JP5594835B2 - Alignment film material and liquid crystal display device - Google Patents

Description

  The present invention relates to an alignment film material to which a photo-alignment method is applied and a liquid crystal display device including an alignment film formed using the alignment film material.

  Normally, the display of a liquid crystal display device changes the alignment direction of the liquid crystal molecules by applying an electric field to the liquid crystal molecules of the liquid crystal layer sandwiched between a pair of substrates, and the resulting change in the optical characteristics of the liquid crystal layer. Done.

  Conventionally, a so-called active drive type liquid crystal display device having a switching element such as a thin film transistor for each pixel is provided with electrodes on each of a pair of substrates sandwiching the liquid crystal layer, and the direction of the electric field applied to the liquid crystal layer is at the substrate interface. The display is represented by a twisted nematic (TN) display method which is set so as to be substantially perpendicular to the liquid crystal and performs display using the optical rotation of liquid crystal molecules constituting the liquid crystal layer. In this TN type liquid crystal display device, a narrow viewing angle is the biggest problem.

  On the other hand, the liquid crystal molecules constituting the liquid crystal layer are rotated in a plane substantially parallel to the substrate so that the electric field generated using the comb electrode formed on one of the pair of substrates has a component substantially parallel to the substrate surface. An IPS system that operates and performs display using the birefringence of a liquid crystal layer is disclosed in the following Patent Document 1, Patent Document 2, and the like. This IPS system has advantages such as a wider viewing angle and lower load capacity than the conventional TN system due to in-plane switching of liquid crystal molecules, and it is promising as a new liquid crystal display device replacing the TN system. In recent years, it has made rapid progress.

  Patent Document 1 listed below describes a liquid crystal display device having a contrast of 320 by forming an alignment film between a spacer bead and a liquid crystal layer using a material that imparts liquid crystal alignment ability by irradiation of polarized light. Patent Document 2 listed below describes a liquid crystal display device having a contrast of 250 by an alignment method in which linearly polarized light is irradiated onto a polymer film.

  An IPS liquid crystal display device (hereinafter referred to as “IPS-TFT-LCD”) having excellent viewing angle characteristics (brightness contrast ratio, gradation / tone inversion) and bright display (hereinafter referred to as “IPS-TFT-LCD”) has a large display area, such as a monitor or a television It is a powerful technology for

  In the liquid crystal display device, an alignment control film having a liquid crystal alignment control ability is formed on the interface between the pair of substrates sandwiching the liquid crystal layer and the liquid crystal layer. However, in order to put IPS-TFT-LCDs compatible with larger screens of 20-inch or larger into the future, it is necessary to develop new structures and processes for large-sized display devices (large panels).

  In particular, in an IPS-TFT-LCD having many step structures on the surface facing the liquid crystal layer, it is difficult to perform uniform alignment treatment over the large screen on the alignment control film. The margin for performing the alignment treatment on the alignment control film is significantly narrower than that of the conventional TN system, particularly the currently mainstream normally open TN system (light display at low voltage, dark display at high voltage). The reason why the margin is narrow is three points described in (1), (2) and (3) below.

(1) In a step structure IPS-TFT-LCD, it is necessary to dispose a large number of elongated electrodes (sometimes referred to as interdigital electrodes) having a width of about several μm in principle. Therefore, a fine step structure is formed.

  The size of the step is determined by the thickness of the electrode and the shape of various films formed thereon, but is usually 10 nm or more. In the high transmittance pixel structure, the inorganic insulating film is formed thick, and the unevenness below the inorganic insulating film is flattened to some extent.

  Therefore, the step of the alignment control film having a high transmittance pixel structure is mainly caused by the electrode on the organic insulating film. An alignment control film (also referred to as an alignment film) made of a polymer film such as polyimide is formed on the uppermost layer of these films.

  In the conventional mass production technique, the alignment control film is rubbed to give liquid crystal alignment ability (initial alignment). On the other hand, the rubbing cloth is formed by bundling thin fibers having a thickness of about 10 to 30 μm, and each of these thin fibers substantially has a certain direction in a local portion of the alignment film. A treatment for imparting liquid crystal alignment ability is performed by applying a shearing force of.

  As fibers, there are microfibers of several microns, but for rubbing, rigidity is required to give a certain amount of friction, so those using such ultrafine fibers have been put to practical use. Absent.

