TW201506492A - Liquid crystal display element and radiation-sensitive resin composition - Google Patents

Abstract

The invention provides a liquid crystal display element having a wall-like electrode and improving a display efficiency, and provides a radiation-sensitive resin composition for forming the wall-like electrode. A liquid crystal 4 is sandwiched between a first substrate 2 and a second substrate 3 in a liquid crystal display element 1, and electrodes 5, 6 are disposed on the first substrate 2, wherein the liquid crystal 4 is driven by an electric field applied between the electrodes. The electrodes 5, 6 are set to be the wall-like electrode including wall-like resin portions 9, 10 and conductive portions 11, 12. The conductive portions 11, 12 include a conductive component disposed on a side face of the resin portions 9, 10. The wall-like resin portions 9, 10 are formed by using the radiation-sensitive resin composition including [A] a polymer, and [B] a photo-sensitive agent.

Description

Liquid crystal display element and radiation sensitive resin composition

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 a liquid crystal in a pair of substrates. In the liquid crystal display device, the alignment of the liquid crystal is changed by applying an electric field between the substrates. Further, corresponding to the change in the alignment of the liquid crystal, the light is partially transmitted or blocked. The liquid crystal display element can utilize the characteristics to display an image. The liquid crystal display element has an advantage of being thinner or lighter than a conventional cathode ray tube (CRT) type display device.

The original liquid crystal display element was developed as a display element of a calculator or a clock centered on a character display or the like. Then, by the development of the simple matrix method, the dot matrix display becomes easy, and the use is expanded to display elements of a notebook personal computer.

Then, by developing an active matrix type liquid crystal display element using a thin film transistor (TFT) as a semiconductor device, It is possible to achieve good image quality with excellent contrast ratio or response performance, and also to overcome problems such as colorization and viewing angle expansion, and is also used for a monitor of a desktop computer or the like. In recent years, a wider viewing angle, high-speed response of liquid crystals, and improvement in display quality have been realized, and this has been used as a thin display element for televisions.

On the other hand, corresponding to high definition, liquid crystal display elements are widely used for display elements of portable information devices such as smart phones. Further, recently, in these portable information devices, image quality is further improved, and display efficiency such as high definition and an increase in aperture ratio corresponding thereto are strongly demanded.

For example, a technique described in Patent Document 1 is known as a technique for improving the display efficiency of a liquid crystal display device. In the liquid crystal display device described in Patent Document 1, a pair of electrodes are formed at both ends of a pixel region, and an image signal is supplied to one of the electrodes (source electrode), and the other electrode (common electrode) is supplied as a reference. Common signal. Thus, the liquid crystal display device described in Patent Document 1 has a configuration in which an electric field (referred to as a lateral electric field) parallel to the main surface of the liquid crystal display panel is generated, and the liquid crystal is driven in a plane parallel to the main surface of the liquid crystal display panel.

In the liquid crystal display device described in Patent Document 1, the source electrode and the common electrode have a wall-shaped electrode shape, and the wall-shaped electrode shape is formed not only from the main surface of the first substrate but also toward the second substrate, and The extending direction is formed to be perpendicular to the main surface of the first substrate. In the liquid crystal display device of Patent Document 1, the liquid crystal display device of Patent Document 1 has the same density as the power line in the region close to the first substrate and the region away from the first substrate (the region close to the second substrate). . Moreover, the driving efficiency of the liquid crystal can be improved, and the display efficiency can be improved.

In the same manner as in Patent Document 1, the technique of driving liquid crystal in a plane parallel to the main surface of the liquid crystal display panel to improve display efficiency is disclosed. In the liquid crystal display device described in Patent Document 2, a step portion is formed in each of a plurality of pixels. The step portion is an insulating film formed in a convex shape at a boundary portion of the pixel. Further, in the liquid crystal display device described in Patent Document 2, a planar electrode including a conductive material such as indium tin oxide (ITO) is provided on the side wall surface of the step portion to form a wall-shaped electrode. In the liquid crystal display device described in Patent Document 2, the wall-shaped electrode is configured by a laminated structure of an insulating film and a conductive film which constitute a step portion.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-214244

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-220575

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

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

Further, the formed wall electrode is effective for high-definition display using a plurality of pixels, and is used to improve display efficiency and to form a uniform and simple formation between a plurality of pixels. That is, the wall electrode is required to have not only high uniformity but also high productivity. Therefore, the convex insulating film constituting the wall electrode is preferably highly uniformly patterned and formed with high productivity.

Therefore, a technique of patterning a convex insulating film with high uniformity and high sensitivity to form a wall electrode with high efficiency is required. Further, it is required to provide a liquid crystal display element having a wall electrode 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 electrode and improved display efficiency.

Further, it is an object of the invention to provide a radiation sensitive resin composition for forming a wall electrode of a liquid crystal display element.

Other objects and advantages of the present invention will be clarified by the following description.

According to a first aspect of the invention, there is provided a liquid crystal display device in which a liquid crystal is interposed between a first substrate and a second substrate disposed opposite to each other, and a surface of the first substrate facing the second substrate is disposed. a counter electrode, and driving the liquid crystal by an electric field applied between the pair of electrodes; and the liquid crystal display element is characterized in that at least one of the pair of electrodes is a wall electrode, and the wall electrode comprises: a wall a resin portion protruding from a surface of the first substrate toward the second substrate side; and a conductive portion including a conductive member, wherein the conductive member is provided in a region including at least a part of a side surface of the resin portion; Further, the wall-shaped resin portion is formed using a radiation-sensitive resin composition containing the [A] polymer and the [B] sensitizer.

In the first aspect of the invention, it is preferable that the electric field applied between the pair of electrodes has a component parallel to a surface of the first substrate facing the second substrate.

In the first aspect of the invention, it is preferable that each of the pair of electrodes is a wall electrode, and the conductive portions of the pair of wall electrodes are configured to have mutually opposing portions.

In a first aspect of the invention, it is preferred to form a radiation sensitive resin composition comprising a [B] sensitizer, wherein the [B] sensitizer is selected from the group consisting of photoradicals. At least one of a polymerization initiator and a photoacid generator.

In the first aspect of the invention, it is preferable that the cross-sectional shape of the wall-shaped resin portion is a forward tapered shape.

In the first aspect of the invention, it is preferred to have an alignment film formed using a photo-aligning agent.

A second aspect of the present invention relates to a radiation sensitive resin composition comprising: [A] polymer; [B-1] photoradical polymerization initiator; and [C] polymerizable compound; and the radiation sensitive resin composition is characterized by: for forming the first aspect of the invention The wall-shaped resin portion of the wall electrode of the liquid crystal display element.

A third aspect of the invention relates to a radiation sensitive resin composition comprising: [A] a polymer; and [B-2] a photoacid generator; and the radiation sensitive resin composition is characterized in that A wall-shaped resin portion for forming a wall electrode of a liquid crystal display element of the first aspect of the invention.

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

According to the second aspect of the present invention, a radiation-sensitive resin composition for forming a wall electrode of a liquid crystal display element is obtained.

According to the third aspect of the invention, a radiation-sensitive resin composition for forming a wall electrode of a liquid crystal display element is obtained.

1, 101, 201‧‧‧ liquid crystal display elements

2‧‧‧1st substrate

3‧‧‧2nd substrate

4‧‧‧LCD

5, 6, 15, 16, 106, 206‧‧‧ electrodes

7‧‧‧liquid crystal molecules

9, 10, 210‧‧‧ Resin Department

11,12,212‧‧‧Electrical Department

17, 18‧‧‧ wiring

FIG. 1 is a cross-sectional view schematically showing a pixel structure in a first example of a liquid crystal display device according to an embodiment of the present invention.

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

FIG. 3 is a cross-sectional view showing a pixel structure at the time of electric field application in the first example of the liquid crystal display device of the embodiment of the present invention.

FIG. 4 is a plan view showing a pixel structure at the time of electric field application in the first example of the liquid crystal display device of the embodiment of the present invention.

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

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

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.

Hereinafter, embodiments of the present invention will be described using the drawings.

