direction of the liquid crystal molecules 7 is 45 degrees or more and less than 90 degrees.

  FIG. 3 is a cross-sectional view schematically showing a pixel structure when an electric field is applied in the first example of the liquid crystal display element of the embodiment of the present invention.

  FIG. 4 is a plan view schematically showing a pixel structure when an electric field is applied in the first example of the liquid crystal display element of the embodiment of the present invention.

  In the liquid crystal display element 1, when an electric field is applied between the electrodes 5 and 6, the liquid crystal 4 is driven as shown in FIGS. 3 and 4. In the liquid crystal display element 1, the liquid crystal 4 has, for example, positive dielectric anisotropy. Therefore, the orientation of the liquid crystal molecules 7 constituting the liquid crystal 4 of the liquid crystal display element 1 changes so that the major axis direction thereof is parallel to the electric field direction between the electrodes 5 and 6.

  At this time, as described above, the electric field applied between the pair of electrodes 5 and 6 using the conductive portions 11 and 12 of the electrodes 5 and 6 is, as described above, the second electric field of the first substrate 2. It has a component parallel to the surface facing the substrate 3. Accordingly, in the liquid crystal display element 1, the liquid crystal molecules 7 of the liquid crystal 4 undergo an orientation change that changes the orientation angle within the plane of the first substrate 2 facing the second substrate 3.

  The liquid crystal display element 1 of the present embodiment capable of driving the liquid crystal 4 described above is polarized on the surface opposite to the side in contact with the liquid crystal 4 in each of the first substrate 2 and the second substrate 3. A plate (not shown) can be provided.

  The pair of polarizing plates further sandwich the first substrate 2 and the second substrate 3 that sandwich the liquid crystal 4. Therefore, the liquid crystal display element 1 can change the light transmittance by changing the orientation of the liquid crystal molecules 7 of the liquid crystal 4 by applying an electric field by arranging the polarization transmission axes of the pair of polarizing plates at a predetermined angle.

  That is, the liquid crystal display element 1 of the present embodiment can constitute a so-called birefringence mode liquid crystal display element. The liquid crystal display element 1 is a polarizing plate whose orientation is changed within the plane by applying an electric field while the major axis (optical axis) direction of the liquid crystal molecules 7 of the liquid crystal 4 is substantially parallel to the substrate surface. The light transmittance is changed by changing the angle formed with the axis. The liquid crystal display element 1 uses the change in light transmittance due to the application of the electric field for displaying an image.

  As described above, in the liquid crystal display element 1 of the present embodiment, the pair of electrodes 5 and 6 to which an electric field is applied are provided so as to protrude from the surface of the first substrate 2 toward the second substrate 3. It is a wall electrode. The liquid crystal display element 1 can efficiently form an electric field parallel to the mutually opposing substrate surfaces of the first substrate 2 and the second substrate 3 that sandwich the liquid crystal 4. As a result, the liquid crystal display element 1 of the present embodiment can achieve high display efficiency.

  In the liquid crystal display element 1 which is the first example of the liquid crystal display element of the embodiment of the present invention shown in FIGS. 1 to 4, only one pixel portion is shown, and a pair of electrodes 5 is provided for the one pixel. , 6 are shown. However, the liquid crystal display element 1 which is the first example of the embodiment of the present invention is not limited to such a structure. The liquid crystal display element 1 has a plurality of pixels, and a wall-like electrode can be arranged in each pixel. Moreover, the liquid crystal display element 1 which is the 1st example of embodiment of this invention can have a wall-shaped electrode of arrangement different from the electrodes 5 and 6.

  FIG. 5 is a plan view schematically showing another example of the wall electrode of the liquid crystal display element of the embodiment of the present invention.

  FIG. 5 schematically shows the structure of the electrodes 15 and 16 arranged in one pixel portion of the liquid crystal display element 1 (not shown) by a plan view. In the example shown in FIG. 5, a region between a pair of electrodes 15 and 16 adjacent to each other and adjacent to each other constitutes a subpixel, and a plurality of subpixels constitute one pixel. At this time, both the electrode 15 and the electrode 16 can be wall electrodes. In that case, the electrodes 15 and 16 have a wall-shaped resin portion projecting from one substrate surface toward the other substrate side, and conductive portions arranged on both side surfaces of the resin portion. Preferably, it is configured.

  That is, in another example of the wall electrode of the liquid crystal display element of this embodiment, as shown in FIG. 5, a plurality of electrodes 15 that are wall electrodes are connected to the wiring 17 and arranged in a comb shape. A plurality of electrodes 16 as wall electrodes are connected to the wiring 18 and arranged in a similar comb shape. And the comb-tooth part of two comb-shaped arrangement | positioning is arrange | positioned so that it may mutually bite, and the electrode 15 and the electrode 16 are arranged so that it may line up alternately. In other words, each of the plurality of electrodes 15 arranged in a comb shape is arranged so as to face one of the plurality of electrodes 16 arranged in a comb shape, thereby forming an electrode group in the pixel. Since the wall-like electrode in the pixel has such a structure, the liquid crystal display element of this embodiment can control the distance between a pair of electrodes to which an electric field is applied independently of the size of the pixel. As a result, the liquid crystal display element of this embodiment can easily apply an electric field to the liquid crystal and can drive the liquid crystal with high efficiency.

  Moreover, in the liquid crystal display element 1 which is the 1st example of the liquid crystal display element of embodiment of this invention of FIGS. 1-4, all of a pair of electrodes 5 and 6 to which an electric field is applied are 1st board | substrates. 2 is a wall-like electrode projecting from the surface 2 toward the second substrate 3, and one of the electrodes 5, 6 is a linear electrode formed on the substrate surface of the first substrate 2. be able to.