  Since the electrode spacing in the IPS system is about 10 to 30 μm, which is the same as the diameter of the fiber, rubbing in the vicinity of the step is not sufficient, and the orientation tends to be disturbed. This disturbance in orientation causes an increase in black level and a decrease in image quality such as a decrease in contrast ratio and nonuniform luminance.

(2) Orientation angle In the IPS-TFT-LCD, the initial orientation direction must be set by shifting the initial orientation direction by a certain angle or more from the direction in which the electrode extends in principle or the direction perpendicular thereto. Here, the electrode refers to a signal wiring electrode, a common electrode in a pixel, and a pixel electrode.

  In order to define the direction of initial orientation by rubbing, it is necessary to rub in a predetermined angle direction with fibers of about 10 to 30 μm as described above, but it extends in a certain direction such as a signal wiring electrode, a common electrode in a pixel, and a pixel electrode. Due to the wiring and the step at the end thereof, the fibers are dragged in the step direction from the set angle, and the orientation is disturbed, thereby causing a reduction in image quality such as an increase in black level.

(3) Dark level sinking One feature of the IPS-TFT-LCD is that the dark level (black display) sinking is good. Therefore, the disorder of orientation is more conspicuous than other methods.

  In the conventional normally open type TN system, the dark level is obtained with a high voltage applied. In this case, at a high voltage, most of the liquid crystal molecules are aligned in the electric field direction which is one direction perpendicular to the substrate surface, and a dark level is obtained due to the relationship between the liquid crystal molecule arrangement and the arrangement of the polarizing plates. Therefore, the uniformity of the dark level does not depend much on the initial alignment state at low voltage in principle.

  Furthermore, the human eye recognizes uneven luminance as a relative ratio of luminance, and reacts close to a logarithmic scale, so it is sensitive to changes in the dark level. From this point of view, the conventional normally open type TN method in which liquid crystal molecules are forcibly arranged in one direction at a high voltage is insensitive to the initial alignment bear.

  On the other hand, since the IPS system displays a dark level at a low voltage or zero voltage, it is sensitive to disturbance of the initial alignment state. In particular, an arrangement in which the liquid crystal molecular alignment directions are homogeneously aligned on the upper and lower substrates, the light transmission axis of one polarizing plate is parallel to the liquid crystal molecular alignment direction, and the other polarizing plate is orthogonal (birefringence mode). In other words, the polarized light incident on the liquid crystal layer propagates the linearly polarized light with little disturbance. This is useful for sinking dark levels. The transmittance T in the birefringence mode can be generally expressed by the following formula.

  T = T0 · sin2 {2θ (E)} · sin2 {(π · deff · Δn) / λ}

  Here, T0 is a coefficient, which is a numerical value mainly determined by the transmittance of the polarizing plate used in the liquid crystal panel, and θ (E) is formed by the alignment direction of liquid crystal molecules (effective optical axis of the liquid crystal layer) and the polarization transmission axis. Angle, E is the applied electric field strength, deff is the effective thickness of the liquid crystal layer, Δn is the refractive index anisotropy of the liquid crystal, and λ is the wavelength of light.

  Further, here, the effective thickness deff of the liquid crystal layer deff The product of the refractive index anisotropy Δn of the liquid crystal, that is, deff · Δn is referred to as retardation. Note that the thickness deff of the liquid crystal layer here is not the thickness of the entire liquid crystal layer, but corresponds to the thickness of the liquid crystal layer that actually changes the alignment direction when a voltage is applied.

  This is because the liquid crystal molecules in the vicinity of the interface of the liquid crystal layer do not change the orientation direction even when a voltage is applied due to the influence of anchoring at the interface. Therefore, if the thickness of the entire liquid crystal layer sandwiched between the substrates is dLC, there is always a relationship of def <dLC between the thickness dLC and diff, and the difference is between the liquid crystal material used for the liquid crystal panel and the liquid crystal Although it differs depending on the interface in contact with the layer, for example, the type of alignment film material, it can be estimated to be approximately 20 nm to 40 nm.

As apparent from the above equation, the term sin ² {2θ (E)} depends on the electric field strength, and the luminance can be adjusted by changing the angle θ according to the electric field strength E.

  In order to obtain a normally closed type, the polarizing plate is set so that θ = 0 ° when no voltage is applied, so that it acts so as to be sensitive to disturbance in the initial alignment direction.

As described above, in the IPS system, alignment uniformity is a very important factor, and the problem of the rubbing method currently used is becoming clear.