Further, in the present invention, the "radiation" to be irradiated during exposure includes visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

<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 device according to an embodiment of the present invention.

In the liquid crystal display element 1 of the first example of the embodiment of the present invention, the liquid crystal 4 is sandwiched between the first substrate 2 and the second substrate 3 that are opposed to each other, and the first substrate 2 is paired with the second substrate 3. a pair of electrodes 5, 6 are disposed on the facing surface by being applied to The electric field between the pair of electrodes 5 and 6 drives the liquid crystal display element of the liquid crystal 4.

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 intervals are fixed to each other by a sealing material (not shown) provided in the peripheral portion.

Examples of the material constituting the first substrate 2 and the second substrate 3 include glass such as soda lime glass or alkali free glass, bismuth, polyethylene terephthalate, and polyparaphenylene. Butane dicarboxylate, polyether oxime, polycarbonate, aromatic polyamine, polyamidimide, polyimine, and the like. Further, for these substrates, an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition may be performed as needed.

It is preferable to provide an alignment film (not shown) on the opposing surface of each of the first substrate 2 and the second substrate 3. For example, the alignment film may be provided on the surface of the first substrate 2 and the second substrate 3 that is in contact with the liquid crystal 4, and on the surface of the electrodes 5 and 6 that are in contact with the liquid crystal 4, which will be described later. Further, the alignment film can be formed, for example, by using a polymer material such as polyimide. In addition, when necessary, the alignment film can be subjected to an alignment treatment such as a rubbing treatment or a photo-alignment treatment to achieve uniform alignment of the liquid crystal 4 sandwiched between the first substrate 2 and the second substrate 3.

The pair of electrodes 5 and 6 of the liquid crystal display element 1 are wall electrodes, and the wall electrodes include wall-like resin portions 9 and 10 which are protruded from the surface of the first substrate 2 toward the second substrate 3 side; The film-shaped conductive portions 11 and 12 include conductive members provided on the side faces of the resin portions 9 and 10. The conductive portions 11 and 12 are respectively disposed on A region including at least a part of mutually opposing side faces of the resin portions 9, 10. In other words, the conductive portions 11 and 12 of the electrodes 5 and 6 serving as the wall electrodes are sandwiched between the liquid crystals 4 and have mutually opposing portions.

Further, as shown in, for example, FIG. 1 , the conductive portions 11 and 12 of the electrodes 5 and 6 serving as the wall electrodes may be provided on the entire surface of the side faces of the resin portions 9 and 10 facing each other. Further, the conductive portions of the electrodes 5 and 6 may be provided only on a part of the side faces of the resin portions 9 and 10 that face each other.

The conductive portions 11 and 12 of the electrodes 5 and 6 are each formed using a conductive member in the same manner. Examples of the conductive member constituting the conductive portions 11 and 12 include indium tin oxide (ITO), zinc oxide-doped aluminum-doped zinc oxide (AZO), or gallium-doped zinc oxide (gallium doped). Transparent conductive materials such as Zinc Oxide, GZO).

The wall-shaped resin portions 9 and 10 of the electrodes 5 and 6 each contain an insulating resin in the same manner. Further, the electrodes 5 and 6 have a wall-shaped electrode shape, and the wall-shaped electrode shape is formed so as to protrude from the surface of the first substrate 2 toward the second substrate 3 in accordance with the configuration of the wall-shaped resin portions 9 and 10, and The extending direction is formed to be perpendicular to the main surface of the first substrate.

Therefore, the electric fields applied between the pair of electrodes 5 and 6 using the conductive portions 11 and 12 of the electrodes 5 and 6 have a component parallel to the surface of the first substrate 2 opposed to the second substrate 3. The liquid crystal display element 1 drives the liquid crystal 4 from the initial alignment state by the electric field applied between the pair of electrodes 5 and 6, and causes the liquid crystal 4 to be in the plane of the first substrate 2 facing the second substrate 3. Orientation changes.

Further, by providing the wall-shaped electrodes 5 and 6 as described above, the liquid crystal display element 1 is in a region close to the first substrate 2 to a region away from the first substrate 2 (a region close to the second substrate 3). The density of the power lines is also made the same, 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. 2 to 4.

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

As shown in FIG. 2, the liquid crystal display element 1 of the first example of the liquid crystal display device of the embodiment of the present invention constitutes a liquid crystal molecule of a rod shape by the action of the alignment film (not shown). 7 evenly aligned. In other words, in the initial alignment state when the voltage of the liquid crystal 4 is not applied between the counter electrodes 5 and 6, the liquid crystal molecules 7 are shown as rod-shaped in the longitudinal direction of the electrodes 5 and 6 shown in FIG. 2 . Evenly aligned in a manner that forms several angles. More specifically, in the direction in which the electric field is formed between the electrodes 5 and 6 when a voltage is applied between the counter electrodes 5 and 6, (in FIG. 2, the direction of the electric field is indicated by an arrow; the same applies to FIGS. 3 and 4 which will be described later. The liquid crystal 4 is uniformly aligned so that the angle formed by the long 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 showing a pixel structure at the time of electric field application in the first example of the liquid crystal display device of the embodiment of the present invention.

FIG. 4 is a plan view showing a pixel structure at the time of electric field application in the first example of the liquid crystal display device of the embodiment of the present invention.

Further, 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 liquid crystal molecules 7 constituting the liquid crystal 4 of the liquid crystal display element 1 are aligned so that the longitudinal direction thereof is parallel to the direction of the electric field between the electrodes 5 and 6.

At this time, as described above, the electric fields applied to the pair of electrodes 5 and 6 using the conductive portions 11 and 12 of the electrodes 5 and 6 have the electric field opposed to the second substrate 3 of the first substrate 2 as described above. Parallel component of the face. Therefore, in the liquid crystal display element 1, the liquid crystal molecules 7 of the liquid crystal 4 change the alignment of the alignment angle in the plane of the first substrate 2 facing the second substrate 3.

In the liquid crystal display element 1 of the present embodiment, which can drive the liquid crystal 4, the polarizing plate is disposed on the surface opposite to the side contacting the liquid crystal 4 in the first substrate 2 and the second substrate 3 (not shown). ) to set.

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

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 applied by an electric field, and the orientation of the long axis (optical axis) of the liquid crystal molecules 7 of the liquid crystal 4 is substantially parallel to the substrate surface, and the orientation thereof is changed in the plane, and the polarizing plate set to a predetermined angle is changed. The angle formed by the axis changes the light transmittance. Moreover, the liquid crystal display element 1 will be applied by the electric field The change in light transmittance caused by the addition is used for the display of an image.

As described above, the pair of electrodes 5 and 6 to which the electric field is applied to the liquid crystal display element 1 of the present embodiment are all wall electrodes that are protruded from the surface of the first substrate 2 toward the second substrate 3. 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 sandwiching 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 of the first example of the liquid crystal display device of the embodiment of the present invention, only one pixel portion is displayed, and a pair of electrodes 5 are disposed on the one pixel. The structure of 6. 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 configuration. The liquid crystal display element 1 has a plurality of pixels, and a wall-shaped electrode can be disposed on each pixel. Moreover, the liquid crystal display element 1 which is the first example of the embodiment of the present invention may have a wall-shaped electrode which is different from the electrodes 5 and 6.

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

Fig. 5 schematically shows the configuration of the electrodes 15, 16 disposed on one pixel portion of the liquid crystal display element 1 (not shown) by a plan view. In the example shown in FIG. 5, the area between the pair of electrodes 15 and the electrodes 16 which are adjacent to each other and the electrode 16 constitute a sub-pixel, and the plurality of sub-pixels constitute one pixel. At this time, both the electrode 15 and the electrode 16 may be wall electrodes. In this case, the electrodes 15 and 16 preferably include a wall-shaped resin portion that protrudes from one of the substrate faces toward the other substrate side, and the conductive portion is disposed in the Resin department The sides of both.

