WO2015016087A1 - 液晶表示素子および感放射線性樹脂組成物 - Google Patents
液晶表示素子および感放射線性樹脂組成物 Download PDFInfo
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- WO2015016087A1 WO2015016087A1 PCT/JP2014/069192 JP2014069192W WO2015016087A1 WO 2015016087 A1 WO2015016087 A1 WO 2015016087A1 JP 2014069192 W JP2014069192 W JP 2014069192W WO 2015016087 A1 WO2015016087 A1 WO 2015016087A1
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- liquid crystal
- crystal display
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- electrode
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133377—Cells with plural compartments or having plurality of liquid crystal microcells partitioned by walls, e.g. one microcell per pixel
Definitions
- the present invention relates to a liquid crystal display element and a radiation sensitive resin composition.
- the liquid crystal display element is configured by sandwiching liquid crystal between a pair of substrates.
- an orientation change is caused in a liquid crystal by applying an electric field between substrates. Then, light is partially transmitted or shielded corresponding to the change in the orientation of the liquid crystal.
- a liquid crystal display element can display an image using such characteristics.
- the liquid crystal display element has an advantage that it can be made thinner and lighter than a conventional CRT display device.
- the liquid crystal display element at the beginning of development was used as a display element for calculators and clocks centered on character display. After that, the simple matrix method was developed, and the dot matrix display became easy.
- TFT Thin Film Transistor
- LCD Thin Film Transistor
- liquid crystal display elements are widely used as display elements for portable information devices such as smartphones in response to high definition. Recently, in such portable information devices, further improvement in image quality has been demanded, and improvement in display efficiency such as higher definition and corresponding aperture ratio has been strongly demanded.
- a technique described in Patent Document 1 As a technique for improving the display efficiency of a liquid crystal display element, for example, a technique described in Patent Document 1 is known.
- a pair of electrodes is formed at both ends of a pixel region, a video signal is supplied to one electrode (source electrode), and the other electrode (common electrode) serves as a reference. Supply a common signal.
- the liquid crystal display device described in Patent Document 1 generates an electric field (referred to as a transverse electric field) parallel to the main surface of the liquid crystal display panel, and the liquid crystal is a surface parallel to the main surface of the liquid crystal display panel. It is the structure which drives in the inside.
- the source electrode and the common electrode are formed so as to protrude from the main surface of the first substrate toward the second substrate, and the extending direction thereof is the main surface of the first substrate. It is a wall-like electrode shape formed so as to be perpendicular to.
- the liquid crystal display device of Patent Document 1 has the same density of lines of electric force even in a region far from the region close to the first substrate (region close to the second substrate). Like that. And the drive efficiency of a liquid crystal can be improved and display efficiency can be improved.
- Patent Document 2 describes a technique for improving display efficiency by driving a liquid crystal in a plane parallel to the main surface of the liquid crystal display panel, as in Patent Document 1.
- a stepped portion is formed for each region of a large number of pixels.
- the step portion is an insulating film formed in a convex shape at the boundary portion of the pixel.
- a planar electrode made of a conductive material such as ITO (Indium Tin Oxide) is provided on the side wall surface of the stepped portion to form a wall-shaped electrode. That is, in the liquid crystal display device described in Patent Document 2, the wall-like electrode is configured to have a stacked structure of an insulating film and a conductive film that form a stepped portion.
- the wall-like electrode has a laminated structure including an insulating film and a conductive film.
- an insulating film patterned in a convex shape is formed on one of the substrates sandwiching the liquid crystal, and then a patterned conductive film is provided on the side wall surface of the insulating film to form a wall shape.
- a method of forming an electrode is effective.
- the formed wall electrode is for improving display efficiency so as to be effective for high-definition display using a plurality of pixels, and is formed uniformly and simply between the plurality of pixels. Is required. That is, the wall electrode is required to be formed with high uniformity and high productivity. Therefore, the convex insulating film constituting the wall electrode is preferably patterned with high uniformity and formed with high productivity.
- an object of the present invention is to provide a liquid crystal display element having a wall-like electrode and improved display efficiency.
- Another object of the present invention is to provide a radiation sensitive resin composition used for forming a wall electrode of a liquid crystal display element.
- a liquid crystal is sandwiched between a first substrate and a second substrate which are arranged to face each other.
- a pair of electrodes are arranged on the surface of the first substrate facing the second substrate,
- a liquid crystal display element that drives liquid crystal by an electric field applied between a pair of electrodes, At least one of the pair of electrodes is provided in a region including a wall-shaped resin portion projecting from the surface of the first substrate toward the second substrate side and at least a part of the side surface of the resin portion.
- the wall-shaped resin part The present invention relates to a liquid crystal display element formed by using a radiation sensitive resin composition containing [A] a polymer and [B] a photosensitizer.
- the electric field applied between the pair of electrodes preferably has a component parallel to the surface of the first substrate facing the second substrate.
- each of the pair of electrodes is a wall electrode
- the conductive portions of the pair of wall electrodes are preferably configured to have portions facing each other.
- the [B] photosensitizer contains at least one selected from a photo radical polymerization initiator and a photo acid generator.
- the wall-shaped resin portion preferably has a forward tapered shape in cross section.
- an alignment film formed using a photo-alignment agent it is preferable to have an alignment film formed using a photo-alignment agent.
- the second aspect of the present invention is: [A] polymer, [B-1] Radiation-sensitive resin composition containing a radical photopolymerization initiator and [C] a polymerizable compound, the wall-shaped resin of the wall-shaped electrode of the liquid crystal display element according to the first aspect of the present invention It is related with the radiation sensitive resin composition characterized by being used for formation of a part.
- the third aspect of the present invention is: A radiation-sensitive resin composition comprising [A] a polymer and [B-2] a photoacid generator, wherein the wall-shaped resin portion of the wall-shaped electrode of the liquid crystal display element according to the first aspect of the present invention It is related with the radiation sensitive resin composition characterized by being used for formation.
- a liquid crystal display element having a wall-like electrode and improved display efficiency can be obtained.
- a radiation sensitive resin composition used for forming a wall electrode of a liquid crystal display element is obtained.
- a radiation sensitive resin composition used for forming a wall electrode of a liquid crystal display element is obtained.
- radiation irradiated upon exposure includes visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.
- FIG. 1 is a cross-sectional view schematically showing a pixel structure in a first example of a liquid crystal display element of an embodiment of the present invention.
- a liquid crystal display element 1 which is a first example of an embodiment of the present invention sandwiches a liquid crystal 4 between a first substrate 2 and a second substrate 3 which are arranged to face each other.
- This is a liquid crystal display element in which a pair of electrodes 5 and 6 are disposed on the surface facing the substrate 3 and the liquid crystal 4 is driven by an electric field applied between the pair of electrodes 5 and 6.
- the distance between the first substrate 2 and the second substrate 3 is usually 2 ⁇ m or more and 20 ⁇ m or less, that is, 2 ⁇ m to 20 ⁇ m, and these are fixed to each other by a sealing material (not shown) provided in the periphery. Yes.
- the material constituting the first substrate 2 and the second substrate 3 examples include glass such as soda lime glass and non-alkali glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, Examples thereof include polyamideimide and polyimide.
- these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
- the alignment film can be provided on the surfaces of the first substrate 2 and the second substrate 3 that are in contact with the liquid crystal 4 and the surfaces of the electrodes 5 and 6 that will be described later that are in contact with the liquid crystal 4.
- the alignment film can be formed using a polymer material such as polyimide, for example.
- the alignment film is subjected to alignment treatment such as rubbing treatment or photo-alignment treatment, if necessary, so that the liquid crystal 4 sandwiched between the first substrate 2 and the second substrate 3 is uniformly aligned. Can be realized.
- Each of the pair of electrodes 5 and 6 of the liquid crystal display element 1 includes wall-shaped resin portions 9 and 10 protruding from the surface of the first substrate 2 toward the second substrate 3 side, 10 is a wall-like electrode having film-like conductive portions 11 and 12 made of a conductive member provided on the side surface of the plate.