  Generally, in rubbing alignment treatment, problems related to the rubbing treatment method, such as TFT damage due to static electricity generated by friction, rubbing of the tip of the rubbing cloth, orientation failure due to dust, and frequent replacement of the rubbing cloth There are many.

  In order to solve these problems of rubbing alignment treatment, a so-called “rubbing-less” alignment method in which liquid crystals are aligned without rubbing has been studied, and various methods have been proposed. Among them, a photo-alignment method has been proposed in which the surface of a polymer film is irradiated with polarized ultraviolet rays or the like and liquid crystal molecules are aligned without rubbing treatment.

  As an example, the method disclosed in Non-Patent Document 1 below is characterized in that the liquid crystal is aligned in a certain direction by irradiation with polarized light without requiring a conventional rubbing treatment.

  According to this photo-alignment method, there are no problems such as scratches on the film surface or static electricity due to the rubbing method, and it is advantageous that it is simpler as a manufacturing process when considering industrial production. Attention has been focused on as a new liquid crystal alignment treatment method that does not use.

  As a liquid crystal alignment film material used in previous reports, it was proposed to use a polymer compound in which a photoreactive group was introduced into the side chain of the polymer because of the need to obtain photochemical sensitivity to polarized light. ing.

  A typical example is polyvinyl cinnamate. In this case, it is considered that the liquid crystal is oriented by developing anisotropy in the polymer film by dimerization at the side chain portion by light irradiation.

  In addition, it has been proposed that low molecular dichroic azo dyes can be dispersed in a polymer material and liquid crystal molecules can be aligned in a certain direction by irradiating polarized light onto the film surface. ing.

  Furthermore, it has been reported that liquid crystal molecules are aligned by irradiating a specific polyimide film with polarized ultraviolet rays or the like. In this case, it is considered that the liquid crystal alignment is expressed by decomposing the polyimide main chain in a certain direction by light irradiation.

Japanese Patent No. 3303766 JP 11-218765 A

Gibbons et al., “Nature”, 351, 49 (1991) (W.M. Gibbons et al., Nature, 351, 49 (1991))

  As described above, a photo-alignment method by light irradiation has been proposed and studied as a rubbing-less alignment method for solving the problems of the rubbing alignment method, but has the following problems in practice.

  In the polymer material system in which a photoreactive group is introduced into a polymer side chain represented by polyvinyl cinnamate, the thermal stability of orientation is not sufficient, and sufficient reliability is still obtained in terms of practicality. Not in.

  In this case, it is considered that the structural part that develops the alignment of the liquid crystal is the side chain portion of the polymer, and therefore it is not necessarily preferable for aligning the liquid crystal molecules more uniformly and obtaining a stronger alignment. .

  In addition, when a low-molecular dichroic dye is dispersed in a polymer, the dye itself that orients the liquid crystal is a low-molecular substance, which is a problem in terms of thermal or light reliability from a practical viewpoint. Is left behind.

  Furthermore, in the method of irradiating a specific polyimide with polarized ultraviolet rays, although the polyimide itself has high reliability such as heat resistance, it is considered that its orientation mechanism is caused by decomposition by light. It is difficult to ensure sufficient reliability in terms of surface.

  In other words, in the future, when applying this liquid crystal alignment using polarized light irradiation, it is necessary not only to align the liquid crystal initially but also to develop a more stable alignment from the viewpoint of reliability. The

  In consideration of actual industrial application, it is desired to select a thermally stable polymer structure. In these respects, the polymer materials conventionally proposed for liquid crystal alignment by light irradiation are not necessarily sufficient in terms of alignment force and stability, which is a big problem for realizing rubbing-less alignment by light irradiation. It is the actual situation.

  Therefore, an object of the present invention is to solve the problem that the manufacturing margin of the alignment process, which is an inherent problem of the IPS-TFT-LCD, is narrow, and to reduce the occurrence of display defects due to fluctuations in the initial alignment direction. Another object of the present invention is to provide a particularly large liquid crystal display device that realizes stable liquid crystal alignment and has high image quality with an increased contrast ratio.

  Another object of the present invention is to provide a liquid crystal display device with high image quality and high definition that is excellent in mass productivity.