In another example of the wall electrode of the liquid crystal display device of the present embodiment, as shown in FIG. 5, a plurality of electrodes 15 as wall electrodes are connected to the wiring 17, and are arranged in a comb shape, and the other wiring 18 is provided. A plurality of electrodes 16 as wall electrodes are connected to each other and arranged in the same comb shape. Further, the comb-tooth portions arranged in two comb types are arranged to be engaged with each other, and the electrodes 15 and the electrodes 16 are alternately arranged. In other words, the plurality of electrodes 15 that can be comb-shaped are arranged in such a manner as to face one of the plurality of electrodes 16 arranged in a comb shape, thereby constituting an electrode group in the pixel. Since the wall electrode in the pixel has the above configuration, the liquid crystal display element of the present embodiment can control the distance between the pair of electrodes to which the electric field is applied independently of the size of the pixel. As a result, the liquid crystal display element of the present embodiment facilitates application of an electric field to the liquid crystal, and high-efficiency liquid crystal driving can be performed.

In the liquid crystal display element 1 of the first example of the liquid crystal display device of the embodiment of the present invention, the pair of electrodes 5 and 6 to which an electric field is applied are all oriented from the surface of the first substrate 2 toward the second. The wall electrode is protruded from the substrate 3, but one of the electrodes 5 and 6 may be a linear electrode formed on the substrate surface of the first substrate 2.

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

The liquid crystal display element 101 of the second example of the embodiment of the present invention has the same configuration as that of the liquid crystal display element 1 of FIGS. 1 to 4 except that the configuration of the electrodes 106 in the pair of electrodes 5 and 106 is different. Therefore, the composition of the common The same symbols are denoted and the repeated description is omitted.

The liquid crystal display element 101 of the second example of the embodiment of the present invention shown in FIG. 6 has a pair of electrodes 5 and 106 similarly to the liquid crystal display element 1. Further, among the pair of electrodes 5 and 106 of the liquid crystal display element 101, the electrode 5 includes a wall-shaped resin portion 9 which is protruded from the surface of the first substrate 2 toward the second substrate 3 side, and a conductive portion 11 including A film-shaped conductive member provided on the side surface of the resin portion 9.

On the other hand, in the liquid crystal display element 101, the electrode 106 is a film-shaped linear electrode provided on the surface of the first substrate 2. The conductive member constituting the electrode 106 may be a transparent conductive material such as ITO or a zinc oxide-based AZO or GZO.

Further, in the liquid crystal display element 101, when an electric field is applied between the electrodes 5 and 106, the liquid crystal molecules 7 of the liquid crystal 4 are changed in alignment. 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 change the alignment of the alignment angle in the plane of the first substrate 2 opposed to the second substrate 3.

In the liquid crystal display element 101 of the present embodiment, a polarizing plate (not shown) may be disposed on the first substrate 2 and the second substrate 3 on the side opposite to the side in contact with the liquid crystal 4, in the same manner as the liquid crystal display element 1. Settings.

Therefore, the liquid crystal display element 101 of the present embodiment constitutes a liquid crystal display element of a birefringence mode in the same manner as the liquid crystal display element 1. The liquid crystal display element 101 is applied by an electric field, and the orientation of the long axis (optical axis) of the liquid crystal molecules 7 of the liquid crystal 4 is substantially parallel to the substrate surface, and the orientation is changed in the plane. The light transmittance is changed by an angle with the axis of the polarizing plate set to a predetermined angle. Moreover, the liquid crystal display element 101 can use a change in light transmittance caused by the application of the electric field for display of an image.

Further, in the liquid crystal display element 101 of the second example of the embodiment of the present invention, the electrode 5 serving as the wall electrode may be disposed at the end of the pixel and become a linear electrode with respect to one pixel. The electrode 106 is disposed inside the pixel. In this case, it is preferable to use two or more electrodes 5 as wall electrodes to be disposed at the end of the pixel, and to arrange the inside of the pixel using at least one electrode 106. By providing such an arrangement of the electrodes, an electric field can be applied between the respective electrodes 5 and the electrodes 106 inside the pixels, and an electric field can be efficiently formed in the pixels.

Further, the liquid crystal display element of the embodiment of the present invention can constitute an active matrix type liquid crystal display element. In this case, for example, in the liquid crystal display element 1 of the first example of the liquid crystal display device of the embodiment of the present invention, the wiring (not shown) and the signal line (not shown) are wired on the first substrate 2. Each of the pixels is connected to each other at an 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 respectively connected to a scan driving circuit (not shown) and a signal driving circuit (not shown), and an arbitrary voltage can be applied to each scanning line or signal line. Further, when the active device is a TFT, a germanium electrode (not shown) of the TFT is connected to the signal line, and a source electrode (not shown) of the TFT is electrically connected to the electrode 6, for example.

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

The 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 liquid crystal display element.

Further, in the liquid crystal display device of the embodiment of the present invention, it is not necessary to form the upper end portion of the wall-shaped electrode 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 configuration is not essential. When the electrodes 5 and 6 are wall electrodes protruding from the surface of the first substrate 2 toward the second substrate 3 side, the upper end portions of the electrodes 5 and 6 may not 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 be configured such that the upper end portion does not come into contact with the surface of the second substrate 3 opposed thereto. In other words, in the liquid crystal display device 1, at least one of the electrode 5 and the electrode 6 may be formed by providing a gap between the upper end portion of the electrode 5 and the electrode 6 and the second substrate 3 opposed thereto.

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.

In the liquid crystal display element 201 of the third example of the liquid crystal display device of the embodiment of the present invention, the liquid crystal display element 201 of the pair of electrodes 5 and 206 to which an electric field is applied is different from the liquid crystal of FIGS. 1 to 4 . Display element 1 has the same knot Structure. Therefore, the same components as those of the liquid crystal display element 1 will be denoted by the same reference numerals, and overlapping description will be omitted.

In the liquid crystal display element 201 shown in FIG. 7, the upper end portion of the electrode 206 opposed to the electrode 5 is configured not to be in contact with the second substrate 3. The electrode 206 of the liquid crystal display element 201 is a wall electrode, and the wall electrode includes a wall-shaped resin portion 210 that protrudes from the surface of the first substrate 2 toward the second substrate 3 side, and a film-shaped conductive portion 212. It includes a conductive member provided on the side surface of the resin portion 210. Further, a gap is formed between the upper end portion of the electrode 206 and the second substrate 3 opposed thereto.

Further, in the liquid crystal display device of the embodiment of the present invention, both of the pair of opposed wall electrodes may be configured such that the upper end portion thereof does not contact the surface of the opposing substrate. For example, in the liquid crystal display element 1 of FIG. 1 , the upper end portions of both the electrode 5 and the electrode 6 may not be in contact with the surface of the opposing second substrate 3 .

Further, in the liquid crystal display device 1, when a plurality of the electrodes 5 and 6 are present, a part of the plurality of electrodes 5 or a part of the plurality of electrodes 6 may be an upper end portion not be the same as the second substrate 3. Surface contact structure. Further, in the case where both of the plurality of electrodes 5 and the plurality of electrodes 6 are provided, a part of each of the plurality of electrodes 5 and the plurality of electrodes 6 may be configured such that the upper end portion does not contact the surface of the second substrate 3.

In the liquid crystal display device of the embodiment of the present invention, the electrode serving as the wall electrode on the first substrate and the second substrate sandwiching the liquid crystal is the second substrate facing the second substrate. In the case of a surface contact structure, the electricity can be The pole is utilized as a gap holding material (spacer) for maintaining the distance between the substrates.

For example, in the liquid crystal display element 1 shown in FIG. 1, 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 can be used as the first substrate 2 and the second substrate. 2 spacers for the distance between the substrates between the substrates 3 are utilized.

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

In the conventional liquid crystal display device, in order to maintain a gap between a pair of substrates which are opposed to each other by sandwiching a liquid crystal, a technique in which spherical polymer beads are dispersed as a spacer between the substrates is used. In the case of such a technique, polymer beads are unevenly dispersed on the substrate, and unevenness occurs in the gap between the substrates. Moreover, since such a gap is uneven, there is a case where uneven brightness occurs at the time of image display.