  FIG. 6 is a cross-sectional view schematically showing a pixel structure in a second example of the liquid crystal display element of the embodiment of the present invention.

  6 is the same as the liquid crystal display element 1 of FIGS. 1 to 4 except that the structure of the electrode 106 of the pair of electrodes 5 and 106 is different. It has a structure. Therefore, the same components are denoted by the same reference numerals, and redundant description is omitted.

  A liquid crystal display element 101, which is a second example of the embodiment of the present invention shown in FIG. 6, has a pair of electrodes 5 and 106 like the liquid crystal display element 1 described above. Of the pair of electrodes 5 and 106 of the liquid crystal display element 101, the electrode 5 includes a wall-shaped resin portion 9 projecting from the surface of the first substrate 2 toward the second substrate 3, and a resin. And a conductive portion 11 made of a film-like conductive member provided on the side surface of the portion 9.

  On the other hand, in the liquid crystal display element 101, the electrode 106 is a film-like linear electrode provided on the surface of the first substrate 2. Examples of the conductive member that can constitute the electrode 106 include transparent conductive materials such as ITO and zinc oxide-based AZO and GZO.

  In the liquid crystal display element 101, when an electric field is applied between the electrodes 5 and 106, the orientation of the liquid crystal molecules 7 of the liquid crystal 4 changes. At this time, the electric field applied between the pair of electrodes 5 and 106 has a component parallel to the surface of the first substrate 2 facing the second substrate 3. Therefore, in the liquid crystal display element 101, the liquid crystal molecules 7 of the liquid crystal 4 undergo an orientation change that changes the orientation angle within the plane of the first substrate 2 facing the second substrate 3.

  As with the liquid crystal display element 1, the liquid crystal display element 101 of the present embodiment has a polarizing plate (not shown) on the side opposite to the side in contact with the liquid crystal 4 in each of the first substrate 2 and the second substrate 3. Can be provided.

  Accordingly, the liquid crystal display element 101 of the present embodiment constitutes a birefringence mode liquid crystal display element as in the liquid crystal display element 1 described above. By applying an electric field, the liquid crystal display element 101 changes the orientation in the plane while the major axis (optical axis) direction of the liquid crystal molecules 7 of the liquid crystal 4 is substantially parallel to the substrate surface, and the axis of the polarizing plate set at a predetermined angle. The light transmittance is changed by changing the angle formed by. The liquid crystal display element 101 can use the change in light transmittance due to the application of the electric field for image display.

  In the liquid crystal display element 101 as the second example of the embodiment of the present invention, the electrode 5 that forms a wall electrode is arranged at the end of the pixel for one pixel, and the electrode 106 that forms a linear electrode. Can also be placed inside the pixel. In that case, it is preferable to arrange two or more wall-like electrodes 5 at the end of the pixel and to arrange at least one electrode 106 inside the pixel. With such an electrode arrangement structure, an electric field can be applied between each of the electrodes 5 and the electrode 106 in the pixel, and an efficient electric field can be formed in the pixel.

  Further, the liquid crystal display element of the embodiment of the present invention can constitute an active matrix type liquid crystal display element. In that case, for example, in the liquid crystal display element 1 which is the first example of the liquid crystal display element of the embodiment of the present invention, scanning lines (not shown) and signal lines (not shown) are provided on the first substrate 2. Each pixel is connected to each intersection of the scanning line and the signal line via an active element (not shown) such as a TFT.

  The scanning line and the signal line are connected to a scanning driving circuit (not shown) and a signal driving circuit (not shown), respectively, and an arbitrary voltage can be applied to each scanning line or signal line. When the active element is a TFT, the drain electrode (not shown) of the TFT is connected to the signal line, and the source electrode (not shown) of the TFT is electrically connected to the electrode 6, for example.

  Further, a common line (not shown) is disposed on the first substrate 2 in parallel with the signal line, connected to all pixels, and a common voltage is applied to all pixels from a common voltage generation circuit (not shown). It can be applied. Specifically, the electrode 5 is connected to the common line, and a common voltage is applied to each pixel.

  Liquid crystal 4 is sealed between the first substrate 2 and the second substrate 3, and the liquid crystal display element 1 can constitute an active matrix type liquid crystal display element.

  In the liquid crystal display element according to the embodiment of the present invention, it is not essential that the upper end portion of the wall-shaped electrode is in contact with the opposing substrate. For example, in the liquid crystal display element 1 shown in FIG. 1, the upper end portions of the electrodes 5 and 6 are configured to be in contact with the surface of the opposing second substrate 3, but such a structure is not essential. If the electrodes 5 and 6 are wall-like electrodes protruding from the surface of the first substrate 2 toward the second substrate 3, their upper end portions do not have to be in contact with the second substrate 3. .

  Therefore, for example, in the liquid crystal display element 1, at least one of the electrode 5 and the electrode 6 may have a structure in which the upper end portion does not contact the surface of the second substrate 3 facing it. That is, in the liquid crystal display element 1, at least one of the electrode 5 and the electrode 6 can be configured by providing a gap between the upper end portion thereof and the second substrate 3 facing the upper end portion.

  FIG. 7 is a cross-sectional view schematically showing a pixel structure in a third example of the liquid crystal display element of the embodiment of the present invention.

  A liquid crystal display element 201, which is a third example of the liquid crystal display element of the embodiment of the present invention shown in FIG. 7, is different from that shown in FIGS. 4 has the same structure as the liquid crystal display element 1. Therefore, the same components as those of the liquid crystal display element 1 are denoted by the same reference numerals, and redundant description is omitted.