- the conductive portions 11 and 12 are provided in regions including at least a part of the side surfaces of the resin portions 9 and 10 facing each other. That is, the conductive portions 11 and 12 of the electrodes 5 and 6 forming the wall electrode are configured to have portions facing each other with the liquid crystal 4 interposed therebetween.
- the conductive portions 11 and 12 of the electrodes 5 and 6 forming the wall electrode can be provided on the entire surfaces of the resin portions 9 and 10 facing each other as shown in FIG.
- the conductive portions of the electrodes 5 and 6 may be provided only on part of the side surfaces of the resin portions 9 and 10 that face each other.
- the conductive portions 11 and 12 of the electrodes 5 and 6 are similarly formed using a conductive member.
- the conductive members constituting the conductive portions 11 and 12 include transparent conductive materials such as ITO (Indium Tin Oxide), zinc oxide-based AZO (Aluminum doped Zinc Oxide), and GZO (Gallium doped Zinc Oxide). it can.
- the wall-like resin portions 9 and 10 of the electrodes 5 and 6 are similarly made of an insulating resin.
- the electrodes 5 and 6 are formed so as to protrude from the surface of the first substrate 2 toward the second substrate 3 according to the structure of the wall-shaped resin portions 9 and 10, and the extending direction thereof is the first.
- a wall-like electrode is formed so as to be perpendicular to the main surface of the substrate.
- the electric field applied between the pair of electrodes 5 and 6 using the conductive portions 11 and 12 of the electrodes 5 and 6 is a component parallel to the surface of the first substrate 2 facing the second substrate 3.
- the liquid crystal 4 is driven from the initial alignment state by an electric field applied between the pair of electrodes 5 and 6, and the first substrate 2 is in a plane facing the second substrate 3. Change orientation.
- the liquid crystal display element 1 can generate electric lines of force even in a region far from the region close to the first substrate 2 (region close to the second substrate 3).
- the driving efficiency of the liquid crystal 4 can be improved and the display efficiency can be improved.
- FIG. 2 is a plan view schematically showing a pixel structure in the first example of the liquid crystal display element of the embodiment of the present invention.
- the liquid crystal display element 1 which is the first example of the liquid crystal display element of the embodiment of the present invention is illustrated in a rod shape that constitutes the liquid crystal 4 by the action of the alignment film (not shown) described above.
- the liquid crystal molecules 7 are uniformly aligned. That is, in the liquid crystal 4, in the initial alignment state when no voltage is applied between the electrodes 5 and 6, the liquid crystal molecules 7 illustrated in a rod shape with respect to the longitudinal direction of the electrodes 5 and 6 shown in FIG. Are uniformly oriented to form an angle of More specifically, the above-described electric field formation direction formed between the electrodes 5 and 6 when a voltage is applied between the electrodes 5 and 6 (in FIG. 2, the electric field direction is indicated by an arrow. The same applies to FIG. 4), and the liquid crystal 4 is uniformly aligned so that the angle formed by the major axis (optical axis) direction of the liquid crystal molecules 7 is 45 degrees or more and less than 90 degrees.
- FIG. 3 is a cross-sectional view schematically showing a pixel structure when an electric field is applied in the first example of the liquid crystal display element of the embodiment of the present invention.
- FIG. 4 is a plan view schematically showing a pixel structure when an electric field is applied in the first example of the liquid crystal display element of the embodiment of the present invention.
- the liquid crystal 4 when an electric field is applied between the electrodes 5 and 6, the liquid crystal 4 is driven as shown in FIGS.
- the liquid crystal 4 has, for example, positive dielectric anisotropy. Therefore, the orientation of the liquid crystal molecules 7 constituting the liquid crystal 4 of the liquid crystal display element 1 changes so that the major axis direction thereof is parallel to the electric field direction between the electrodes 5 and 6.
- the electric field applied between the pair of electrodes 5 and 6 using the conductive portions 11 and 12 of the electrodes 5 and 6 is, as described above, the second electric field of the first substrate 2. It has a component parallel to the surface facing the substrate 3. Accordingly, in the liquid crystal display element 1, the liquid crystal molecules 7 of the liquid crystal 4 undergo an orientation change that changes the orientation angle within the plane of the first substrate 2 facing the second substrate 3.
- the liquid crystal display element 1 of the present embodiment capable of driving the liquid crystal 4 described above is polarized on the surface opposite to the side in contact with the liquid crystal 4 in each of the first substrate 2 and the second substrate 3.
- a plate (not shown) can be provided.
- the liquid crystal display element 1 can change the light transmittance by changing the orientation of the liquid crystal molecules 7 of the liquid crystal 4 by applying an electric field by arranging the polarization transmission axes of the pair of polarizing plates at a predetermined angle.
- the liquid crystal display element 1 of the present embodiment can constitute a so-called birefringence mode liquid crystal display element.
- the liquid crystal display element 1 is a polarizing plate whose orientation is changed within the plane by applying an electric field while the major axis (optical axis) direction of the liquid crystal molecules 7 of the liquid crystal 4 is substantially parallel to the substrate surface.
- the light transmittance is changed by changing the angle formed with the axis.
- the liquid crystal display element 1 uses the change in light transmittance due to the application of the electric field for displaying an image.
- the pair of electrodes 5 and 6 to which an electric field is applied are provided so as to protrude from the surface of the first substrate 2 toward the second substrate 3. It is a wall electrode.
- the liquid crystal display element 1 can efficiently form an electric field parallel to the mutually opposing substrate surfaces of the first substrate 2 and the second substrate 3 that sandwich the liquid crystal 4. As a result, the liquid crystal display element 1 of the present embodiment can achieve high display efficiency.
- the liquid crystal display element 1 which is the first example of the liquid crystal display element according to the embodiment of the present invention shown in FIGS. 1 to 4, only one pixel portion is shown, and a pair of electrodes 5 is provided for the one pixel. , 6 are shown.
- the liquid crystal display element 1 which is the first example of the embodiment of the present invention is not limited to such a structure.
- the liquid crystal display element 1 has a plurality of pixels, and a wall-like electrode can be arranged in each pixel.
- the liquid crystal display element 1 which is the 1st example of embodiment of this invention can have a wall-shaped electrode of arrangement different from the electrodes 5 and 6.
- FIG. 5 is a plan view schematically showing another example of the wall-like electrode of the liquid crystal display element according to the embodiment of the present invention.
- FIG. 5 schematically shows the structure of the electrodes 15 and 16 arranged in one pixel portion of the liquid crystal display element 1 (not shown) by a plan view.
- a region between a pair of electrodes 15 and 16 adjacent to each other and adjacent to each other constitutes a subpixel, and a plurality of subpixels constitute one pixel.
- both the electrode 15 and the electrode 16 can be wall electrodes.
- the electrodes 15 and 16 have a wall-shaped resin portion projecting from one substrate surface toward the other substrate side, and conductive portions arranged on both side surfaces of the resin portion. Preferably, it is configured.
- a plurality of electrodes 15 that are wall electrodes are connected to the wiring 17 and arranged in a comb shape.
- a plurality of electrodes 16 as wall electrodes are connected to the wiring 18 and arranged in a similar comb shape.
- positioning is arrange
- each of the plurality of electrodes 15 arranged in a comb shape is arranged so as to face one of the plurality of electrodes 16 arranged in a comb shape, thereby forming an electrode group in the pixel.
- the liquid crystal display element of this embodiment can control the distance between a pair of electrodes to which an electric field is applied independently of the size of the pixel. As a result, the liquid crystal display element of this embodiment can easily apply an electric field to the liquid crystal and can drive the liquid crystal with high efficiency.
- liquid crystal display element 1 which is the first example of the liquid crystal display element of the embodiment of the present invention shown in FIGS. 2 is a wall-like electrode projecting from the surface 2 toward the second substrate 3, and one of the electrodes 5, 6 is a linear electrode formed on the substrate surface of the first substrate 2. be able to.