In the liquid crystal display element 1 of the embodiment of the present invention, as described above, the electrodes 5 and 6 can be used as a spacer provided between the first substrate 2 and the second substrate 3 as described above. 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, 201, generation of gap unevenness between the substrates is suppressed, and display defects such as uneven brightness can be reduced.

Further, in the liquid crystal display element 201, the upper end portion of the electrode 206 is not in contact with the second substrate 3. However, for the liquid crystal display element 201, by the user, etc., for example For example, when pressing to recess the second substrate 3 toward the liquid crystal 4 side is applied, the electrode 206 can be used as a supporting material for suppressing deformation of the recess.

In the liquid crystal display device of the embodiment of the present invention described above, an electric field parallel to the substrate surface on which the liquid crystal is sandwiched can be efficiently formed, and in order to achieve the above effect, the structure of the electrode serving as the wall electrode is particularly important.

As described above, the electrode of the liquid crystal display device of the present embodiment includes a wall-shaped resin portion that is protruded from the surface of the first substrate toward the second substrate side, and the conductive portion. The portion includes a conductive member provided in a region including at least a part of a side surface of the resin portion. Further, the electrode has a shape conforming to the structure of the resin portion. In other words, the electrode of the liquid crystal display device of the present embodiment is formed not only from the surface of the first substrate toward the second substrate, but also has a wall shape in which the extending direction thereof is perpendicular to the main surface of the first substrate. shape.

In the electrode which is a wall electrode of the liquid crystal display element of the present embodiment, the resin portion preferably has a trapezoidal cross-sectional shape or a rectangular shape (rectangular or square). In particular, the resin portion preferably has a forward tapered shape to be described later on the first substrate. In addition, 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 device of the present embodiment, the electrode serving as the wall electrode has a laminated structure of a resin portion and a conductive portion as a conductive film.

In the electrode of the liquid crystal display device of the present embodiment, the formation of the conductive portion can be performed by a known method. That is, after the resin portion is formed, it is based on a known method. In the method, a conductive film such as ITO is formed on the resin portion. Further, the conductive film can be patterned by a known method to form a conductive portion.

Therefore, in the liquid crystal display device of the present embodiment, in order to form an electrode serving as a wall electrode with high productivity between a plurality of pixels, the formation of the resin portion becomes important. That is, the resin portion constituting the electrode is preferably formed by highly uniform patterning.

Therefore, in the formation of the wall electrode including the resin portion and the conductive portion, the technique of patterning the resin portion with high sensitivity and high uniformity to form an electrode as a wall electrode is particularly important.

Therefore, the formation of the resin portion of the electrode serving as the wall electrode of the present embodiment will be described in more detail below. In particular, a radiation-sensitive resin composition suitable for forming a resin portion which is provided on a surface of one of a pair of substrates sandwiching a liquid crystal and facing the other substrate facing each other will be described. Side and stand out.

<Inductive Radiation Resin Composition>

In the formation of the resin portion of the electrode forming the wall electrode of the liquid crystal display device of the embodiment of the present invention, the radiation sensitive resin composition of the embodiment of the present invention is used.

The radiation sensitive resin composition of the embodiment of the present invention comprises a [A] polymer and a [B] sensitizer. The radiation sensitive resin composition of the present embodiment has a susceptibility to radiation.

The radiation-sensitive resin composition of the embodiment of the present invention can be applied to a radiation-sensitive resin group for forming a positive pattern which is dissolved by light to be developed by development. The product and the portion of the radiation-sensitive resin composition for forming a negative pattern that is insolubilized by irradiation with light are formed.

As the radiation-sensitive resin composition for positive pattern formation, a [B-2] photoacid generator can be used as the [B] component, that is, the [B] sensitizer. Further, as the radiation-sensitive resin composition for forming a negative pattern, a [B-1] photoradical polymerization initiator can be used as the component [B], that is, [B] a sensitizer.

In other words, at least one of the [B-1] photoradical polymerization initiator and the [B-2] photoacid generator can be used as the [B] sensitizer in the radiation sensitive resin composition of the embodiment of the present invention. It can be used for negative pattern forming purposes or positive pattern forming applications.

The radiation sensitive resin composition of the present embodiment has the above-described sensibility of radiation, and can be easily formed into a fine and delicate pattern by radiation exposure and sensitization. In other words, in the radiation sensitive resin composition of the present embodiment, the resin portion of the electrode on which the wall electrode is formed protruding on the substrate can be formed with high precision. Further, by containing the [D] hardening accelerator described later, curing at a lower temperature such as 200 ° C or lower is achieved. At the same time, it has storage stability, and has sufficient resolution and radiation sensitivity. Hereinafter, each component of the radiation sensitive resin composition of the present embodiment will be described in detail.

<[A]polymer>

Although the [A] polymer is contained as the resin component contained in the radiation sensitive resin composition, in view of the patterning of the resin portion of the present embodiment, the [A] polymer is preferably an alkali-soluble resin. The alkali-soluble resin has a base as long as it has a carboxyl group The developable resin is not particularly limited. Further, the alkali-soluble resin may contain a compound having an epoxy group.

Examples of the compound having an epoxy group include a compound having two or more oxyheteropropyl 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'-epoxycyclohexanecarboxylic acid ester, 2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl Adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4' - Epoxy-6'-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol (3) , 4-epoxycyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), 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 group. Benzene, bis{[1-ethyl(3-oxetanyl)]methyl}ether, bis(3-ethyl-3-oxetanylmethyl)ether, and the like.

Examples of the epoxy compound which may be contained in the other [A] polymer, and examples of the compound having a glycidyl group include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether. Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, a diglycidyl ether of a bisphenol compound such as hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether or brominated bisphenol S diglycidyl ether; 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol II a polyglycidyl ether of a polyhydric alcohol such as a glycidyl ether; a polycondensation of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; Glycerol ether; phenol novolac type epoxy resin; cresol novolak type epoxy resin; polyphenol type epoxy resin; cyclic aliphatic epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid; Glycidyl ester; epoxidized soybean oil, epoxidized linseed oil, and the like.

Such commercially available products include, for example, bisphenol A type epoxy resins: Epikote (registered trademark) 1001, Epikote 1002, Epikote 1003, Eppi Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above, Japan Epoxy Resin Co., Ltd.) ); bisphenol F type epoxy resin can be cited as: Epikote (registered trademark) 807 (Nippon Epoxy Co., Ltd.), etc.; phenol novolac type epoxy resin: Epikote (registered trademark) 152, Epikote 154, Epikote 157S65 (The above, Japan Epoxy Resin Co., Ltd.), EPPN (registered trademark) 201, EPPN 202 (above, Nippon Kayaku Co., Ltd.), etc.; cresol novolac type epoxy resin: EOCN (registered trademark) 102, EOCN 103S, EOCN 104S, EOCN 1020, EOCN 1025, EOCN 1027 (above, Nippon Kayaku Co., Ltd.), Epikote (registered trademark) 180S75 (Japan Epoxy Resin Co., Ltd.), etc.; Epikote (registered trademark) 1032H60, Epikote XY--000 (above, Japan Epoxy Co., Ltd.), etc.; cyclic aliphatic epoxy resin can be listed as: CY-175, CY -177, CY-179, Araldite (registered trademark) CY-182, Araldite 192, 184 (above, Ciba Specialty Chemicals), ERL-4234, 4299 4221, 4206 (above, UCC), Shodine 509 (Showa Denko), Epiclon 200, Epiclon 40 0 (above, Dainippon Ink Co., Ltd.), Epikote (registered trademark) 871, Epikote 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (above) , Celanese Coatings, etc.; aliphatic polyglycidyl ethers can be listed as: Epolite 100MF (Kyoeisha Chemical Co., Ltd.), Epiol (registered trademark) TMP (Japan) Grease Division) and so on.

Among these commercially available products, a phenol novolak type epoxy resin and a polyphenol type epoxy resin are preferable.