  In the liquid crystal display element 201 shown in FIG. 7, the upper end portion of the electrode 206 facing the electrode 5 is not in contact with the second substrate 3. The electrode 206 of the liquid crystal display element 201 includes a wall-shaped resin portion 210 protruding from the surface of the first substrate 2 toward the second substrate 3 side, and a conductive member provided on the side surface of the resin portion 210. A wall-like electrode having a film-like conductive portion 212 made of A gap is provided between the upper end portion of the electrode 206 and the second substrate 3 facing the electrode 206.

  In the liquid crystal display element of the embodiment of the present invention, it is also possible to have a structure in which the upper end portions of both of the pair of wall-shaped electrodes facing each other do not contact the surface of the facing substrate. For example, in the liquid crystal display element 1 of FIG. 1, it is possible to have a structure in which the upper ends of both the electrode 5 and the electrode 6 do not come into contact with the surface of the second substrate 3 that is opposed.

  In the liquid crystal display element 1, when there are a plurality of electrodes 5 and 6, a part of the plurality of electrodes 5 or a part of the plurality of electrodes 6 is formed, and an upper end portion is a surface of the second substrate 3. It is possible to have a structure that does not contact with. Further, a part of each of the plurality of electrodes 5 and the plurality of electrodes 6 may have a structure in which the upper end portion does not contact the surface of the second substrate 3.

  At this time, in the liquid crystal display element according to the embodiment of the present invention, of the first substrate and the second substrate sandwiching the liquid crystal, the electrode forming the wall-like electrode provided on the first substrate is opposed. When the structure is in contact with the surface of the second substrate, the electrode can be used as a gap retaining material (spacer) for maintaining the distance between the substrates.

  For example, the liquid crystal display element 1 shown in FIG. 1 is configured such that the upper end portions of the electrodes 5 and 6 are in contact with the surface of the second substrate 3, and the electrodes 5 and 6 are connected to the first substrate 2 and the second substrate 2. It can be used as a spacer for maintaining the distance between the substrates 3.

  In the liquid crystal display element 201 shown in FIG. 7, the upper end portion of the electrode 5 is configured to be in contact with the surface of the second substrate 3, and the electrode 5 is connected to the first substrate 2, the second substrate 3, and the like. It can be used as a spacer for maintaining the distance between the substrates.

  In a conventional liquid crystal display element, in order to maintain a gap between a pair of substrates arranged to face each other so as to sandwich liquid crystal, a technique of dispersing spherical polymer beads between substrates as a spacer has been used. In such a technique, polymer beads are not evenly dispersed on the substrate, and the gap between the substrates may be uneven. Such gap unevenness may cause uneven brightness when displaying an image.

  For example, in the liquid crystal display element 1 according to the embodiment of the present invention, the electrodes 5 and 6 are used as spacers provided between the first substrate 2 and the second substrate 3 as described above. be able to. Similarly, in the liquid crystal display element 201, the electrode 5 can be used as a spacer. Therefore, in the liquid crystal display elements 1 and 201, the occurrence of gap unevenness between the substrates is suppressed, and display defects such as luminance unevenness can be reduced.

  In the liquid crystal display element 201, the electrode 206 has an upper end portion that is not in contact with the second substrate 3. However, for example, when the user presses the liquid crystal display element 201 so that the second substrate 3 is recessed toward the liquid crystal 4, the electrode 206 is used as a support material for suppressing the recess deformation. Can be used.

  The liquid crystal display element of the embodiment of the present invention described above can efficiently form an electric field parallel to the substrate surface sandwiching the liquid crystal. In order to realize such an effect, the structure of the electrode forming the wall electrode Is particularly important.

  As described above, the electrode of the liquid crystal display element of this embodiment includes at least one of the wall-shaped resin portion projecting from the surface of the first substrate toward the second substrate side and the side surface of the resin portion. And a conductive portion made of a conductive member provided in a region including the portion. And the electrode is provided with the shape according to the structure of a resin part. That is, the electrodes of the liquid crystal display element of the present embodiment are formed so as to protrude from the surface of the first substrate toward the second substrate, and the extending direction thereof is perpendicular to the main surface of the first substrate. And has a wall-like shape.

  In the electrode forming the wall electrode of the liquid crystal display element of the present embodiment, it is preferable that the resin portion has a trapezoidal shape or a rectangular shape (rectangle or square). In particular, the resin portion preferably has a forward tapered shape described later on the first substrate. As described above, the conductive portion of the electrode is formed of a conductive material such as ITO to form a film and is disposed in a region including the side wall surface of the resin portion. In the liquid crystal display element of this embodiment, the electrode forming the wall electrode has a laminated structure of a resin portion and a conductive portion that is a conductive film.

  In such an electrode of the liquid crystal display element of this embodiment, the conductive portion can be formed using a known method. That is, after forming the resin portion, a conductive film such as ITO is formed on the resin portion according to a known method. Then, the conductive part can be formed by patterning the conductive film using a known method.

  Therefore, in the liquid crystal display element of the present embodiment, when an electrode that forms a wall-like electrode is to be formed between a plurality of pixels with high productivity and high productivity, it is important to form a resin portion. In other words, the resin part constituting the electrode is preferably formed by highly uniform patterning.

  Therefore, in forming a wall-shaped electrode composed of a resin portion and a conductive portion, a technique of patterning the resin portion with high sensitivity and high uniformity to form an electrode that is a wall-shaped electrode is particularly important.