- FIG. 6 is a cross-sectional view schematically showing a pixel structure in a second example of the liquid crystal display element of the embodiment of the present invention.
- a liquid crystal display element 101 which is a second example of the embodiment of the present invention shown in FIG. 6, is the same as the liquid crystal display element 1 shown in FIGS. It has a structure. Therefore, the same components are denoted by the same reference numerals, and redundant description is omitted.
- the liquid crystal display element 101 which is the 2nd example of embodiment of this invention shown in FIG. 6 has a pair of electrodes 5 and 106 similarly to the liquid crystal display element 1 mentioned above.
- the electrode 5 includes a wall-shaped resin portion 9 projecting from the surface of the first substrate 2 toward the second substrate 3, and a resin.
- a conductive portion 11 made of a film-like conductive member provided on the side surface of the portion 9.
- the electrode 106 is a film-like linear electrode provided on the surface of the first substrate 2.
- the conductive member that can constitute the electrode 106 include transparent conductive materials such as ITO and zinc oxide-based AZO and GZO.
- the liquid crystal molecules 7 of the liquid crystal 4 change in orientation.
- the electric field applied between the pair of electrodes 5 and 106 has a component parallel to the surface of the first substrate 2 facing the second substrate 3. Therefore, in the liquid crystal display element 101, the liquid crystal molecules 7 of the liquid crystal 4 undergo an orientation change that changes the orientation angle within the plane of the first substrate 2 facing the second substrate 3.
- the liquid crystal display element 101 of the present embodiment has a polarizing plate (not shown) on the side opposite to the side in contact with the liquid crystal 4 in each of the first substrate 2 and the second substrate 3. Can be provided.
- the liquid crystal display element 101 of the present embodiment constitutes a birefringence mode liquid crystal display element as in the liquid crystal display element 1 described above.
- the liquid crystal display element 101 changes the orientation in the plane while the major axis (optical axis) direction of the liquid crystal molecules 7 of the liquid crystal 4 is substantially parallel to the substrate surface, and the axis of the polarizing plate set at a predetermined angle.
- the light transmittance is changed by changing the angle formed by.
- the liquid crystal display element 101 can use the change in light transmittance due to the application of the electric field for image display.
- the electrode 5 that forms a wall electrode is arranged at the end of the pixel for one pixel, and the electrode 106 that forms a linear electrode. Can also be placed inside the pixel. In that case, it is preferable to arrange two or more wall-like electrodes 5 at the end of the pixel and to arrange at least one electrode 106 inside the pixel. With such an electrode arrangement structure, an electric field can be applied between each of the electrodes 5 and the electrode 106 in the pixel, and an efficient electric field can be formed in the pixel.
- the liquid crystal display element of the embodiment of the present invention can constitute an active matrix type liquid crystal display element.
- scanning lines (not shown) and signal lines (not shown) are provided on the first substrate 2.
- Each pixel is connected to each intersection of the scanning line and the signal line via an active element (not shown) such as a TFT.
- the scanning line and the signal line are connected to a scanning driving circuit (not shown) and a signal driving circuit (not shown), respectively, and an arbitrary voltage can be applied to each scanning line or signal line.
- the active element is a TFT
- the drain electrode (not shown) of the TFT is connected to the signal line
- the source electrode (not shown) of the TFT is electrically connected to the electrode 6, for example.
- a common line (not shown) is disposed on the first substrate 2 in parallel with the signal line, connected to all pixels, and a common voltage is applied to all pixels from a common voltage generation circuit (not shown). It can be applied. Specifically, the electrode 5 is connected to the common line, and a common voltage is applied to each pixel.
- 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 type liquid crystal display element.
- the upper end portion of the wall-shaped electrode is in contact with the opposing substrate.
- the upper end portions of the electrodes 5 and 6 are configured to be in contact with the surface of the opposing second substrate 3, but such a structure is not essential. If the electrodes 5 and 6 are wall-like electrodes protruding from the surface of the first substrate 2 toward the second substrate 3, their upper end portions do not have to be in contact with the second substrate 3. .
- At least one of the electrode 5 and the electrode 6 may have a structure in which the upper end portion does not contact the surface of the second substrate 3 facing it. That is, in the liquid crystal display element 1, at least one of the electrode 5 and the electrode 6 can be configured by providing a gap between the upper end portion thereof and the second substrate 3 facing the upper end portion.
- FIG. 7 is a cross-sectional view schematically showing a pixel structure in a third example of the liquid crystal display element of the embodiment of the present invention.
- a liquid crystal display element 201 which is a third example of the liquid crystal display element according to the embodiment of the present invention shown in FIG. 7, has the same structure as that of the electrode 206 of the pair of electrodes 5 and 206 to which an electric field is applied. 4 has the same structure as the liquid crystal display element 1. Therefore, the same components as those of the liquid crystal display element 1 are denoted by the same reference numerals, and redundant description is omitted.
- the electrode 206 of the liquid crystal display element 201 includes a wall-shaped resin portion 210 protruding from the surface of the first substrate 2 toward the second substrate 3 side, and a conductive member provided on the side surface of the resin portion 210.
- a wall-like electrode having a film-like conductive portion 212 made of A gap is provided between the upper end portion of the electrode 206 and the second substrate 3 facing the electrode 206.
- liquid crystal display element it is possible to have a structure in which the upper end portions of both of the pair of wall electrodes facing each other do not contact the surface of the facing substrate.
- the liquid crystal display element 1 of FIG. 1 it is possible to have a structure in which the upper ends of both the electrode 5 and the electrode 6 do not come into contact with the surface of the second substrate 3 that is opposed.
- liquid crystal display element 1 when there are a plurality of electrodes 5 and 6, a part of the plurality of electrodes 5 or a part of the plurality of electrodes 6 is formed, and an upper end portion is a surface of the second substrate 3. It is possible to have a structure that does not contact with. Further, a part of each of the plurality of electrodes 5 and the plurality of electrodes 6 may have a structure in which the upper end portion does not contact the surface of the second substrate 3.
- the electrode forming the wall-like electrode provided on the first substrate is opposed.
- the electrode can be used as a gap retaining material (spacer) for maintaining the distance between the substrates.
- the liquid crystal display element 1 shown in FIG. 1 is configured such that the upper end portions of the electrodes 5 and 6 are in contact with the surface of the second substrate 3, and the electrodes 5 and 6 are connected to the first substrate 2 and the second substrate 2. It can be used as a spacer for maintaining the distance between the substrates 3.
- the upper end portion of the electrode 5 is configured to be in contact with the surface of the second substrate 3, and the electrode 5 is connected to the first substrate 2, the second substrate 3, and the like. It can be used as a spacer for maintaining the distance between the substrates.
- a technique of dispersing spherical polymer beads between substrates as a spacer has been used in order to maintain a gap between a pair of substrates arranged so as to sandwich liquid crystal.
- polymer beads are not evenly dispersed on the substrate, and the gap between the substrates may be uneven. Such gap unevenness may cause uneven brightness when displaying an image.
- the electrodes 5 and 6 are used as spacers provided between the first substrate 2 and the second substrate 3 as described above. be able to.
- the electrode 5 can be used as a spacer. Therefore, in the liquid crystal display elements 1 and 201, the occurrence of gap unevenness between the substrates is suppressed, and display defects such as luminance unevenness can be reduced.
- the electrode 206 has an upper end portion that is not in contact with the second substrate 3.
- the electrode 206 is used as a support material for suppressing the recess deformation. Can be used.
- the liquid crystal display element of the embodiment of the present invention described above can efficiently form an electric field parallel to the substrate surface sandwiching the liquid crystal.
- the structure of the electrode forming the wall electrode Is particularly important.
- the electrode of the liquid crystal display element of this embodiment includes at least one of the wall-shaped resin portion projecting from the surface of the first substrate toward the second substrate side and the side surface of the resin portion. And a conductive portion made of a conductive member provided in a region including the portion. And the electrode is provided with the shape according to the structure of a resin part. That is, the electrodes of the liquid crystal display element of the present embodiment are formed so as to protrude from the surface of the first substrate toward the second substrate, and the extending direction thereof is perpendicular to the main surface of the first substrate. And has a wall-like shape.