In addition, as the [A] polymer contained in the radiation sensitive resin composition, a resin containing a constituent unit having a carboxyl group and a constituent unit having a polymerizable group, and a resin having alkali developability can be used.

In this case, the structural unit having a polymerizable group is preferably at least one constituent unit selected from the group consisting of a structural unit having an epoxy group and a constituent unit having a (meth)acryloxy group. . By including the specific constituent unit in the [A] polymer, a cured film having excellent surface hardenability and deep hardenability can be formed, and a resin portion serving as an electrode of the wall electrode can be formed.

The constituent unit having a (meth) acryloxy group can be formed, for example, by a method of reacting an epoxy group in a copolymer with (meth)acrylic acid, and a carboxyl group in the copolymer and having an epoxy group. a method of reacting a (meth) acrylate, a method of reacting a hydroxyl group in a copolymer with a (meth) acrylate having an isocyanate group, and an acid anhydride moiety in the copolymer and a (meth)acrylic acid hydroxyl group A method in which an ester is subjected to a reaction, and the like. Among these methods, a method of reacting a carboxyl group in the copolymer with a (meth) acrylate having an epoxy group is particularly preferred.

The [A] polymer comprising a structural unit having a carboxyl group and a constituent unit having an epoxy group as a polymerizable group may be at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. (hereinafter also referred to as "(A1) compound"), and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as "(A2) compound") It is synthesized by copolymerization. In this case, the [A] polymer is a copolymer comprising the following constituent unit: a constituent unit formed of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a ring-containing ring. A constituent unit formed by an unsaturated compound of an oxy group.

The [A] polymer can be, for example, a compound (A1) which provides a carboxyl group-containing constituent unit and a (A2) compound which provides an epoxy group-containing constituent unit in the presence of a polymerization initiator in a solvent. Copolymerization to manufacture. Further, (A3) a hydroxyl group-containing unsaturated compound (hereinafter also referred to as "(A3) compound)) which provides a hydroxyl group-containing constituent unit may be further added to form a copolymer. Further, when the [A] polymer comprising a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group is produced, not only the (A1) compound, the (A2) compound, and the (A3) compound may be added. Further, a compound (A4) (an unsaturated compound derived from a constituent unit other than the constituent unit of the (A1) compound, the (A2) compound, and the (A3) compound) is further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) compound]

Examples of the compound (A1) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, and a mono[(meth)acryloxyalkylalkyl]ester of a polyvalent carboxylic acid.

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

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

Examples of the anhydride of the unsaturated dicarboxylic acid include an anhydride of the compound exemplified as the dicarboxylic acid.

The mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid may, for example, be succinic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, phthalic acid mono [2- (Methyl) propylene methoxyethyl] ester and the like.

Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferred, and acrylic acid and methyl groups are more preferable in terms of copolymerization reactivity, solubility in an aqueous alkali solution, and ease of availability. Acrylic acid, maleic anhydride.

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

The ratio of the use of the compound (A1) is preferably from 5% by mass to 30% by mass based on the total of the (A1) compound and the (A2) compound (optional (A3) compound and (A4) compound), more preferably 10% by mass to 25% by mass. By using the ratio of the use of the compound (A1) to 5% by mass to 30% by mass, the solubility of the [A] polymer in an aqueous alkali solution is optimized, and an insulating film excellent in radiation sensitivity is obtained, which is suitable for formation. A resin portion that becomes an electrode of a wall electrode.

[(A2) compound]

The (A2) compound is an epoxy group-containing unsaturated compound having a radical polymerizable property. Examples of the epoxy group include an oxoheteryl 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, and 2-methyl glycidol methacrylate. Ester, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-Ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid 3,4- Epoxycyclohexylmethyl ester and the like. Among these compounds, glycidyl methacrylate, 2-methyl glycidyl methacrylate, and methacrylic acid are preferred from the viewpoints of improvement in copolymerization reactivity and solvent resistance of the resin portion of the electrode. -6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexane methacrylate Ester, 3,4-epoxycyclohexyl acrylate, and the like.

Examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-2-methyloxetane. , 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(2-propene oxime Oxyethyl)oxetane, 3-(2-propenyloxyethyl)-2-ethyloxetane, 3-(2-propenyloxyethyl)-3-B Acrylate such as oxetane, 3-(2-propenyloxyethyl)-2-phenyloxetane; 3-(methacryloxymethyl)oxetane , 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-( Methyl propylene methoxymethyl)-2-phenyl oxetane, 3-(2-methylpropenyloxyethyl) oxetane, 3-(2-methylpropene oxime Benzyl)-2-ethyloxetane, 3-(2-methylpropenyloxyethyl)-3-ethyloxetane, 3-(2-methylpropane Methyl acrylate such as ethionyloxyethyl)-2-phenyloxetane or 3-(2-methylpropenyloxyethyl)-2,2-difluorooxetane .

Among these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-(methacryloxymethyl)-3-ethyloxy is preferred. Heterocyclic butane. These (A2) compounds may be used singly or in combination of two or more.

The ratio of the (A2) compound to be used is preferably from 5% by mass to 60% by mass based on the total of the (A1) compound and the (A2) compound (optional (A3) compound and (A4) compound), more preferably 10% by mass to 50% by mass. By using the ratio of the use of the compound (A2) to 5% by mass to 60% by mass, a resin portion having an electrode which is a wall electrode having excellent curability or the like can be formed.

[(A3) compound]

The (A3) compound may, for example, be a (meth) acrylate having a hydroxyl group, a (meth) acrylate having a phenolic hydroxyl group, or a hydroxystyrene.

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

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

Examples of the acrylate having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. A methacrylate having a phenolic hydroxyl group can be exemplified: 2-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, and the like.

The hydroxystyrene is preferably o-hydroxystyrene, p-hydroxystyrene, or α-methyl-p-hydroxystyrene. These (A3) compounds may be used singly or in combination of two or more.

The ratio of use of the compound (A3) is preferably from 1% by mass to 30% by mass based on the total of the (A1) compound, the (A2) compound, and the (A3) compound (optionally any (A4) compound), more preferably 5 mass% to 25% by mass.

[(A4) compound]

The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the (A1) compound, the (A2) compound, and the (A3) compound. Examples of the (A4) compound include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a chain alkyl acrylate, a cyclic alkyl acrylate, an aryl methacrylate, and an aryl acrylate. An ester, an unsaturated dicarboxylic acid diester, a maleimide compound, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton or the like, and other unsaturated compounds.

Examples of the chain alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, butyl methacrylate, and methacrylic acid. 2-ethylhexyl ester, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-yl methacrylate, Tricyclo [ 0.45.1.0 ^2,6 ] 癸-8-yloxyethyl methacrylate, isodecyl methacrylate, and the like.

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

The cyclic alkyl acrylate may, for example, be cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-yl acrylate, acryl tricyclo[5.2.1.0 ^2,6 ]癸-8-yloxyethyl ester, isodecyl acrylate, and the like.

Examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate.

Examples of the aryl acrylate include phenyl acrylate and benzyl acrylate.

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

Examples of the maleimide compound include N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, and N- (4-hydroxyphenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-butylenedimino-3-methyleneimine Benzoate, N-butanediamine-4-butyleneimine butyrate, N-butylenedimino-6-m-butyleneimine hexanoate, N - Dibutyl imino-3-butanediimide propionate, N-(9-acridinyl) maleimide, and the like.

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

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, and 3-(methyl)propenyloxytetrahydrofuran-2-one. Wait.

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

Among these (A4) compounds, preferred are methacrylic chain alkyl esters, methacrylic cyclic alkyl esters, aryl methacrylates, maleimide compounds, tetrahydrofuran skeletons, and unsaturated groups. An aromatic compound, a cyclic alkyl acrylate. Among these compounds, in terms of copolymerization reactivity and solubility in an aqueous alkali solution, styrene, methyl methacrylate, butyl methacrylate, n-lauryl methacrylate, and the like are particularly preferable. Benzyl methacrylate, tricyclo [5.0.1.02 ^2,6 ] 癸-8-yl methacrylate, p-methoxy styrene, 2-methylcyclohexyl acrylate, N-phenyl cis-butene Yttrium, N-cyclohexylmethyleneimine, tetrahydrofurfuryl methacrylate.