  Therefore, in the following, the formation of the resin portion of the electrode forming the wall electrode according to the present embodiment will be described in more detail. In particular, a radiation-sensitive resin composition that is provided on one surface of a pair of substrates that sandwich a liquid crystal and is preferably used to form a resin portion that protrudes toward the opposite substrate side. explain.

<Radiation sensitive resin composition>
In the liquid crystal display element of the embodiment of the present invention, the radiation-sensitive resin composition of the embodiment of the present invention is used for forming the resin portion of the electrode forming the wall electrode.

  The radiation sensitive resin composition of the embodiment of the present invention comprises [A] a polymer and [B] a photosensitizer. The radiation sensitive resin composition of this embodiment has radiation sensitivity.

  The radiation-sensitive resin composition of the embodiment of the present invention includes a radiation-sensitive resin composition for forming a positive pattern in which a portion irradiated with light is dissolved by development, and a negative in which a portion irradiated with light is insolubilized. Any of the radiation sensitive resin compositions for forming the mold pattern can be applied.

  In the radiation-sensitive resin composition for forming a positive pattern, [B-2] photoacid generator can be used as the [B] photosensitive agent which is the [B] component. And the radiation sensitive resin composition for negative pattern formation can use [B-1] radical photopolymerization initiator as [B] photosensitive agent which is a [B] component.

  That is, the radiation-sensitive resin composition of the embodiment of the present invention has at least one selected from [B-1] photoradical polymerization initiator and [B-2] photoacid generator as [B] photosensitizer. Can be used for negative pattern formation or positive pattern formation.

  The radiation-sensitive resin composition of the present embodiment has the radiation sensitivity described above, and can easily form a fine and elaborate pattern by exposure / development utilizing the radiation sensitivity. That is, the radiation sensitive resin composition of this embodiment can form the resin part of the electrode which makes the wall-shaped electrode protrudingly provided on the substrate with high accuracy. And by containing [D] hardening accelerator mentioned later, hardening at lower temperature, such as 200 degrees C or less, is implement | achieved, for example. In addition, it has storage stability and sufficient resolution and radiation sensitivity. Hereinafter, each component of the radiation sensitive resin composition of this embodiment is explained in full detail.

<[A] polymer>
[A] polymer is contained as a resin component contained in the radiation-sensitive resin composition, but considering the patterning of the resin part of this embodiment, an alkali-soluble resin should be selected as the [A] polymer. Is preferred. The alkali-soluble resin is not particularly limited as long as it has a carboxyl group and has alkali developability. And alkali-soluble resin can contain the compound which has an epoxy group.

  Examples of the compound having an epoxy group include compounds having two or more oxiranyl groups, oxetanyl groups, glycidyl groups, and 3,4-epoxycyclohexyl groups in one molecule.

  Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-ethylene glycol) (Epoxycyclohexylmethyl) ether , Ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

  Examples of the compound having two or more oxetanyl groups (1,3-epoxy structure) in one molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1- Ethyl (3-oxetanyl)] methyl} ether, bis (3-ethyl-3-oxetanylmethyl) ether, and the like.

As an epoxy compound which can be contained in other [A] polymer, as a compound having a glycidyl group, for example,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

As these commercial products, for example,
As bisphenol A type epoxy resins, Epicoat (registered trademark) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, Japan Epoxy Resin Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat (registered trademark) 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolak type epoxy resin, Epicoat (registered trademark) 152, 154, 157 S65 (above, Japan Epoxy Resin), EPPN (registered trademark) 201, 202 (above, Nippon Kayaku) etc .;
Examples of cresol novolac type epoxy resins include EOCN (registered trademark) 102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 180S75 (Japan Epoxy Resin Co., Ltd.)
As a polyphenol type epoxy resin, Epicoat (registered trademark) 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite (registered trademark) CY-182, 192, 184 (above, Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206. (Above, U.C.C), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat (registered trademark) 871, 872 (above, Japan Epoxy Resin Co., Ltd.) ), ED-5661, the same 5562 (above, Celanese Coating), etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (Kyoeisha Chemical Co., Ltd.), Epiol (registered trademark) TMP (Nippon Yushi Co., Ltd.), and the like.
Of these, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  And as [A] polymer which a radiation sensitive resin composition contains, resin which has the structural unit which has a carboxyl group, and the structural unit which has a polymeric group, and resin which has alkali developability can be used.

  In that case, the structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. [A] When a polymer contains the said specific structural unit, the cured film which has the outstanding surface curability and deep part curability can be formed, and the resin part of the electrode which makes a wall-shaped electrode can be formed.

  The structural unit having a (meth) acryloyloxy group is, for example, a method of reacting an epoxy group in a copolymer with (meth) acrylic acid, a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the copolymer By a method of reacting (meth) acrylic acid ester having an isocyanate group with a hydroxyl group in a copolymer, a method of reacting (meth) acrylic acid hydroxy ester at an acid anhydride site in the copolymer, etc. Can be formed. Among these, a method of reacting a carboxyl group in the copolymer with a (meth) acrylic ester having an epoxy group is preferable.

  [A] polymer containing the structural unit which has a carboxyl group, and the structural unit which has an epoxy group as a polymeric group is at least 1 sort (s) selected from the group which consists of (A1) unsaturated carboxylic acid and unsaturated carboxylic anhydride. (Hereinafter also referred to as “(A1) compound”) and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”). In this case, the [A] polymer includes a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound. It becomes a copolymer containing.