- the resin portion has a trapezoidal shape or a rectangular shape (rectangle or square).
- the resin portion preferably has a forward tapered shape described later on the first substrate.
- 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.
- the electrode forming the wall electrode has a laminated structure of a resin portion and a conductive portion that is a conductive film.
- the conductive portion can be formed using a known method. That is, after forming the resin portion, a conductive film such as ITO is formed on the resin portion according to a known method. Then, the conductive part can be formed by patterning the conductive film using a known method.
- the resin part constituting the electrode is preferably formed by highly uniform patterning.
- a technique for forming an electrode that is a wall electrode by patterning the resin portion with high sensitivity and high uniformity is particularly important.
- a radiation-sensitive resin composition that is provided on one surface of a pair of substrates that sandwich a liquid crystal and is preferably used to form a resin portion that protrudes toward the opposite substrate side. explain.
- the radiation-sensitive resin composition of the embodiment of the present invention is used for forming the resin portion of the electrode forming the wall electrode.
- the radiation-sensitive resin composition of the embodiment of the present invention contains [A] a polymer and [B] a photosensitizer.
- the radiation sensitive resin composition of this embodiment has radiation sensitivity.
- the radiation-sensitive resin composition of the embodiment of the present invention includes a radiation-sensitive resin composition for forming a positive pattern in which a portion irradiated with light is dissolved by development, and a negative in which a portion irradiated with light is insolubilized. Any of the radiation sensitive resin compositions for forming the mold pattern can be applied.
- [B-2] photoacid generator can be used as the [B] photosensitive agent which is the [B] component.
- [B-1] photo radical polymerization initiator can be used as the [B] photosensitive agent that is the [B] component.
- the radiation-sensitive resin composition of the embodiment of the present invention has at least one selected from [B-1] photoradical polymerization initiator and [B-2] photoacid generator as [B] photosensitizer. Can be used for negative pattern formation or positive pattern formation.
- the radiation-sensitive resin composition of the present embodiment has the above-mentioned radiation sensitivity, and can easily form a fine and elaborate pattern by exposure and development utilizing the radiation sensitivity. That is, the radiation sensitive resin composition of this embodiment can form the resin part of the electrode which makes the wall-shaped electrode protrudingly provided on the substrate with high accuracy. And by containing [D] hardening accelerator mentioned later, hardening at lower temperature, such as 200 degrees C or less, is implement
- [D] hardening accelerator mentioned later hardening at lower temperature, such as 200 degrees C or less, is implement
- it has storage stability and sufficient resolution and radiation sensitivity.
- each component of the radiation sensitive resin composition of this embodiment is explained in full detail.
- [A] polymer is contained as a resin component contained in the radiation-sensitive resin composition, but considering the patterning of the resin part of this embodiment, an alkali-soluble resin should be selected as the [A] polymer. Is preferred.
- the alkali-soluble resin is not particularly limited as long as it has a carboxyl group and has alkali developability. And alkali-soluble resin can contain the compound which has an epoxy group.
- Examples of the compound having an epoxy group include compounds having two or more oxiranyl groups, oxetanyl groups, glycidyl groups, and 3,4-epoxycyclohexyl groups in one molecule.
- Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4 Epoxycyclohexylmethyl) A Le, ethylenebis (3,4-epoxycyclo
- Examples of the compound having two or more oxetanyl groups (1,3-epoxy structure) in one molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis ⁇ [1- Ethyl (3-oxetanyl)] methyl ⁇ ether, bis (3-ethyl-3-oxetanylmethyl) ether, and the like.
- an epoxy compound which can be contained in other [A] polymer as a compound having a glycidyl group, for example, Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether
- aliphatic polyglycidyl ether examples include Epolite 100MF (Kyoeisha Chemical Company), Epiol (registered trademark) TMP (Nippon Yushi Co., Ltd.) and the like. Of these, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.
- the [A] polymer contained in the radiation-sensitive resin composition may be a resin containing a structural unit having a carboxyl group and a structural unit having a polymerizable group, and a resin having alkali developability.
- the structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group.
- the cured film which has the outstanding surface curability and deep part curability can be formed, and the resin part of the electrode which makes a wall-shaped electrode can be formed.
- the structural unit having a (meth) acryloyloxy group is, for example, a method of reacting an epoxy group in a copolymer with (meth) acrylic acid, a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the copolymer
- a method of reacting (meth) acrylic acid ester having an isocyanate group with a hydroxyl group in a copolymer a method of reacting (meth) acrylic acid hydroxy ester at an acid anhydride site in the copolymer, etc. Can be formed.
- a method of reacting a carboxyl group in the copolymer with a (meth) acrylic ester having an epoxy group is preferable.
- [A] polymer containing the structural unit which has a carboxyl group, and the structural unit which has an epoxy group as a polymeric group is at least 1 sort (s) selected from the group which consists of (A1) unsaturated carboxylic acid and unsaturated carboxylic anhydride. (Hereinafter also referred to as “(A1) compound”) and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”).
- the [A] polymer includes a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound. It becomes a copolymer containing.
- This [A] polymer is, for example, copolymerizing a compound (A1) giving a carboxyl group-containing structural unit and a compound (A2) giving an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) may be further added to form a copolymer.
- Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.
- Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
- Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
- anhydrides of unsaturated dicarboxylic acids include the anhydrides of the compounds exemplified as the dicarboxylic acid.
- Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate. It is done.
- acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
- (A1) compounds may be used alone or in admixture of two or more.
- the use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10% by mass to 25% by mass is more preferable.
- (A1) By using the compound in a proportion of 5% by mass to 30% by mass, the solubility of [A] polymer in an alkaline aqueous solution can be optimized, and an insulating film having excellent radiation sensitivity can be obtained. It becomes suitable for formation of the resin part of the electrode which makes an electrode.
- the compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability.
- examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).
- Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid.
- Epoxy heptyl methacrylic acid 6,7-epoxy heptyl, ⁇ -ethylacrylic acid-6,7-epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like.
- glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and the like are preferable from the viewpoints of copolymerization reactivity and solvent resistance of the resin portion of the electrode.
- an unsaturated compound having an oxetanyl group for example, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl)
- (A2) compounds glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (A2) compounds may be used alone or in combination of two or more.
- the proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass% to 50 mass% is more preferable.
- Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
- Examples of the acrylate ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.
- methacrylic acid ester having a hydroxyl group examples include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.
- Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate.
- Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.
- hydroxystyrene As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and ⁇ -methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.
- the proportion of the compound (A3) used is preferably 1% by mass to 30% by mass based on the total of the compound (A1), the compound (A2) and the compound (A3) (optional (A4) compound if necessary). 5% by mass to 25% by mass is more preferable.
- (A4) A compound will not be restrict
- Examples of (A4) compounds include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.
- chain alkyl ester of methacrylic acid examples include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
- cyclic alkyl ester of methacrylic acid examples include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.
- acrylic acid chain alkyl ester examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.
- cyclic alkyl ester of acrylic acid examples include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate].
- methacrylic acid aryl ester examples include phenyl methacrylate and benzyl methacrylate.
- acrylic acid aryl ester examples include phenyl acrylate and benzyl acrylate.
- Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.
- maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
- Examples of the unsaturated aromatic compound include styrene, ⁇ -methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene and the like.
- Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
- Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.
- Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.
- methacrylic acid chain alkyl ester methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable.
- styrene methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.
- the use ratio of the (A4) compound is preferably 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).
- Photosensitive agent contained in the radiation-sensitive resin composition of the embodiment of the present invention includes a compound capable of initiating polymerization by generating radicals in response to radiation (that is, [B-1] initiation of photoradical polymerization. Agent) or a compound that generates an acid in response to radiation (that is, [B-2] photoacid generator).
- Examples of such [B-1] photoradical polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds and the like. These compounds may be used alone or in combination of two or more.