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

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

<[B] sensitizer>

The [B] sensitizer contained in the radiation sensitive resin composition of the embodiment of the present invention may be a compound capable of inducing radiation by inducing radiation to generate a radical (ie, [B-1] photoradical polymerization. A starting agent) or a compound that induces an acid to generate an acid (ie, [B-2] photoacid generator).

Examples of such a [B-1] photoradical polymerization initiator include an O-indenyl hydrazine compound, an acetophenone compound, a biimidazole compound, and the like. These compounds may be used singly or in combination of two or more.

Examples of the O-indenyl hydrazine compound include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzylidene fluorenyl)], and ethyl ketone-1-[9-B -6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(0-ethylindenyl), 1-(9-ethyl-6-benzylidene) -9H-carbazol-3-yl)-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole 3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzylidene)-9H-carbazole-3- Ethyl]-ethane-1-ketooxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoguanidino)-9H-oxime Zyrid-3-yl]-1-(O-ethylindenyl), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)- 9H-carbazol-3-yl]-1-(O-acetylindenyl), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)- 9H-carbazol-3-yl]-1-(O-acetylindenyl), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl -1,3-dioxolyl)methoxybenzylidenyl}-9H-indazol-3-yl]-1-(O-ethylindenyl) and the like.

Among these compounds, preferred is: 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzylidenehydrazine)], ethyl ketone-1-[9-ethyl -6-(2-methylbenzimidyl)-9H-carbazole-3- 1-(O-ethylindenyl), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-carbazole -3-yl]-1-(O-acetylindenyl), or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1, 3-Dioxolyl)methoxybenzylidenyl}-9H-indazol-3-yl]-1-(O-ethylindenyl).

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and 2-dimethylamino group- 2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl) -2-morpholinylpropan-1-one and the like.

The α-hydroxyketone compound may, for example, be 1-phenyl-2-hydroxy-2-methylpropan-1-one or 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

The acetophenone compound is preferably an α-amino ketone compound, particularly preferably: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-( 4-Methylthiophenyl)-2-morpholinylpropan-1-one.

The biimidazole compound is preferably, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-double (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or 2,2'-bis(2,4,6-trichlorobenzene -4,4',5,5'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-Tetraphenyl-1,2'-biimidazole.

[B-1] The photoradical polymerization initiator may be used singly or in combination of two or more kinds as described above. The content ratio of the [B-1] photoradical polymerization initiator is preferably from 1 part by mass to 40 parts by mass, more preferably from 5 parts by mass to 30 parts by mass, per 100 parts by mass of the [A] polymer. When the ratio of use of the [B-1] photoradical polymerization initiator is from 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition can be formed to have high solvent resistance even at a low exposure amount. A cured film having high hardness and high adhesion can provide a resin portion of an electrode having such excellent characteristics.

In addition, the [B-2] photoacid generator which is a [B] photosensitive agent of the radiation sensitive resin composition of the present embodiment may, for example, be an oxime sulfonate compound, a phosphonium salt, a sulfonium imide compound, or a halogen-containing compound. a compound, a diazomethane compound, an anthraquinone compound, a sulfonate compound, a carboxylate compound, or the like. Further, these [B-2] photoacid generators may be used singly or in combination of two or more.

The oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (1).

In the 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, and an aryl group having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, and the aryl group are substituted with a substituent.

The alkyl group represented by R ^a in the 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-2. An alicyclic group or the like containing a bridged cyclic alicyclic group, such as an oxopurpurinyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

The alicyclic hydrocarbon group represented by R ^a is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. 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, 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 diphenylphosphonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazolium salt, and tetrahydrothiophenium salt.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)butaneimine, N-(camphorsulfonyloxy)butadienimide, and N-(4-methylbenzene). Sulfosulfonyloxy)butanediamine, N-(2-trifluoromethylphenylsulfonyloxy)butanediamine, N-(4-fluorophenylsulfonyloxy)butane Imine, N-(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylbenzene Alkyl sulfonyloxy) phthalimide, N-(2-fluorophenylsulfonyloxy) phthalate Amine, N-(trifluoromethylsulfonyloxy)diphenylmethylene iodide, N-(camphorsulfonyloxy)diphenylbutyleneimide, 4-methylbenzene Alkylsulfonyloxy)diphenylbutyleneimine and the like.

[B-2] The photoacid generator is preferably an oxime sulfonate compound, a phosphonium salt or a sulfonium imide compound, more preferably an oxime sulfonate compound.

Further, the onium salt is preferably a tetrahydrothiophene salt or a benzyl phosphonium salt, more preferably 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate, benzyl Further, 4-hydroxyphenylmethylphosphonium hexafluorophosphate, more preferably 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate. The sulfonate compound is preferably a haloalkylsulfonate, more preferably N-hydroxynaphthylimine-triflate. By using the [B-2] photoacid generator as the compound, the radiation sensitive resin composition of the present embodiment obtained can improve sensitivity and solubility.

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

<[C] polymerizable compound>

The radiation sensitive resin composition of the embodiment of the present invention may contain not only the [A] polymer and the [B] sensitizer but also the [C] polymerizable compound. The radiation sensitive resin composition of the present embodiment can be used as a negative pattern formation by selecting [B-1] photoradical polymerization initiator as [B] sensitizer and further containing [C] polymerizable compound. A radiation sensitive resin composition was used.

The [C] polymerizable compound which can be contained in the radiation sensitive resin composition of the present embodiment includes, for example, ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, and 1 ,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, bisphenoxyethanol fluorodi(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, 2-hydroxy-3-( Methyl) propylene methoxy propyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol Tris (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri{2-(methyl) propylene methoxy ethoxylate a phosphate ester, an ethylene oxide-modified dipentaerythritol hexaacrylate, a succinic acid-modified pentaerythritol triacrylate, and the like, and may also be exemplified by having a linear alkyl group and a fat. (meth)acrylic acid obtained by reacting a compound having a ring structure and having two or more isocyanato groups with a compound having one or more hydroxyl groups in the molecule and having three to five (meth) acryloxy groups A urethane compound or the like.

[C] The polymerizable compound may be used singly or in combination of two or more.

The content of the [C] polymerizable compound in the radiation sensitive resin composition of the embodiment of the present invention is preferably 20 parts by mass to 200 parts by mass, and more preferably 40 parts by mass, based on 100 parts by mass of the [A] polymer. 160 parts by mass. When the ratio of use of the [C] polymerizable compound is in the above range, the adhesion is excellent even at a low exposure. A cured film having sufficient hardness can also be formed in an amount, and a resin portion of the electrode having the above-described characteristics can be provided.

<[D] hardening accelerator>

The radiation sensitive resin composition of the present embodiment may further contain a [D] hardening accelerator in addition to the [A] polymer and the [B] sensitizer. [D] The curing accelerator is preferably a compound which exhibits a function of promoting hardening, and for example, a resin portion which forms an electrode by low-temperature curing at 200 ° C or lower is preferable.

The [D] hardening accelerator may be selected from the group consisting of 4,4'-diaminodiphenylanthracene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoro Methyl)benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl a group consisting of a compound having an electron attracting group and an amine group in a molecule such as -4-nitroaniline, a tertiary amine compound, a guanamine compound, a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring. At least one compound.

The radiation sensitive resin composition of the present embodiment accelerates the hardening of the radiation sensitive linear resin composition by containing a [D] hardening accelerator selected from the specific compound group, and can achieve low temperature hardening by the film. Further, the resin portion forming the electrode at a low temperature can be specifically formed at 200 ° C or lower. Further, by using the [D] hardening accelerator, the storage stability of the radiation sensitive resin composition can be improved.

<Other ingredients>

The radiation sensitive resin composition of the present embodiment may contain other optional components in addition to the essential component such as [A] polymer or the [D] curing accelerator.