  To achieve the above object, the present invention is formed on a pair of substrates, at least one of which is transparent, a liquid crystal layer disposed between the pair of substrates, and one of the pair of substrates, An electrode group for applying, a plurality of active elements connected to these electrodes, an alignment control film disposed between at least one of the liquid crystal layer and the pair of substrates, and the pair of substrates A polarizing means which is formed on at least one of the substrates and changes the optical characteristics according to the molecular alignment state of the liquid crystal layer, and at least one of the alignment control films is a photoreactive polyimide and / or polyamic acid. The alignment control film is formed by irradiating light polarized in a substantially straight line.

  Further, the invention is characterized in that an electric field applied to the liquid crystal layer is substantially parallel to a substrate surface on which the electrode group is formed.

  Further, the present invention is characterized in that the major axis direction of the liquid crystal molecules in the liquid crystal layer on the alignment control film is parallel or orthogonal (perpendicular) to the polarization axis polarized in a substantially straight line irradiated with light. In particular, the photoreactive alignment control film is desirably a polyamic acid or polyimide composed of at least a cyclobutanetetracarboxylic dianhydride as an acid anhydride and at least an aromatic diamine compound as a diamine.

（但し、Ｒ1，Ｒ2，Ｒ3，Ｒ4はそれぞれ独立に水素原子、フッ素原子、塩素原子、臭素原子、フェニル基又は炭素数１〜６のアルキル基、アルコキシ基又はビニル基[−(ＣＨ2)m−ＣＨ＝ＣＨ2,ｍ＝０，１，２]、又はアセチル基[−(ＣＨ2)m−ＣＨ≡ＣＨ2,ｍ＝０，１，２]） The cyclobutanetetracarboxylic dianhydride and derivatives thereof are compounds represented by the following general formulas [Compound 1] to [Compound 3].

(However, R1, R2, R3, and R4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a vinyl group [— (CH2) m— CH = CH2, m = 0, 1, 2] or acetyl group [-(CH2) m-CH≡CH2, m = 0, 1, 2])

（但し、化合物４から化合物１９のＲ1〜Ｒ8及び化合物２０のＲ1、Ｒ2はそれぞれ独立に水素原子、フッ素原子、塩素原子、又は炭素数１〜６のアルキル基、アルコキシ基、又はビニル基[−(ＣＨ2)m−ＣＨ＝ＣＨ2,ｍ＝０，１，２]、又はアセチル基[−(ＣＨ2)m−ＣＨ≡ＣＨ2,ｍ＝０，１，２]を示す。また、化合物１０〜１２においてＸは−ＣＨ２−,−ＮＨ−,−ＣＯ−,−Ｏ−,−Ｓ−の結合基を示す。また、化合物２０のＲ3、Ｒ4及び化合物２１、２２のＲ1はそれぞれ独立に炭素数１〜６のアルキル基を示す。） Further, the aromatic diamine compound contains at least one compound selected from the group consisting of the following general formulas [compound 4] to [compound 22].

(However, R1 to R8 of Compound 4 to Compound 19 and R1 and R2 of Compound 20 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a vinyl group [- (CH2) m-CH = CH2, m = 0,1,2] or an acetyl group [-(CH2) m-CH≡CH2, m = 0,1,2]. X represents a bonding group of —CH 2 —, —NH—, —CO—, —O—, —S—, wherein R 3 and R 4 of Compound 20 and R 1 of Compounds 21 and 22 each independently represent 1 to 6 represents an alkyl group.)

  Further, by making the orientation control film as thin as 1 nm to 100 nm, it is effective to improve the light transmittance and to improve the efficiency of the photoreaction by irradiation of polarized light. Further, when a liquid crystal display device is manufactured, it is effective to apply a voltage for driving the liquid crystal to the liquid crystal layer effectively.

  Further, the film thickness of the alignment control film on the electrode is reduced to 1 nm to 50 nm, and further to 1 nm to 30 nm, so that between each electrode / alignment control film / liquid crystal layer / alignment control film / electrode in each pixel of the liquid crystal display device. It is possible to reduce the direct current voltage component (so-called residual DC voltage) remaining in the image, which is effective in improving afterimage and image sticking characteristics.

  Further, the present invention is characterized in that the pretilt angle of the liquid crystal layer of the liquid crystal display device is 1 degree or less. Also, with the conventional rubbing alignment method, the electrode step edge acts as a fiber guide for the rubbing cloth, and the fiber is drawn in the direction in which the step extends, or the fiber does not reach the corner of the step and the alignment process can be performed. Orientation failure may occur.