- O-acyloxime compound examples include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -octane-1-one oxime- O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H.
- 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.
- acetophenone compounds include ⁇ -aminoketone compounds and ⁇ -hydroxyketone compounds.
- ⁇ -aminoketone compounds examples include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.
- Examples of the ⁇ -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like.
- the acetophenone compound is preferably an ⁇ -aminoketone compound, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are preferred.
- biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5′-Tetraphenyl-1,2′-biimidazole is preferred, of which 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is more preferred.
- the radical photopolymerization initiator can be used alone or in admixture of two or more as described above.
- the content ratio of the radical photopolymerization initiator is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymer [A].
- the photo-radical polymerization initiator By using the photo-radical polymerization initiator in a proportion of 1 to 40 parts by mass, the radiation-sensitive resin composition has a high solvent resistance, a high hardness, and a low exposure amount. A cured film having high adhesion can be formed, and an electrode resin portion having excellent characteristics can be provided.
- [B-2] photoacid generator that is [B] photosensitizer of the radiation sensitive resin composition of the present embodiment includes, for example, oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, Examples thereof include diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds.
- These [B-2] photoacid generators may be used alone or in combination of two or more.
- oxime sulfonate compound a compound containing an oxime sulfonate group represented by the following formula (1) is preferable.
- R a is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.
- the alkyl group represented by R a in the above formula (1) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.
- the linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent.
- the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- And alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group.
- Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, 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.
- onium salt examples include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and the like.
- sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl).
- the photoacid generator is preferably an oxime sulfonate compound, an onium salt or a sulfonimide compound, more preferably an oxime sulfonate compound.
- the onium salt is preferably a tetrahydrothiophenium salt or a benzylsulfonium salt, and is 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexanium. Fluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable.
- the obtained radiation-sensitive resin composition of the present embodiment can improve sensitivity and solubility.
- the content of the photoacid generator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polymer component [A]. .
- the content of the photoacid generator can be set in the above range, the sensitivity of the radiation-sensitive resin composition of the present embodiment can be optimized, and a cured film having a high surface hardness can be formed.
- the resin portion of the electrode can be provided.
- the radiation sensitive resin composition of the embodiment of the present invention can contain a [C] polymerizable compound together with the [A] polymer and the [B] photosensitive agent.
- the negative pattern formation is performed by selecting [B-1] photoradical polymerization initiator as [B] photosensitizer and further containing [C] polymerizable compound. It can be suitably used as a radiation sensitive resin composition.
- Examples of the [C] polymerizable compound that can be contained in the radiation-sensitive resin composition of the present embodiment include ⁇ -carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, and 1,6-hexanediol diene.
- the polymerizable compound may be used alone 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 preferably 40 parts by mass to 100 parts by mass of the polymer [A]. 160 parts by mass is more preferable.
- [C] By setting the use ratio of the polymerizable compound in the above range, a cured film having excellent adhesion and sufficient hardness even at a low exposure amount can be formed, and a resin part of an electrode excellent in such characteristics can be provided. .
- the radiation-sensitive resin composition of the present embodiment can further contain [D] a curing accelerator in addition to the above-mentioned [A] polymer and [B] photosensitizer.
- a curing accelerator is a compound that functions to accelerate curing, and is suitable, for example, from the viewpoint of realizing formation of a resin portion of an electrode by low-temperature curing at 200 ° C. or lower.
- Curing accelerators include 4,4′-diaminodiphenyl sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, 3-aminobenzene Compounds having an electron-withdrawing group and an amino group in the molecule such as ethyl sulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, Mention may be made of at least one compound selected from the group consisting of tertiary amine compounds, amide compounds, thiol compounds, blocked isocyanate compounds and imidazole ring-containing compounds.
- the radiation-sensitive resin composition of the present embodiment contains [D] a curing accelerator selected from the above-mentioned specific compound group, whereby the curing of the radiation-sensitive resin composition is promoted and the film is cured at low temperature. It is possible to realize the low-temperature formation of the resin part of the electrode, specifically, the formation at 200 ° C. or lower. Furthermore, the storage stability of a radiation sensitive resin composition can also be improved by using the above-mentioned [D] hardening accelerator.
- the radiation sensitive resin composition of this embodiment can contain other optional components in addition to the essential components such as the [A] polymer and the [D] curing accelerator.
- the radiation-sensitive resin composition of the present embodiment can contain a surfactant, a storage stabilizer, an adhesion aid, a heat resistance improver, and the like, as other components, as long as the effects of the present invention are not impaired. .
- a surfactant e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate
- the radiation-sensitive resin composition according to the embodiment of the present invention if necessary, in addition to the [A] polymer and the [B] photosensitizer, in addition to the [D] curing accelerator, does not impair the desired effect.
- the other optional components described above are prepared by mixing at a predetermined ratio.
- the radiation sensitive resin composition of the present embodiment is preferably used in a solution state after being dissolved in an appropriate solvent.
- [A] polymer and [B] photosensitizer, and [C] polymerizable compound contained as needed are uniformly dissolved or dispersed, Those that do not react with the components are used.
- the solvent is preferably a solvent that uniformly dissolves or disperses the [D] curing accelerator and other optional components and does not react with each component.
- Examples of the solvent used in the preparation of the radiation sensitive resin composition of the present embodiment include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, and propylene glycol mono Examples include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.
- the content of the solvent in the radiation-sensitive resin composition of the present embodiment is not particularly limited, the solvent of the radiation-sensitive resin composition is selected from the viewpoints of applicability and stability of the resulting radiation-sensitive resin composition.
- the total concentration of each removed component is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass.
- a solid content concentration (a component other than the solvent in the composition solution) corresponding to a desired film thickness value or the like is set in the above concentration range.
- the solution-like composition thus prepared is preferably used for forming a resin part of an electrode that forms a wall electrode after being filtered using a Millipore filter having a pore diameter of about 0.5 ⁇ m.
- [1] A step of forming a coating film of the radiation-sensitive resin composition of the present embodiment on a substrate (hereinafter sometimes referred to as “[1] step”).
- [2] A step of irradiating at least a part of the coating film of the radiation-sensitive resin composition formed in the step [1] (hereinafter sometimes referred to as “[2] step”).
- [3] A step of developing the coating film irradiated with radiation in the [2] step (hereinafter sometimes referred to as “[3] step”).
- [4] A step of heat-curing the coating film developed in the step [3] (hereinafter sometimes referred to as “step [4]”).
- a coating film of the radiation sensitive resin composition of the present embodiment is formed on the substrate.
- glass such as soda lime glass or non-alkali glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, polyimide, or the like can be used.
- the substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
- the liquid crystal display element of the embodiment of the present invention is an active matrix type liquid crystal display element
- a substrate scanning lines and signal lines are wired in a matrix, and each intersection of the scanning lines and the signal lines.
- an active element such as a TFT can be provided, and a substrate formed so that a common line is wired in parallel with the signal line and connected to all pixels can be used.
- Examples of the coating method of the radiation sensitive resin composition of the present embodiment include a spray method, a roll coating method, a spin coating method (sometimes referred to as a spin coating method or a spinner method), a slit coating method (slits).
- An appropriate method such as a bar coating method or an ink jet coating method may be employed.
- the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.
- the solvent is preferably evaporated by heating (prebaking) the coating surface. A film can be formed.
- the temperature is preferably 70 ° C. to 120 ° C., and the time is preferably about 1 minute to 15 minutes.
- the film thickness after pre-baking of the coating film is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably about 1.0 ⁇ m to 7.0 ⁇ m.
- a part of the coating film formed on the substrate in the step [1] is irradiated with radiation.
- a part of the coating film is irradiated with radiation. For example, it can be performed through a photomask having a predetermined pattern.
- Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable.
- the radiation irradiation amount (also referred to as exposure amount) is a value obtained by measuring the intensity of irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.) of 10 J / m 2 to 10,000 J / can be m 2, preferably 100J / m 2 ⁇ 5000J / m 2, 200J / m 2 ⁇ 3000J / m 2 is more preferable.