  This [A] polymer is, for example, copolymerizing a compound (A1) giving a carboxyl group-containing structural unit and a compound (A2) giving an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) may be further added to form a copolymer. Furthermore, in the manufacture of the [A] polymer containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group, together with the compound (A1), the compound (A2) and the compound (A3), (A4 ) Compounds (unsaturated compounds giving structural units other than the structural units derived from the compounds (A1), (A2) and (A3)) can be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) Compound]
Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

  Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like. It is done.

  Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.

  These (A1) compounds may be used alone or in combination of two or more.

  The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-25 mass% are more preferable. (A1) By using the compound in a proportion of 5% by mass to 30% by mass, the solubility of [A] polymer in an alkaline aqueous solution is optimized, and an insulating film having excellent radiation sensitivity is obtained. It becomes suitable for formation of the resin part of the electrode which makes an electrode.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. Epoxy heptyl, methacrylic acid 6,7-epoxy heptyl, α-ethylacrylic acid-6,7-epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and the like are preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the resin part of the electrode.

As an unsaturated compound having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

  Of these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (A2) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-50 mass% are more preferable. (A2) By making the usage-amount of a compound into 5 mass%-60 mass%, the resin part of the electrode which makes the wall-shaped electrode which has the outstanding sclerosis | hardenability etc. can be formed.

[(A3) Compound]
Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.

  Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

  Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.

  Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

  As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass based on the sum of the compound (A1), the compound (A2) and the compound (A3) (optional (A4) compound if necessary). 5 mass%-25 mass% are more preferable.

[(A4) Compound]
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. Examples of (A4) compounds include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
Examples of the cyclic alkyl ester of methacrylic acid include, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^{2, 6} ] decan-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate]. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.

  These (A4) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A4) used is preferably 10% by mass to 80% by mass based on the total of the compound (A1), the compound (A2) and the compound (A4) (and any (A3) compound).

<[B] Photosensitive agent>
[B] Photosensitizer contained in the radiation-sensitive resin composition of the embodiment of the present invention includes a compound capable of initiating polymerization by generating radicals in response to radiation (that is, [B-1] initiation of photoradical polymerization. Agent) or a compound that generates an acid in response to radiation (that is, [B-2] photoacid generator).

  Examples of such [B-1] photoradical polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds may be used alone or in combination of two or more.

  Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -octane-1-one oxime- O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  As the acetophenone compound, an α-aminoketone compound is preferable, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are preferred.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, of which 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Biimidazole is more preferred.

  [B-1] The radical photopolymerization initiator can be used alone or in admixture of two or more as described above. [B-1] The content ratio of the radical photopolymerization initiator is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymer [A]. [B-1] By setting the use ratio of the photo radical polymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition has a high solvent resistance, a high hardness and a low exposure amount. A cured film having high adhesion can be formed, and an electrode resin portion having excellent characteristics can be provided.

  Next, as [B-2] photoacid generator which is [B] photosensitizer of the radiation sensitive resin composition of this embodiment, for example, an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, Examples thereof include diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. These [B-2] photoacid generators may be used alone or in combination of two or more.

  As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (1) is preferable.

In the above formula (1), R ^a is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

The alkyl group represented by R ^a in the above formula (1) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- Examples thereof include alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptylfluoropropyl group, and the like.

As an alicyclic hydrocarbon group represented by said Ra, ^a C4-C12 alicyclic hydrocarbon group is preferable. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ^a is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl Reimido, N-(4-methylphenyl-sulfonyloxy) include diphenyl maleimides and the like.

  [B-2] The photoacid generator is preferably an oxime sulfonate compound, an onium salt, or a sulfonimide compound, and more preferably an oxime sulfonate compound.

  The onium salt is preferably a tetrahydrothiophenium salt or a benzylsulfonium salt, such as 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable. [B-2] By using a photoacid generator as the above compound, the obtained radiation-sensitive resin composition of the present embodiment can improve sensitivity and solubility.

  [B-2] The content of the photoacid generator is preferably 0.1 part by mass to 10 parts by mass and more preferably 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the polymer component [A]. . [B-2] By setting the content of the photoacid generator within the above range, the sensitivity of the radiation-sensitive resin composition of the present embodiment can be optimized, and a cured film having a high surface hardness can be formed. The resin portion of the electrode can be provided.

<[C] polymerizable compound>
The radiation sensitive resin composition of the embodiment of the present invention can contain a [C] polymerizable compound together with the [A] polymer and the [B] photosensitive agent. The radiation-sensitive resin composition of this embodiment selects a [B-1] photoradical polymerization initiator as a [B] photosensitizer, and further contains a [C] polymerizable compound, thereby forming a negative pattern. It can be suitably used as a radiation sensitive resin composition.

  Examples of the [C] polymerizable compound that can be contained in the radiation-sensitive resin composition of the present embodiment include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, and 1,6-hexanediol diene. (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate , Dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate, trimethylol Lopantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri {2- (meth) acryloyloxy In addition to ethyl} phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, etc., a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and a molecule Examples thereof include a urethane (meth) acrylate compound obtained by reacting a compound having one or more hydroxyl groups and having 3 to 5 (meth) acryloyloxy groups.

  [C] A polymeric compound may be used independently and may be used in mixture of 2 or more types.

  As content of the [C] polymeric compound in the radiation sensitive resin composition of embodiment of this invention, 20 mass parts-200 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 40 mass parts- 160 parts by mass is more preferable. [C] By setting the use ratio of the polymerizable compound in the above range, a cured film having excellent adhesion and sufficient hardness even at a low exposure amount can be formed, and a resin part of an electrode excellent in such characteristics can be provided. .