  In particular, when at least one of the pixel electrode, the common electrode, or the common electrode wiring is formed of a transparent electrode, the alignment state in the vicinity of the electrode step is conspicuous, and the present invention is effective.

  In particular, when the transparent electrode is composed of an ion-doped titanium oxide film or an ion-doped zinc oxide film (ZnO), the present invention works effectively.

  On the other hand, when the pixel electrode and the common electrode facing it are arranged in parallel to each other and have a zigzag bent structure, the liquid crystal alignment film may be inferior in adhesion to the underlying organic insulating film. When the rubbing alignment treatment is performed, display defects such as peeling of the alignment film may occur. In such a case, the present invention is effective.

  The present invention is particularly effective when the common electrode and / or the pixel electrode is formed on the organic insulating film and the liquid crystal alignment film is formed on the organic insulating film and the electrode.

  In addition, the present invention is characterized in that the alignment control directions of the liquid crystal molecules at the two interfaces between the liquid crystal layer and the alignment control film formed on the pair of substrates are substantially the same direction.

  And this invention is characterized by providing a liquid crystal aligning process by irradiating polarized light to a liquid crystal aligning film.

  According to the present invention, the light wavelength of polarized light used for the alignment treatment is in the range of 200 to 400 nm. Furthermore, the present invention is more effective when using polarized light having at least two types of wavelengths, that is, light having the first wavelength and light having the second wavelength, which are polarized substantially linearly, used for the alignment treatment.

  In addition, the present invention is characterized in that the liquid crystal alignment control film has a glass transition temperature of 250 ° C. or higher.

  Furthermore, the present invention is more effective by adding at least one of heating, infrared irradiation, far-infrared irradiation, electron beam irradiation, and radiation irradiation when imparting liquid crystal alignment ability to the liquid crystal alignment film by polarized light irradiation. Act on. When imparting liquid crystal alignment ability by irradiating the alignment control film with polarized light, by applying heating, infrared irradiation, far-infrared irradiation, electron beam irradiation, and radiation irradiation, liquid crystal alignment ability provision by polarized irradiation is accelerated. Inducing a cross-linking reaction or the like is effective in promoting and stabilizing the liquid crystal alignment ability.

  In particular, the present invention operates more effectively by performing at least one of heating, infrared irradiation, far-infrared irradiation, electron beam irradiation, and radiation irradiation with the time of overlapping with the polarized irradiation treatment.

  The present invention also works effectively by performing the imidization baking treatment of the alignment control film and the polarization irradiation treatment with time overlap. In particular, when the liquid crystal alignment film is subjected to at least one of heating, infrared irradiation, far-infrared irradiation, electron beam irradiation, and radiation irradiation in addition to polarized light irradiation, the temperature of the alignment control film is 100 ° C to 400 ° C. It is desirable that the temperature be in the range of 150 ° C to 300 ° C.

  Also, the heating, infrared irradiation, and far infrared irradiation treatments can be combined with the imidization baking treatment of the orientation control film, and are effective.

  In the present invention, the target contrast is 500: 1 or more, and the time for eliminating the target afterimage is 5 minutes or less. In addition, the time for eliminating the afterimage is determined by a method defined in the following embodiment. In the present invention, since the target contrast is improved by the high contrast of 500: 1 or higher, the afterimage of the afterimage is lower than the conventional low contrast afterimage evaluation of about 200: 1. The criterion for disappearance was strict, and the time required for eliminating the target afterimage was set within 5 minutes.

  As described above, according to the present invention, in the IPS liquid crystal display device, the inherent problem that the manufacturing margin of the alignment process is narrow is solved, the occurrence of display defects due to the change in the initial alignment direction is reduced, and It is possible to provide a liquid crystal display device that realizes stable liquid crystal alignment, is excellent in mass productivity, and has high quality image quality with an increased contrast ratio.

  As described above, according to the present invention, in the IPS liquid crystal display device, the inherent problem that the manufacturing margin of the alignment process is narrow is solved, the occurrence of display defects due to the change in the initial alignment direction is reduced, and It is possible to provide a liquid crystal display device that realizes stable liquid crystal alignment, is excellent in mass productivity, and has high quality image quality with an increased contrast ratio.