- OAI model 356, manufactured by Optical Associates Inc. illuminometer
- the radiation-sensitive resin composition used for forming the resin portion of the electrode forming the wall electrode is compared with a conventionally known technique, for example, a composition for forming a resin spacer in a liquid crystal display element.
- a conventionally known technique for example, a composition for forming a resin spacer in a liquid crystal display element.
- High radiation sensitivity For example, even if the radiation irradiation amount is 700 J / m 2 or less, and even 600 J / m 2 or less, the resin portion of the electrode can be used as a cured film having a desired film thickness, good shape, excellent adhesion, and high hardness. Obtainable.
- Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline, An aqueous solution of an alkaline compound such as 8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, it is possible to use the surfactant alone or in addition to the above-mentioned water-soluble organic solvent and an appropriate amount.
- inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate
- quaternary ammonium salts such as tetramethylammonium hydroxide and t
- the developing method may be any of a liquid piling method, a dipping method, a shower method, a spray method, and the like.
- the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Following the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then air drying with compressed air or compressed nitrogen is performed, whereby a desired pattern of the resin portion of the electrode is obtained.
- the coating film forming the resin part pattern of the electrode obtained in the step [3] is cured (also referred to as post-baking) by a suitable heating device such as a hot plate or oven. Thereby, the resin part of the electrode which makes the wall-shaped electrode as a cured film is obtained.
- the curing temperature can be 200 ° C. or lower. Furthermore, an insulating film having sufficient characteristics can be obtained even when the temperature is less than 180 ° C., which is suitable for formation on the resin substrate.
- the curing temperature is preferably 100 ° C. to 200 ° C., and more preferably 150 ° C. to 180 ° C. in order to achieve both low temperature curing and heat resistance at a high level.
- the curing time is preferably 5 minutes to 30 minutes on a hot plate, and preferably 30 minutes to 180 minutes in an oven.
- the resin part of the electrode forming the wall electrode is preferably a forward tapered shape (a shape in which the width gradually decreases as the cross-sectional shape of the pattern becomes farther from the bottom side),
- the taper angle (the angle formed by the tangent of the edge of the cross-sectional shape of the pattern and the edge, hereinafter the same) is preferably 80 ° or less, and more preferably 60 ° or less.
- the liquid crystal aligning agent is a photo-aligning agent described later.
- the electroconductive part which consists of ITO etc. on the resin part, and the electrode which makes a wall-shaped electrode can be formed.
- substrate with which the electrode which makes a wall-shaped electrode was formed can be used suitably for the liquid crystal display elements of embodiment of this invention mentioned above.
- the liquid crystal display element of this embodiment is provided using a substrate on which an electrode forming a wall electrode is formed, it is preferable to provide an alignment film for controlling the alignment of the liquid crystal on the substrate. Therefore, next, the alignment film of the embodiment of the present invention that can be provided in the liquid crystal display element of the present embodiment will be described, and in particular, the liquid crystal alignment agent of the embodiment of the present invention that forms the alignment film will be described.
- liquid crystal aligning agent of the embodiment of the present invention a known liquid crystal aligning agent can be used.
- the coating film formed from the liquid crystal aligning agent is subjected to a rubbing treatment or a photo-alignment treatment by polarized light irradiation to impart liquid crystal alignment ability.
- a liquid crystal aligning agent of this invention it is preferable that it is a liquid crystal aligning agent (henceforth a photo-aligning agent) which expresses liquid crystal aligning ability by performing a photo-alignment process.
- the photoalignment agent may contain a polymer having a photoalignment structure.
- the photo-alignment structure is a concept including both a photo-alignment group and a decomposition type photo-alignment part. Specifically, groups derived from various compounds that exhibit photoalignment by photoisomerization, photodimerization, photolysis, photofleece transition, etc.
- photoalignment structure for example, azobenzene or its Azobenzene-containing group containing derivative as basic skeleton, group having cinnamic acid structure containing cinnamic acid or its derivative as basic skeleton, chalcone-containing group containing chalcone or its derivative as basic skeleton, benzophenone or its derivative as basic skeleton
- a group having a cinnamic acid structure, a cyclobutane skeleton structure-containing group, and an aromatic ester structure-containing group are preferable. These can be obtained, for example, according to the methods described in JP-A-6-287453, JP-A-9-297313, and Japanese Patent Application No. 2013-60878.
- Examples of the basic skeleton of the above polymer include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, and polyolefin. , Polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane are preferable.
- the photoalignment agent further contains a polymer other than the polymer having the photoalignment structure described above, a curing agent, a curing catalyst, a curing accelerator, an epoxy compound, a functional silane compound, a surfactant, a photosensitizer, and the like. be able to.
- the liquid crystal aligning agent of this embodiment is applied using a substrate on which an electrode forming a wall electrode is formed as described above.
- the coating method include a roll coater method, a spinner method, a printing method, and an ink jet method.
- the substrate coated with the liquid crystal alignment agent is pre-baked, and then post-baked to form a coating film.
- Pre-bake conditions are, for example, a temperature of 40 ° C. to 120 ° C. and a time of 0.1 minutes to 5 minutes.
- the temperature of the post-bake condition is preferably 120 ° C. to 250 ° C., more preferably 150 ° C. to 230 ° C., and further preferably 180 ° C. to 230 ° C.
- the post-baking time varies depending on the heating device such as a hot plate or an oven, but is usually preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes.
- the film thickness of the coating film after post-baking is preferably 0.001 ⁇ m to 1 ⁇ m, more preferably 0.005 ⁇ m to 0.5 ⁇ m.
- the solid content concentration of the liquid crystal aligning agent used when applying the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) takes viscosity, volatility, etc. into consideration However, it is preferably 1 to 10% by weight.
- liquid crystal alignment control ability is imparted by irradiating the above-mentioned coating film with linearly polarized light, partially polarized radiation, or non-polarized radiation. Such irradiation of polarized radiation corresponds to the alignment treatment of the alignment film.
- ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used.
- ultraviolet rays including light having a wavelength of 200 nm to 400 nm as radiation.
- irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go.
- the direction of irradiation needs to be an oblique direction.
- the irradiation dose of radiation preferably an amount of less than 10000 J / m 2 A at 1 J / m 2 or more, more preferably 10J / m 2 ⁇ 3000J / m 2.
- the post-baked coating film can be used as the alignment film.
- the coating film after post-baking is subjected to a rubbing process (rubbing process) with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, etc. to control liquid crystal alignment. It is possible to give the ability.
- the thus-produced substrate on which the electrode forming the wall electrode of this embodiment and the alignment film are formed can be suitably used for the production of the liquid crystal display element of the embodiment of the present invention.
- the above-mentioned substrate on which the electrode forming the wall electrode and the alignment film are formed is used as the first substrate.
- an alignment film is formed by the same method as described above, using the second substrate as the second substrate.
- the first substrate and the second substrate using the sealing material are bonded together and the liquid crystal is sealed, and then the polarizing plate is bonded and the liquid crystal display element according to the embodiment of the present invention is manufactured. be able to.
- the liquid crystal display element of the embodiment of the present invention can constitute a color liquid crystal display element.
- the liquid crystal display element of the embodiment of the present invention having high display efficiency can be manufactured by forming the electrode forming the wall electrode on the substrate and forming the alignment film.
- the liquid crystal display element of the present invention can exhibit high display efficiency by forming a wall-like electrode using the radiation-sensitive resin composition of the present invention and driving a liquid crystal using the electrode. Therefore, the liquid crystal display element of the present invention is suitable not only for applications such as large-sized liquid crystal TVs, but also for display elements of portable information devices such as smartphones, which have recently been strongly demanded for low power consumption and high image quality. is there.