The radiation sensitive resin composition of the present embodiment may contain, as an additional component, a surfactant, a storage stabilizer, an adhesion aid, a heat resistance improving agent, and the like, as long as the effects of the present invention are not impaired. These optional components may be used singly or in combination of two or more.

<Preparation of a radiation sensitive resin composition>

The radiation sensitive resin composition of the embodiment of the present invention can be produced by the following operations: except for the [A] polymer and the [B] sensitizer, etc., and without the [D] hardening accelerator, without damaging the Within the range in which the effect is desired, the other optional components are mixed at a predetermined ratio as needed. The radiation sensitive resin composition of the present embodiment is preferably used in a solution state by being dissolved in a suitable solvent.

The solvent for preparing the radiation sensitive resin composition can be uniformly dissolved or dispersed by using the [A] polymer and the [B] photosensitive agent, and optionally the [C] polymerizable compound, and does not react with each component. Solvent. Further, the solvent is preferably a solvent which uniformly dissolves or disperses the [D] hardening accelerator or other optional components and does not react with the respective components.

Examples of the solvent for preparing the radiation sensitive resin composition of the present embodiment include an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol monoalkyl ether, and a diethylene glycol dioxane. Alkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester, and the like.

The content of the solvent in the radiation-sensitive resin composition of the present embodiment is not particularly limited, but is preferably a radiation-sensitive resin composition from the viewpoints of applicability, stability, and the like of the obtained radiation-sensitive resin composition. Each of the solvent The total concentration of the components is 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass. In the case of preparing a solution of the radiation sensitive resin composition, the solid content concentration (component other than the solvent in the composition solution) which satisfies the desired film thickness or the like is actually set within the concentration range.

The solution-like composition prepared as described above is preferably a resin portion for forming an electrode serving as a wall electrode after filtration using a millipore filter having a pore diameter of about 0.5 μm.

Next, a method of forming a resin portion of an electrode serving as a wall electrode using the radiation sensitive resin composition of the present embodiment will be described.

<Method of Forming Resin Portion of Electrode>

In the step of forming the resin portion of the electrode forming the wall electrode, the step of forming the resin portion on the substrate using the radiation sensitive resin composition of the present embodiment is included as a main step. In the step of forming the resin portion, patterning or the like of the coating film obtained by using the radiation-sensitive resin composition of the present embodiment is performed.

In the method of forming the resin portion of the electrode of the wall electrode, in order to form the resin portion having a desired shape on the substrate, it is preferable to include at least the following steps [1] to [4].

[1] a step of forming a coating film of the radiation-sensitive resin composition of the present embodiment on a substrate (hereinafter referred to as "[1] step"); [2] sensitizing radiation formed in the step [1] a step of irradiating at least a part of the coating film of the resin composition (hereinafter sometimes referred to as "[2] step)); [3] a step of developing the coating film irradiated with radiation in the step [2] (hereinafter, The time is referred to as "[3] step"); [4] The step of heat-curing the developed coating film in the step [3] (hereinafter sometimes referred to as "[4] step").

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

[[1] Steps]

In the production of the resin portion which is the electrode of the wall electrode, in the step [1], the coating film of the radiation sensitive resin composition of the present embodiment is formed on the substrate. The material of the substrate can be, for example, glass such as soda lime glass or alkali-free glass, bismuth, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, aromatic polyfluorene. Amine, polyamidimide, polyimine, and the like. Further, as the substrate, an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition may be performed in advance.

Further, in the case where the liquid crystal display element of the embodiment of the present invention is an active matrix type liquid crystal display element, a substrate formed by forming a scanning line and a signal line wiring in a matrix shape on the scanning line and the signal line can be used as the substrate. Each of the intersections is provided with an active element such as a TFT, and a common line is wired in parallel with the signal line to be connected to all the pixels.

The coating method of the radiation sensitive resin composition of the present embodiment may be, for example, a spray method, a roll coating method, a spin coating method (also sometimes referred to as a spin coating method or a spinner method), or a slit coating method ( An appropriate method such as a slit die coating method, a bar coating method, or an inkjet coating method may be used. Among these methods, in terms of forming a film having a uniform thickness, a spin coating method or a slit coating method is preferred.

When the coating film of the radiation sensitive resin composition is formed by a coating method, after the radiation sensitive resin composition is applied onto the substrate, it is preferred to heat (pre-bake) the coated surface. The solvent is evaporated to form a coating film.

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

[[2] Steps]

Then, 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 a resin portion of the electrode at a desired position, a part of the coating film is irradiated with radiation, but it may be performed, for example, by a mask having a predetermined pattern.

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

The amount of radiation exposure (also referred to as exposure amount) can be set by using an illuminometer (OAI model 356, manufactured by Optical Associates Inc.) to measure the intensity at the wavelength of 365 nm of the irradiated radiation. ^{10J / m 2 ~ 10,000J / m} 2, preferably ^{100J / m 2 ~ 5000J / m} 2, more preferably ^{200J / m 2 ~ 3000J / m} 2.

The radiation sensitive resin composition for forming the resin portion of the electrode serving as the wall electrode has a high radiation sensitivity as compared with a conventionally known technique such as a composition for forming a resin spacer in the liquid crystal display element. For example, even if the irradiation amount is 700J / m ² or less, and further a thickness of 600J / m ² or less, also may be desired, a good shape, form excellent adhesion and high hardness of the cured film to obtain an electrode Resin department.

[[3] Steps]

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

For the developer to be used for development, for example, an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate, or a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, or choline or 1, can be used. An aqueous solution of a basic compound such as 8-diazabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4.3.0]-5-decene. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be added to the aqueous solution of the basic compound. Further, it is also possible to add only an appropriate amount of the surfactant or to add an appropriate amount of the surfactant while adding the water-soluble organic solvent.

The development method may be any one of a liquid coating method, a dipping method, a shower method, a spray method, and the like, and the development time may be 5 seconds to 300 seconds at normal temperature, and preferably 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, a running water wash is performed for 30 seconds to 90 seconds, and then air-dried by compressed air or compressed nitrogen gas, thereby obtaining a pattern of a resin portion of a desired electrode.

[[4] Steps]

Then, the coating film of the pattern of the resin portion forming the electrode obtained in the step [3] is cured by a suitable heating means such as a hot plate or an oven (also referred to as post-baking). Thereby, the resin portion which is the electrode which becomes a wall electrode of a cured film is obtained.

According to the radiation sensitive resin composition of the present embodiment, the curing temperature can be set to 200 ° C or lower. Further, by forming on the resin substrate, an insulating film having sufficient characteristics can be obtained even at a temperature of preferably 180 ° C or lower. Specifically, it is preferable to set the curing temperature to 100° C. to 200° C., and when it is desired to have low-temperature curing and heat resistance at a high level, it is more preferably 150° C. to 180° C. For example, on the hot plate, the hardening time is preferably set to 5 minutes to 30 minutes, and in the oven, the hardening time is preferably set to 30 minutes to 180 minutes.

According to the above formation method, the resin portion of the electrode serving as the wall electrode can be formed on the substrate. The resin portion of the electrode serving as the wall electrode preferably has a cross-sectional shape of a forward tapered shape (the cross-sectional shape of the pattern is a shape in which the width gradually decreases as it goes away from the bottom edge portion), and more preferably a cross-sectional shape of the cone. The angle (the angle formed by the base of the cross-sectional shape of the pattern and the tangent to the edge portion, the same applies hereinafter) is 80 or less, and particularly preferably 60 or less. By setting the taper angle, light leakage can be reduced in the peripheral portion of the wall electrode and the peripheral portion of the spacer in the case where the wall electrode is used as a spacer. When the photo-aligning agent described later is formed as a liquid crystal alignment agent, the effect is remarkable. Further, as described above, a conductive portion including ITO or the like can be provided on the resin portion in accordance with a known method, and an electrode serving as a wall electrode can be formed. Further, the substrate on which the electrode serving as the wall electrode is formed can be suitably used for the liquid crystal display element of the embodiment of the present invention.