1 is a cross-sectional view of a pixel portion illustrating a pixel configuration of a first embodiment of a liquid crystal display device according to the present invention. 2A and 2B are a plan view and a cross-sectional view of a pixel portion illustrating a pixel configuration of a liquid crystal display device according to a first embodiment of the invention. Sectional drawing of the pixel part explaining the pixel structure of 2nd Embodiment of the liquid crystal display device by this invention. The top view and sectional drawing of the pixel part explaining the pixel structure of the liquid crystal display device which is 2nd Embodiment of the liquid crystal display device by this invention. Sectional drawing of the pixel part explaining the pixel structure of 3rd Embodiment of the liquid crystal display device by this invention. Sectional drawing of the pixel part explaining the pixel structure of 4th Embodiment of the liquid crystal display device by this invention. Sectional drawing of the pixel part explaining the pixel structure of the liquid crystal display device which is 5th Embodiment of the liquid crystal display device by this invention. The top view of the pixel part explaining the pixel structure of the liquid crystal display device which is 5th Embodiment of the liquid crystal display device by this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Hereinafter, a substrate on which an active element such as a thin film transistor is formed is referred to as an active matrix substrate. In addition, when the counter substrate has a color filter, this is also referred to as a color filter substrate.

  In the present invention, the desired contrast as a target is 500: 1 or more, and the time for eliminating the target afterimage is preferably within 5 minutes. Note that the time for eliminating the afterimage is determined by a method defined in the following embodiment. In the present invention, since the target contrast is improved by the high contrast of 500: 1 or higher, the afterimage of the afterimage is lower than the conventional low contrast afterimage evaluation of about 200: 1. The criterion for disappearance was strict, and the time required for eliminating the target afterimage was set within 5 minutes.

  FIG. 1 is a schematic cross-sectional view of the vicinity of one pixel for explaining a first embodiment of a liquid crystal display device according to the present invention.

  FIG. 2 is a schematic view of an active matrix substrate for explaining a configuration in the vicinity of one pixel for explaining the first embodiment of the liquid crystal display device according to the present invention. FIG. 2 (a) is a plan view, and FIG. 2B is a cross-sectional view taken along line AA ′ in FIG. 2A, and FIG. 2C is a cross-sectional view taken along line BB ′ in FIG.

  FIG. 1 corresponds to a part of a cross section taken along line AA ′ in FIG. Note that the cross-sectional views of FIGS. 2 (b) and 2 (c) schematically show the configuration of the main part and schematically show the AA ′ line and BB ′ line in FIG. 2 (a). There is no one-to-one correspondence with the cutting part. For example, in FIG. 2B, the semiconductor film 116 shown in FIG. 1 is not shown, and in FIG. 2C, only one through hole connecting the counter electrode and the common wiring 120 is shown as a representative.

  In the liquid crystal display device of the present embodiment, a gate electrode (scanning signal electrode) 104 and a common wiring (common electrode wiring) 120 (FIG. 2) made of Cr (chromium) are arranged on a glass substrate 101 as an active matrix substrate. A gate insulating film 107 made of silicon nitride is formed so as to cover the gate electrode 104 and the common electrode wiring 120.

  A semiconductor film 116 made of amorphous silicon or polysilicon is disposed on the gate electrode 104 with a gate insulating film 107 interposed therebetween, and functions as an active layer of a thin film transistor (TFT) as an active element.

  In addition, a drain electrode (video signal wiring) 106 and a source electrode (pixel electrode) 105 made of Cr · Mo (chromium / molybdenum) are arranged so as to overlap a part of the pattern of the semiconductor film 116 and cover all of them. Thus, a protective insulating film 108 made of silicon nitride is formed.

  Further, as schematically shown in FIG. 2C, a common electrode (common electrode) connected to the common electrode wiring 120 through a through hole 118 formed through the gate insulating film 107 and the protective insulating film 108. ) 103 is disposed on the overcoat layer (organic protective film) 112.

  Further, as can be seen from FIG. 2A, the common electrode 103 led out from the common electrode wiring 120 through the through hole 118 is opposed to the pixel electrode 105 in a region of one pixel in plan view. Is formed.

  Therefore, in the first embodiment of the present invention, the pixel electrode 105 is disposed further below the protective insulating film 108 below the organic protective film 112, and the common electrode 103 is disposed on the organic protective film 112. It has become. One pixel is configured in a region sandwiched between the plurality of pixel electrodes 105 and the common electrode 103.

  An alignment control film 109 is formed on the surface of the active matrix substrate in which the unit pixels configured as described above are arranged in a matrix, that is, on the organic protective film 112 on which the common electrode 103 is formed.