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Abstract
Description
第1の基板の第2の基板と対向する面に一対の電極を配置して、
一対の電極間に印加される電界により液晶を駆動する液晶表示素子であって、
一対の電極の少なくとも一方が、第1の基板の面から第2の基板側に向けて突設された壁状の樹脂部と、その樹脂部の側面の少なくとも一部を含む領域に設けられた導電性部材からなる導電部とを有する壁状電極であり、
壁状の樹脂部が、
[A]重合体、および
[B]感光剤
を含む感放射線性樹脂組成物を用いて形成されることを特徴とする液晶表示素子に関する。
その一対の壁状電極の導電部はそれぞれ、互いに対向する部分を有するように構成されることが好ましい。
[A]重合体、
[B-1]光ラジカル重合開始剤、および
[C]重合性化合物
を含む感放射線性樹脂組成物であって、本発明の第1の態様の液晶表示素子の壁状電極の壁状の樹脂部の形成に用いられることを特徴とする感放射線性樹脂組成物に関する。
[A]重合体、および
[B-2]光酸発生剤
を含む感放射線性樹脂組成物であって、本発明の第1の態様の液晶表示素子の壁状電極の壁状の樹脂部の形成に用いられることを特徴とする感放射線性樹脂組成物に関する。
図1は、本発明の実施形態の液晶表示素子の第1例における画素構造を模式的に示す断面図である。
本発明の実施形態の液晶表示素子の、壁状電極をなす電極の樹脂部の形成には、本発明の実施形態の感放射線性樹脂組成物が用いられる。
感放射線性樹脂組成物に含有される樹脂成分として[A]重合体を含有するが、本実施形態の樹脂部のパターニングを考慮し、[A]重合体としては、アルカリ可溶性樹脂を選択することが好ましい。アルカリ可溶性樹脂は、カルボキシル基を有することで、アルカリ現像性を有する樹脂であれば、特に限定されない。そして、アルカリ可溶性樹脂には、エポキシ基を有する化合物を含有することができる。
ビスフェノールAジグリシジルエーテル、ビスフェノールFジグリシジルエーテル、ビスフェノールSジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテル、水添ビスフェノールFジグリシジルエーテル、水添ビスフェノールADジグリシジルエーテル、臭素化ビスフェノールAジグリシジルエーテル、臭素化ビスフェノールFジグリシジルエーテル、臭素化ビスフェノールSジグリシジルエーテル等のビスフェノール化合物のジグリシジルエーテル;
1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等の多価アルコールのポリグリシジルエーテル;
エチレングリコール、プロピレングリコール、グリセリン等の脂肪族多価アルコールに1種または2種以上のアルキレンオキサイドを付加することにより得られるポリエーテルポリオールのポリグリシジルエーテル;
フェノールノボラック型エポキシ樹脂;
クレゾールノボラック型エポキシ樹脂;
ポリフェノール型エポキシ樹脂;
環状脂肪族エポキシ樹脂;
脂肪族長鎖二塩基酸のジグリシジルエステル;
高級脂肪酸のグリシジルエステル;
エポキシ化大豆油、エポキシ化アマニ油等が挙げられる。
ビスフェノールA型エポキシ樹脂として、エピコート(登録商標)1001、同1002、同1003、同1004、同1007、同1009、同1010、同828(以上、ジャパンエポキシレジン社)等;
ビスフェノールF型エポキシ樹脂として、エピコート(登録商標)807(ジャパンエポキシレジン社)等;
フェノールノボラック型エポキシ樹脂として、エピコート(登録商標)152、同154、同157S65(以上、ジャパンエポキシレジン社)、EPPN(登録商標)201、同202(以上、日本化薬社)等;
クレゾールノボラック型エポキシ樹脂として、EOCN(登録商標)102、同103S、同104S、1020、1025、1027(以上、日本化薬社)、エピコート(登録商標)180S75(ジャパンエポキシレジン社)等;
ポリフェノール型エポキシ樹脂として、エピコート(登録商標)1032H60、同XY-4000(以上、ジャパンエポキシレジン社)等;
環状脂肪族エポキシ樹脂として、CY-175、同177、同179、アラルダイト(登録商標)CY-182、同192、184(以上、チバ・スペシャルティ・ケミカルズ社)、ERL-4234、4299、4221、4206(以上、U.C.C社)、ショーダイン509(昭和電工社)、エピクロン200、同400(以上、大日本インキ社)、エピコート(登録商標)871、同872(以上、ジャパンエポキシレジン社)、ED-5661、同5662(以上、セラニーズコーティング社)等;
脂肪族ポリグリシジルエーテルとしてエポライト100MF(共栄社化学社)、エピオール(登録商標)TMP(日本油脂社)等が挙げられる。
これらのうち、フェノールノボラック型エポキシ樹脂およびポリフェノール型エポキシ樹脂が好ましい。
(A1)化合物としては、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸の無水物、多価カルボン酸のモノ〔(メタ)アクリロイルオキシアルキル〕エステル等が挙げられる。
(A2)化合物は、ラジカル重合性を有するエポキシ基含有不飽和化合物である。エポキシ基としては、オキシラニル基(1,2-エポキシ構造)またはオキセタニル基(1,3-エポキシ構造)等が挙げられる。
3-(アクリロイルオキシメチル)オキセタン、3-(アクリロイルオキシメチル)-2-メチルオキセタン、3-(アクリロイルオキシメチル)-3-エチルオキセタン、3-(アクリロイルオキシメチル)-2-フェニルオキセタン、3-(2-アクリロイルオキシエチル)オキセタン、3-(2-アクリロイルオキシエチル)-2-エチルオキセタン、3-(2-アクリロイルオキシエチル)-3-エチルオキセタン、3-(2-アクリロイルオキシエチル)-2-フェニルオキセタン等のアクリル酸エステル;
3-(メタクリロイルオキシメチル)オキセタン、3-(メタクリロイルオキシメチル)-2-メチルオキセタン、3-(メタクリロイルオキシメチル)-3-エチルオキセタン、3-(メタクリロイルオキシメチル)-2-フェニルオキセタン、3-(2-メタクリロイルオキシエチル)オキセタン、3-(2-メタクリロイルオキシエチル)-2-エチルオキセタン、3-(2-メタクリロイルオキシエチル)-3-エチルオキセタン、3-(2-メタクリロイルオキシエチル)-2-フェニルオキセタン、3-(2-メタクリロイルオキシエチル)-2,2-ジフルオロオキセタン等のメタクリル酸エステル等が挙げられる。
(A3)化合物としては、水酸基を有する(メタ)アクリル酸エステル、フェノール性水酸基を有する(メタ)アクリル酸エステル、ヒドロキシスチレンが挙げられる。
(A4)化合物は、上記の(A1)化合物、(A2)化合物および(A3)化合物以外の不飽和化合物であれば、特に制限されるものではない。(A4)化合物としては、例えば、メタクリル酸鎖状アルキルエステル、メタクリル酸環状アルキルエステル、アクリル酸鎖状アルキルエステル、アクリル酸環状アルキルエステル、メタクリル酸アリールエステル、アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、マレイミド化合物、不飽和芳香族化合物、共役ジエン、テトラヒドロフラン骨格等をもつ不飽和化合物およびその他の不飽和化合物等が挙げられる。
メタクリル酸環状アルキルエステルとしては、例えば、メタクリル酸シクロヘキシル、メタクリル酸2-メチルシクロヘキシル、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イル、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルオキシエチル、メタクリル酸イソボロニル等が挙げられる。
本発明の実施形態の感放射線性樹脂組成物に含有される[B]感光剤としては、放射線に感応してラジカルを発生し重合を開始できる化合物(すなわち、[B-1]光ラジカル重合開始剤)、または、放射線に感応して酸を発生する化合物(すなわち、[B-2]光酸発生剤)を挙げることができる。
本発明の実施形態の感放射線性樹脂組成物は、[A]重合体および[B]感光剤とともに、[C]重合性化合物を含有することができる。本実施形態の感放射線性樹脂組成物は、[B]感光剤として[B-1]光ラジカル重合開始剤を選択し、さらに、[C]重合性化合物を含有させることで、ネガ型パターン形成用の感放射線性樹脂組成物として好適に使用することが可能である。
本実施形態の感放射線性樹脂組成物は、上述した[A]重合体および[B]感光剤等に加え、さらに[D]硬化促進剤を含有することができる。[D]硬化促進剤は、硬化を促進する機能を果たす化合物であり、例えば、200℃以下の低温硬化による電極の樹脂部の形成を実現する点から好適である。
本実施形態の感放射線性樹脂組成物は、[A]重合体等の必須の成分や、[D]硬化促進剤の他、その他の任意成分を含有することができる。