<[D] Curing accelerator>
The radiation-sensitive resin composition of the present embodiment can further contain [D] a curing accelerator in addition to the above-mentioned [A] polymer and [B] photosensitizer. [D] A curing accelerator is a compound that functions to accelerate curing, and is suitable, for example, from the viewpoint of realizing formation of a resin portion of an electrode by low-temperature curing at 200 ° C. or lower.

  [D] Curing accelerators include 4,4′-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, 3-aminobenzene Compounds having an electron-withdrawing group and an amino group in the molecule such as ethyl sulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, Mention may be made of at least one compound selected from the group consisting of tertiary amine compounds, amide compounds, thiol compounds, blocked isocyanate compounds and imidazole ring-containing compounds.

  The radiation-sensitive resin composition of the present embodiment contains [D] a curing accelerator selected from the above-mentioned specific compound group, whereby the curing of the radiation-sensitive resin composition is promoted and the film is cured at low temperature. It is possible to realize the low-temperature formation of the resin part of the electrode, specifically, the formation at 200 ° C. or lower. Furthermore, the storage stability of a radiation sensitive resin composition can also be improved by using the above-mentioned [D] hardening accelerator.

<Other ingredients>
The radiation sensitive resin composition of this embodiment can contain other optional components in addition to the essential components such as the [A] polymer and the [D] curing accelerator.

  The radiation-sensitive resin composition of the present embodiment can contain a surfactant, a storage stabilizer, an adhesion aid, a heat resistance improver, and the like, as other components, as long as the effects of the present invention are not impaired. . Each of these optional components may be used alone or in combination of two or more.

<Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition according to the embodiment of the present invention, if necessary, in addition to the [A] polymer and the [B] photosensitizer, in addition to the [D] curing accelerator, does not impair the desired effect. The other optional components described above are prepared by mixing at a predetermined ratio. The radiation sensitive resin composition of the present embodiment is preferably used in a solution state after being dissolved in an appropriate solvent.

  As a solvent used for the preparation of the radiation sensitive resin composition, [A] polymer and [B] photosensitizer, and [C] polymerizable compound contained as needed are uniformly dissolved or dispersed, Those that do not react with the components are used. The solvent is preferably a solvent that uniformly dissolves or disperses the [D] curing accelerator and other optional components and does not react with each component.

  Examples of the solvent used in the preparation of the radiation sensitive resin composition of the present embodiment include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, and propylene glycol mono Examples include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.

  Although the content of the solvent in the radiation-sensitive resin composition of the present embodiment is not particularly limited, the solvent of the radiation-sensitive resin composition is selected from the viewpoints of applicability and stability of the resulting radiation-sensitive resin composition. The amount of the total concentration of the removed components is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass. When preparing a solution of a radiation sensitive resin composition, actually, a solid content concentration (a component other than the solvent in the composition solution) corresponding to a desired film thickness value or the like is set in the above concentration range. The

  The solution-like composition thus prepared is preferably used for forming a resin part of an electrode that forms a wall-like electrode after filtration using a Millipore filter having a pore diameter of about 0.5 μm.

  Next, the formation method of the resin part of the electrode which makes the wall-shaped electrode using the radiation sensitive resin composition of this embodiment is demonstrated.

<Method for forming resin part of electrode>
In the process of forming the resin part of the electrode forming the wall electrode, the process of forming the resin part on the substrate using the radiation-sensitive resin composition of the present embodiment described above is included as a main process. In this resin part forming step, patterning of a coating film obtained using the radiation-sensitive resin composition of the present embodiment is performed.

In the method for forming the resin part of the electrode forming the wall electrode, it is preferable to include at least the following steps [1] to [4] so that the resin part having a desired shape is formed on the substrate.
[1] A step of forming a coating film of the radiation-sensitive resin composition of the present embodiment on a substrate (hereinafter sometimes referred to as “[1] step”).
[2] A step of irradiating at least a part of the coating film of the radiation-sensitive resin composition formed in the step [1] (hereinafter sometimes referred to as “[2] step”).
[3] A step of developing the coating film irradiated with radiation in the [2] step (hereinafter sometimes referred to as “[3] step”).
[4] A step of heat-curing the coating film developed in the step [3] (hereinafter sometimes referred to as “step [4]”).

  Hereinafter, the steps [1] to [4] will be described.

[[1] Step]
In the production of the resin part of the electrode forming the wall electrode, in the step [1], a coating film of the radiation sensitive resin composition of the present embodiment is formed on the substrate. As a material for this substrate, for example, glass such as soda lime glass or non-alkali glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, polyimide, or the like can be used. Further, the substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  Further, when the liquid crystal display element of the embodiment of the present invention is an active matrix type liquid crystal display element, as a substrate, scanning lines and signal lines are wired in a matrix, and each intersection of the scanning lines and the signal lines. In addition, an active element such as a TFT can be provided, and a substrate formed so that a common line is wired in parallel with the signal line and connected to all pixels can be used.

  Examples of the coating method of the radiation sensitive resin composition of the present embodiment include a spray method, a roll coating method, a spin coating method (sometimes referred to as a spin coating method or a spinner method), a slit coating method (slits). An appropriate method such as a bar coating method or an ink jet coating method may be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

  When forming the coating film of the radiation sensitive resin composition by the coating method, after applying the radiation sensitive resin composition on the substrate, the solvent is preferably evaporated by heating (prebaking) the coating surface. A film can be formed.

  Although the prebaking conditions described above vary depending on the type of each component constituting the radiation-sensitive resin composition, the blending ratio, etc., the temperature is preferably 70 ° C. to 120 ° C., and the time is preferably about 1 minute to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.