Further, when the liquid crystal display element of the present embodiment is provided using a substrate on which an electrode serving as a wall electrode is formed, it is preferable to provide an alignment film for controlling liquid crystal alignment on the substrate. Therefore, the liquid crystal display which can be provided in the embodiment is The alignment film of the embodiment of the present invention in the element will be described, and in particular, the liquid crystal alignment agent of the embodiment of the present invention which forms the alignment film will be described.

<Liquid alignment agent>

A known liquid crystal alignment agent can be used for the liquid crystal alignment agent of the embodiment of the present invention. The liquid crystal alignment ability is usually imparted by performing a rubbing treatment on a coating film formed of a liquid crystal alignment agent or performing a photoalignment treatment by polarized light irradiation. The liquid crystal alignment agent of the present invention is preferably a liquid crystal alignment agent (hereinafter sometimes referred to as a photoalignment agent) which exhibits liquid crystal alignment ability by performing photoalignment treatment.

The photo-aligning agent can be used as a polymer containing a photo-alignment structure. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposable photo-alignment unit. Specifically, the photo-alignment structure may be a group derived from a plurality of compounds exhibiting photo-alignment by photoisomerization or photodimerization, photolysis, photo-Fries rearrangement, or the like. The group may, for example, be an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, containing chalcone or a derivative containing a chalcone-containing group as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, and a coumarin or a derivative thereof as a basic skeleton a group of a coumarin, a group containing a cyclobutane skeleton structure, a group containing an aromatic ester structure, and the like. Among these groups, a group having a cinnamic acid structure, a group having a cyclobutane skeleton structure, and a group having an aromatic ester structure are preferable. Such a group can be exemplified by, for example, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Obtained by the method described.

The basic skeleton of the polymer may, for example, be polylysine, polyphthalate, polyimide, polyorganosiloxane, poly(meth)acrylate, poly(meth)acrylamide, Polyvinyl ether, polyolefin, etc., preferably poly-proline, polyphthalate, polyimide, polyorganosiloxane.

The photo-aligning agent may further contain: a polymer other than the polymer having a photo-alignment structure, a hardener, a curing catalyst, a hardening accelerator, an epoxy compound, a functional decane compound, a surfactant, and a photosensitizer. Wait.

<Formation of alignment film>

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

For example, a liquid crystal alignment agent of the present embodiment is applied to a substrate on which an electrode serving as a wall electrode is formed as described above to form an alignment film. Examples of the coating method include a roll coater method, a rotator method, a printing method, and an inkjet method.

Then, the substrate coated with the liquid crystal alignment agent is prebaked, and then post-baked, thereby forming a coating film.

Regarding the prebaking conditions, for example, the temperature is from 40 ° C to 120 ° C, and the time is from 0.1 minute to 5 minutes. The post-baking condition temperature is preferably from 120 ° C to 250 ° C, more preferably from 150 ° C to 230 ° C, and particularly preferably from 180 ° C to 230 ° C. Further, the post-baking time varies depending on a heating means such as a hot plate or an oven, and is usually preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 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 of the liquid crystal alignment agent used when coating the liquid crystal alignment agent is concentrated The degree (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably from 1% by weight to 10% by weight.

In the case where a photo-aligning agent is used as the liquid crystal alignment agent, the liquid crystal alignment control ability is imparted by irradiating the coating film with linearly polarized or partially polarized radiation or non-polarized radiation. The irradiation of the polarized radiation corresponds to the alignment treatment of the alignment film.

Here, as the radiation, for example, ultraviolet rays including visible light having a wavelength of 150 nm to 800 nm and visible light rays can be used. It is particularly preferable to use ultraviolet rays containing light having a wavelength of 200 nm to 400 nm as radiation. When the radiation to be used is linearly polarized or partially polarized, the substrate surface may be irradiated from a vertical direction, or may be irradiated from an oblique direction in order to impart a pretilt angle, or the irradiation may be performed in combination. In the case of irradiating non-polarized radiation, the direction of irradiation must be an oblique direction.

Radiation irradiation amount is preferably 1J / m ² or more the amount of 10000J / m ² and less, more preferably ^{10J / m 2 ~ 3000J / m} 2.

When a liquid crystal alignment agent other than the photo-alignment agent is used as the liquid crystal alignment agent, a coating film after post-baking may be used as the alignment film. Further, if necessary, the post-baking coating film may be subjected to treatment (friction treatment) to impart liquid crystal alignment control capability by using a roll wound with a cloth containing fibers such as nylon, crepe, cotton, or the like. Wipe in a certain direction.

The electrode of the present embodiment manufactured as described above is formed as a wall electrode The substrate of the electrode and the alignment film can be suitably used for producing the liquid crystal display element of the embodiment of the present invention.

For example, the substrate on which the electrode serving as the wall electrode and the alignment film are formed is referred to as a first substrate. Further, a substrate disposed opposite to the first substrate is used as the second substrate, and an alignment film is formed in the same manner as described above. In addition, the liquid crystal display element of the embodiment of the present invention can be produced by laminating the first substrate and the second substrate and sealing the liquid crystal, and then bonding the polarizing plate.

Further, when a known color filter substrate having a 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.

In the above manner, an electrode serving as a wall electrode is formed on the substrate to form an alignment film or the like, and a liquid crystal display element of the embodiment of the present invention having high display efficiency can be produced.

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

[Industrial availability]

In the liquid crystal display device of the present invention, a wall-shaped electrode can be formed by using the radiation-sensitive resin composition of the present invention, and driving of a liquid crystal using the same can be performed, thereby exhibiting high display efficiency. Therefore, the liquid crystal display device of the present invention is suitable for applications such as a large-sized liquid crystal TV, and is also suitable for use in a display element of a portable information device such as a smart phone that strongly requires low power consumption and high image quality.

1‧‧‧Liquid display components

2‧‧‧1st substrate

3‧‧‧2nd substrate

4‧‧‧LCD

5, 6‧‧‧ electrodes

7‧‧‧liquid crystal molecules

9, 10‧‧‧ Resin Department

11, 12‧‧‧Electrical Department

Claims (8)

A liquid crystal display device in which a liquid crystal is sandwiched between a first substrate and a second substrate disposed opposite to each other, and a pair of electrodes are disposed on a surface of the first substrate facing the second substrate, and Applying an electric field between the pair of electrodes to drive the liquid crystal; and the liquid crystal display element is characterized in that at least one of the pair of electrodes is a wall electrode, and the wall electrode comprises: a wall resin a portion that protrudes from a surface of the first substrate toward the second substrate side, and a conductive portion that includes a conductive member that is provided in a region including at least a portion of a side surface of the resin portion And the wall-shaped resin portion is formed using a radiation-sensitive resin composition containing the [A] polymer and the [B] sensitizer. The liquid crystal display device according to claim 1, wherein an electric field applied between the pair of electrodes has a component parallel to a surface of the first substrate facing the second substrate. The liquid crystal display device according to claim 1 or 2, wherein the pair of electrodes are the wall electrodes, and the conductive portions of the pair of wall electrodes respectively have portions facing each other. Composition. The liquid crystal display element according to any one of claims 1 to 3, which is formed using a radiation sensitive resin composition containing a [B] sensitizer, [B] The sensitizer is at least one selected from the group consisting of a photoradical polymerization initiator and a photoacid generator. The liquid crystal display device according to any one of the first to fourth aspect, wherein the cross-sectional shape of the wall-shaped resin portion is a forward tapered shape. The liquid crystal display element according to any one of claims 1 to 5, which comprises an alignment film formed using a photoalignment agent. A radiation sensitive resin composition comprising: [A] a polymer; [B-1] a photoradical polymerization initiator; and [C] a polymerizable compound; and the radiation sensitive resin composition is characterized by The wall-shaped resin portion for forming the wall electrode of the liquid crystal display element according to any one of the first to sixth aspects of the invention. A radiation sensitive resin composition comprising: [A] a polymer; and [B-2] a photoacid generator; and the radiation sensitive resin composition is characterized in that it is formed as in the first application patent range The wall-shaped resin portion of the wall electrode of the liquid crystal display element according to any one of the items of the present invention.