本発明の実施形態の感放射線性樹脂組成物は、[A]重合体および[B]感光剤等に加え、[D]硬化促進剤の他、所期の効果を損なわない範囲で必要に応じて上述したその他の任意成分を所定の割合で混合することにより調製される。本実施形態の感放射線性樹脂組成物は、好ましくは適当な溶媒に溶解されて溶液状態で用いられる。
壁状電極をなす電極の樹脂部の形成工程においては、上述した本実施形態の感放射線性樹脂組成物を用いて基板上に樹脂部を形成する工程が主要な工程として含まれる。この樹脂部の形成工程では、本実施形態の感放射線性樹脂組成物を用いて得られた塗膜のパターニング等が行われる。
ように、少なくとも下記の[1]工程~[4]工程を含むことが好ましい。
[1]本実施形態の感放射線性樹脂組成物の塗膜を基板上に形成する工程(以下、「[1]工程」と称することがある。)
[2][1]工程で形成された感放射線性樹脂組成物の塗膜の少なくとも一部に放射線を照射する工程(以下、「[2]工程」と称することがある。)
[3][2]工程で放射線が照射された塗膜を現像する工程(以下、「[3]工程」と称することがある。)
[4][3]工程で現像された塗膜を加熱硬化する工程(以下、「[4]工程」と称することがある。)
壁状電極をなす電極の樹脂部の製造においては、[1]工程において、本実施形態の感放射線性樹脂組成物の塗膜を基板上に形成する。この基板の材料としては、例えば、ソーダライムガラスや無アルカリガラス等のガラス、シリコン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネート、芳香族ポリアミド、ポリアミドイミド、ポリイミド等を用いることができる。さらに、その基板には、所望によりシランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。
次いで、[1]工程で基板上に形成された塗膜の少なくとも一部に、放射線を照射する。このとき、所望の位置に電極の樹脂部を形成するため、塗膜の一部に放射線を照射するが、例えば、所定のパターンを有するフォトマスクを介して行うことができる。
次に、[2]工程の放射線照射後の塗膜を現像して不要な部分を除去し、所定の形状の電極の樹脂部のパターンを得る。
次いで、[3]工程で得られた、電極の樹脂部のパターンをなす塗膜を、ホットプレート、オーブン等の適当な加熱装置により硬化(ポストベークとも言う。)する。これにより、硬化膜としての壁状電極をなす電極の樹脂部が得られる。
本発明の実施形態の液晶配向剤としては公知の液晶配向剤を使用することができる。通常液晶配向剤から形成された塗膜にラビング処理を施したり、偏光照射による光配向処理を施すことによって液晶配向能を付与する。本発明の液晶配向剤としては、光配向処理を施すことにより液晶配向能を発現する液晶配向剤(以下、光配向剤と言うことがある。)であることが好ましい。
次に、本発明の実施形態の配向膜の形成方法について説明する。
2 第1の基板
3 第2の基板
4 液晶
5、6、15、16、106、206 電極
7 液晶分子
9、10、210 樹脂部
11、12、212 導電部
17、18 配線
Claims (8)
- 対向配置された第1の基板および第2の基板の間に液晶を挟持し、
前記第1の基板の前記第2の基板と対向する面に一対の電極を配置して、
前記一対の電極間に印加される電界により前記液晶を駆動する液晶表示素子であって、
前記一対の電極の少なくとも一方が、前記第1の基板の面から前記第2の基板側に向けて突設された壁状の樹脂部と、該樹脂部の側面の少なくとも一部を含む領域に設けられた導電性部材からなる導電部とを有する壁状電極であり、
前記壁状の樹脂部が、
[A]重合体、および
[B]感光剤
を含む感放射線性樹脂組成物を用いて形成されることを特徴とする液晶表示素子。 - 前記一対の電極間に印加される電界は、前記第1の基板の前記第2の基板に対向する面と平行な成分を有することを特徴とする請求項1に記載の液晶表示素子。
- 前記一対の電極はいずれも前記壁状電極であり、
該一対の壁状電極の導電部はそれぞれ、互いに対向する部分を有するように構成されることを特徴とする請求項1または2に記載の液晶表示素子。 - [B]感光剤が光ラジカル重合開始剤および光酸発生剤のうちから選ばれる少なくとも一方を含むことを特徴とする請求項1~3のいずれか1項に記載の液晶表示素子。
- 前記壁状の樹脂部は断面形状が順テーパー形状であることを特徴とする請求項1~4のいずれか1項に記載の液晶表示素子。
- 光配向剤を用いて形成された配向膜を有することを特徴とする請求項1~5のいずれか1項に記載の液晶表示素子。
- [A]重合体、
[B-1]光ラジカル重合開始剤、および
[C]重合性化合物
を含む感放射線性樹脂組成物であって、請求項1~6のいずれか1項に記載の液晶表示素子の前記壁状電極の前記壁状の樹脂部の形成に用いられることを特徴とする感放射線性樹脂組成物。 - [A]重合体、および
[B-2]光酸発生剤
を含む感放射線性樹脂組成物であって、請求項1~6のいずれか1項に記載の液晶表示素子の前記壁状電極の前記壁状の樹脂部の形成に用いられることを特徴とする感放射線性樹脂組成物。
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JP2021124733A (ja) * | 2020-02-05 | 2021-08-30 | Jsr株式会社 | 液晶表示素子の製造方法、感放射線性組成物、層間絶縁膜及び液晶表示素子 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09258265A (ja) * | 1996-03-19 | 1997-10-03 | Sharp Corp | 液晶表示装置 |
JP2009216728A (ja) * | 2008-03-06 | 2009-09-24 | Sumitomo Chemical Co Ltd | 感光性樹脂組成物、これから得られるパターン、及び表示装置 |
JP2009237412A (ja) * | 2008-03-28 | 2009-10-15 | Sanyo Chem Ind Ltd | 感光性樹脂組成物 |
JP2011065090A (ja) * | 2009-09-18 | 2011-03-31 | Hitachi Displays Ltd | 液晶表示装置 |
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JP3334676B2 (ja) * | 1999-05-26 | 2002-10-15 | 松下電器産業株式会社 | 液晶表示装置 |
JP5944752B2 (ja) * | 2012-06-12 | 2016-07-05 | 株式会社ジャパンディスプレイ | 液晶表示装置及びその製造方法 |
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2014
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- 2014-07-18 KR KR1020167002090A patent/KR20160037910A/ko not_active Application Discontinuation
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09258265A (ja) * | 1996-03-19 | 1997-10-03 | Sharp Corp | 液晶表示装置 |
JP2009216728A (ja) * | 2008-03-06 | 2009-09-24 | Sumitomo Chemical Co Ltd | 感光性樹脂組成物、これから得られるパターン、及び表示装置 |
JP2009237412A (ja) * | 2008-03-28 | 2009-10-15 | Sanyo Chem Ind Ltd | 感光性樹脂組成物 |
JP2011065090A (ja) * | 2009-09-18 | 2011-03-31 | Hitachi Displays Ltd | 液晶表示装置 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021124733A (ja) * | 2020-02-05 | 2021-08-30 | Jsr株式会社 | 液晶表示素子の製造方法、感放射線性組成物、層間絶縁膜及び液晶表示素子 |
JP7298631B2 (ja) | 2020-02-05 | 2023-06-27 | Jsr株式会社 | 液晶表示素子の製造方法、感放射線性組成物、層間絶縁膜及び液晶表示素子 |
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JPWO2015016087A1 (ja) | 2017-03-02 |
KR20160037910A (ko) | 2016-04-06 |
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