[[2] Process]
Next, at least a part of the coating film formed on the substrate in the step [1] is irradiated with radiation. At this time, in order to form the resin part of the electrode at a desired position, a part of the coating film is irradiated with radiation. For example, it can be performed through a photomask having a predetermined pattern.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

  The radiation dose (also referred to as exposure dose) is 10 J / m as a value obtained by measuring the intensity of irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.).²-10,000J / m²100 J / m²~ 5000J / m²Is preferable, 200 J / m²~ 3000J / m ²Is more preferable.

The radiation-sensitive resin composition used for forming the resin portion of the electrode forming the wall electrode is compared with a conventionally known technique, for example, a composition for forming a resin spacer in a liquid crystal display element. High radiation sensitivity. For example, even if the radiation irradiation amount is 700 J / m ² or less, and even 600 J / m ² or less, the resin portion of the electrode can be used as a cured film having a desired film thickness, good shape, excellent adhesion, and high hardness. Can be obtained.

[[3] Process]
Next, the coating film after radiation irradiation in the step [2] is developed to remove unnecessary portions, and a pattern of the resin portion of the electrode having a predetermined shape is obtained.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline, An aqueous solution of an alkaline compound such as 8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, it is possible to use the surfactant alone or in addition to the above-mentioned water-soluble organic solvent and an appropriate amount.

  The developing method may be any of a liquid filling method, a dipping method, a shower method, a spraying method, etc., and the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then air drying is performed with compressed air or compressed nitrogen, whereby a desired pattern of the resin portion of the electrode is obtained.

[[4] Process]
Next, the coating film forming the resin part pattern of the electrode obtained in the step [3] is cured (also referred to as post-baking) by a suitable heating device such as a hot plate or oven. Thereby, the resin part of the electrode which makes the wall-shaped electrode as a cured film is obtained.

  According to the radiation sensitive resin composition of the present embodiment, the curing temperature can be 200 ° C. or lower. Furthermore, an insulating film having sufficient characteristics can be obtained even when the temperature is less than 180 ° C., which is suitable for formation on the resin substrate. Specifically, the curing temperature is preferably 100 ° C. to 200 ° C., and more preferably 150 ° C. to 180 ° C. when trying to achieve both low temperature curing and heat resistance at a high level. For example, the curing time is preferably 5 to 30 minutes on a hot plate, and preferably 30 to 180 minutes in an oven.

  According to the above formation method, it is possible to form a resin portion of an electrode forming a wall electrode on a substrate. The resin part of the electrode forming the wall electrode is preferably a forward tapered shape (a shape in which the width gradually decreases as the cross-sectional shape of the pattern becomes farther from the bottom side), The taper angle (the angle formed by the tangent of the edge of the cross-sectional shape of the pattern and the edge, hereinafter the same) is preferably 80 ° or less, and more preferably 60 ° or less. By setting the taper angle as described above, light leakage can be reduced at the periphery of the wall electrode and at the spacer periphery when the wall electrode is used as a spacer. This is particularly effective when the liquid crystal aligning agent is a photo-aligning agent described later. And as above-mentioned, according to a well-known method, it is possible to provide the electroconductive part which consists of ITO etc. on the resin part, and the electrode which makes a wall-shaped electrode can be formed. And the board | substrate with which the electrode which makes a wall-shaped electrode was formed can be used suitably for the liquid crystal display elements of embodiment of this invention mentioned above.

  Moreover, when providing the liquid crystal display element of this embodiment using the board | substrate with which the electrode which makes | forms a wall-like electrode was formed, it is preferable to provide the alignment film for controlling the orientation of a liquid crystal in the board | substrate. Therefore, next, the alignment film of the embodiment of the present invention that can be provided in the liquid crystal display element of the present embodiment will be described, and in particular, the liquid crystal alignment agent of the embodiment of the present invention that forms the alignment film will be described.

<Liquid crystal aligning agent>
As the liquid crystal aligning agent of the embodiment of the present invention, a known liquid crystal aligning agent can be used. Usually, the coating film formed from the liquid crystal aligning agent is subjected to a rubbing treatment or a photo-alignment treatment by polarized light irradiation to impart liquid crystal alignment ability. As a liquid crystal aligning agent of this invention, it is preferable that it is a liquid crystal aligning agent (henceforth a photo-aligning agent) which expresses liquid crystal aligning ability by performing a photo-alignment process.

  As a photo-alignment agent, it is good also as what contains the polymer which has a photo-alignment structure. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposition type photo-alignment part. Specifically, groups derived from various compounds that exhibit photoalignment by photoisomerization, photodimerization, photolysis, photofleece transition, etc. can be employed as the photoalignment structure, for example, azobenzene or its Azobenzene-containing group containing derivative as basic skeleton, group having cinnamic acid structure containing cinnamic acid or its derivative as basic skeleton, chalcone-containing group containing chalcone or its derivative as basic skeleton, benzophenone or its derivative as basic skeleton A benzophenone-containing group, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a cyclobutane skeleton structure-containing group, an aromatic ester structure-containing group, and the like. Among these, a group having a cinnamic acid structure, a cyclobutane skeleton structure-containing group, and an aromatic ester structure-containing group are preferable. These can be obtained, for example, according to the methods described in JP-A-6-287453, JP-A-9-297313, and Japanese Patent Application No. 2013-60878.

  Examples of the basic skeleton of the above polymer include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, and polyolefin. , Polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane are preferable.

  The photoalignment agent further contains a polymer other than the polymer having the photoalignment structure described above, a curing agent, a curing catalyst, a curing accelerator, an epoxy compound, a functional silane compound, a surfactant, a photosensitizer, and the like. be able to.

<Formation of alignment film>
Next, a method for forming an alignment film according to an embodiment of the present invention will be described.

  For forming the alignment film, for example, the liquid crystal aligning agent of the present embodiment is applied using the substrate on which the electrode forming the wall electrode is formed as described above. Examples of the coating method include a roll coater method, a spinner method, a printing method, and an ink jet method.

  Next, the substrate coated with the liquid crystal aligning agent is pre-baked and then post-baked to form a coating film.

  Prebaking conditions are, for example, a temperature of 40 ° C. to 120 ° C. and a time of 0.1 minutes to 5 minutes. The temperature of the post-bake conditions is preferably 120 ° C to 250 ° C, more preferably 150 ° C to 230 ° C, and further preferably 180 ° C to 230 ° C. Moreover, although the time of post-baking changes with heating apparatuses, such as a hotplate and oven, Usually, it is preferably 5 minutes-200 minutes, More preferably, it is 10 minutes-100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

  The solid content concentration of the liquid crystal aligning agent used when applying the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) takes viscosity, volatility, etc. into consideration However, it is preferably 1 to 10% by weight.

  When a photo-alignment agent is used as the liquid crystal aligning agent, liquid crystal alignment control ability is imparted by irradiating the above-mentioned coating film with linearly polarized light, partially polarized light, or non-polarized radiation. Such irradiation of polarized radiation corresponds to the alignment treatment of the alignment film.

  Here, as the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In particular, it is preferable to use ultraviolet rays including light having a wavelength of 200 nm to 400 nm as radiation. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.

The irradiation dose of radiation, preferably an amount of less than 10000 J / ^{m 2} A at 1 J / ^{m 2} or more, more preferably ^{10J / m 2 ~3000J / m 2} .

  When a liquid crystal aligning agent other than the photo-aligning agent is used as the liquid crystal aligning agent, the post-baked coating film can be used as the alignment film. And, if necessary, the coating film after post-baking is subjected to a rubbing process (rubbing process) with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, etc. to control liquid crystal alignment. It is possible to give the ability.

  The thus-produced substrate on which the electrode forming the wall-like electrode and the alignment film are formed can be suitably used for manufacturing the liquid crystal display element of the embodiment of the present invention.

  For example, the above-described substrate on which the electrode forming the wall electrode and the alignment film are formed is used as the first substrate. Then, an alignment film is formed by the same method as described above, using the second substrate as the second substrate. Then, the first substrate and the second substrate using the sealing material are bonded together and the liquid crystal is sealed, and then the polarizing plate is bonded and the liquid crystal display element according to the embodiment of the present invention is manufactured. be able to.

  When a color filter substrate having a known color filter is used as the second substrate, the liquid crystal display element of the embodiment of the present invention can constitute a color liquid crystal display element.

  As described above, the liquid crystal display element of the embodiment of the present invention having high display efficiency can be manufactured by forming the electrode forming the wall electrode on the substrate and forming the alignment film.

  The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

  The liquid crystal display element of this invention can show high display efficiency by forming a wall-shaped electrode using the radiation sensitive resin composition of this invention, and driving the liquid crystal using the same. Therefore, the liquid crystal display element of the present invention is suitable not only for applications such as large-sized liquid crystal TVs, but also for display elements of portable information devices such as smartphones, which have recently been strongly demanded for low power consumption and high image quality. is there.

DESCRIPTION OF SYMBOLS 1, 101, 201 Liquid crystal display element 2 1st board | substrate 3 2nd board | substrate 4 Liquid crystal 5, 6, 15, 16, 106, 206 Electrode 7 Liquid crystal molecule 9, 10, 210 Resin part 11, 12, 212 Conductive part 17 18 wiring

Claims (8)

A liquid crystal is sandwiched between the first substrate and the second substrate disposed opposite to each other;
A pair of electrodes are disposed on a surface of the first substrate facing the second substrate,
A liquid crystal display element for driving the liquid crystal by an electric field applied between the pair of electrodes,
At least one of the pair of electrodes is in a region including a wall-shaped resin portion projecting from the surface of the first substrate toward the second substrate, and at least a part of a side surface of the resin portion. A wall-like electrode having a conductive portion made of a conductive member provided,
The wall-shaped resin part is
[A] A liquid crystal display element formed using a radiation-sensitive resin composition containing a polymer and [B] a photosensitizer.   The liquid crystal display element according to claim 1, wherein the electric field applied between the pair of electrodes has a component parallel to a surface of the first substrate facing the second substrate. Each of the pair of electrodes is the wall electrode,
The liquid crystal display element according to claim 1, wherein the conductive portions of the pair of wall-shaped electrodes are configured to have portions facing each other.   [B] The liquid crystal display element according to any one of claims 1 to 3, wherein the photosensitive agent contains at least one selected from a photo radical polymerization initiator and a photo acid generator.   The liquid crystal display element according to claim 1, wherein the wall-shaped resin portion has a forward tapered shape in cross section.   The liquid crystal display element according to claim 1, further comprising an alignment film formed using a photoalignment agent. [A] polymer,
It is a radiation sensitive resin composition containing [B-1] radical photopolymerization initiator and [C] polymeric compound, Comprising: The said wall shape of the liquid crystal display element of any one of Claims 1-6 A radiation-sensitive resin composition used for forming the wall-shaped resin portion of an electrode. A radiation-sensitive resin composition comprising [A] a polymer and [B-2] a photoacid generator, wherein the wall-shaped electrode of the liquid crystal display element according to any one of claims 1 to 6 is used. A radiation-sensitive resin composition used for forming the wall-shaped resin portion.

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