  On the other hand, as shown in FIG. 1, the color filter layer 111 is arranged on the glass substrate 102 constituting the counter substrate so as to be divided for each pixel by a light shielding portion (black matrix) 113, and the color filter layer 111 and the light shielding part 113 are covered with an organic protective film 112 made of a transparent insulating material. Further, an alignment control film 109 is also formed on the organic protective film 112 to constitute a color filter substrate.

  These alignment control films 109 are provided with liquid crystal alignment capability by irradiation with ultraviolet linearly polarized light extracted using a pile polarizer with a quartz plate laminated using a high-pressure mercury lamp as a light source.

  A glass substrate 101 constituting an active matrix substrate and a glass substrate 102 constituting a counter electrode are arranged opposite to each other on the surface of the alignment control film 109, and a liquid crystal layer (liquid crystal composition layer) composed of liquid crystal molecules 110 therebetween. 110 'is arranged.

  A polarizing plate 114 is formed on each of the outer surfaces of the glass substrate 101 constituting the active matrix substrate and the glass substrate 102 constituting the counter electrode.

  As described above, an active matrix liquid crystal display device using thin film transistors (that is, a TFT liquid crystal display device) is configured.

  In this TFT liquid crystal display device, the liquid crystal molecules 110 constituting the liquid crystal composition layer 110 ′ are aligned substantially parallel to the opposing surfaces of the substrates 101 and 102 when no electric field is applied. Homogeneous alignment is performed in a state in which the initial alignment direction is specified.

  Here, when a voltage is applied to the gate electrode 104 to turn on the thin film transistor (TFT), an electric field 117 is applied to the liquid crystal composition layer due to a potential difference between the pixel electrode 105 and the common electrode 103, and thus the dielectric property of the liquid crystal composition. The liquid crystal molecules 110 constituting the liquid crystal composition layer change the direction in the electric field direction by the interaction between the anisotropy and the electric field. At this time, display can be performed by changing the light transmittance of the present liquid crystal display device by the refractive anisotropy of the liquid crystal composition layer and the action of the polarizing plate 114.

  The organic protective film 112 may be formed using a thermosetting resin such as an acrylic resin, an epoxy acrylic resin, or a polyimide resin that is excellent in insulation and transparency. Further, as the organic protective film 112, a photocurable transparent resin may be used, or an inorganic material such as a polysiloxane resin may be used. Furthermore, the organic protective film 112 may also serve as the alignment control film 109.

  As described above, according to the first embodiment, the non-contact photo-alignment method is used instead of the rubbing alignment process in which the liquid crystal alignment control ability of the alignment control film 109 is directly rubbed with a buff cloth. Thus, there is no local disturbance of orientation, and uniform orientation can be provided over the entire display region.

  Next, a second embodiment of the liquid crystal display device according to the present invention will be described. FIG. 3 is a schematic sectional view of the vicinity of one pixel for explaining a second embodiment of the liquid crystal display device according to the present invention.

  FIG. 4 is a schematic view of an active matrix substrate for explaining a configuration in the vicinity of one pixel for explaining a second embodiment of the liquid crystal display device according to the present invention. FIG. 4 (a) is a plan view, and FIG. 4B is a cross-sectional view taken along line AA ′ in FIG. 4A, and FIG. 4C is a cross-sectional view taken along line BB ′ in FIG.

  FIG. 3 shows a part of a cross section taken along the line AA ′ in FIG. Note that the cross-sectional views of FIG. 4B and FIG. 4C schematically show the configuration of the main part, and are schematically shown by the lines AA ′ and BB ′ in FIG. There is no one-to-one correspondence with the cutting part. For example, FIG. 4B does not show the semiconductor film 116 shown in FIG.

  In the liquid crystal display device according to the second embodiment of the present invention, the gate electrode 104 and the common electrode wiring 120 made of Cr are arranged on the glass substrate 101 constituting the active matrix substrate, and the gate electrode 104 and the common electrode wiring are arranged. A gate insulating film 107 made of silicon nitride is formed so as to cover 120.

  A semiconductor film 116 made of amorphous silicon or polysilicon is disposed on the gate electrode 104 through a gate insulating film 107 so as to function as an active layer of a thin film transistor (TFT) as an active element.

  Further, a drain electrode 106 and a source electrode (pixel electrode) 105 made of chromium / molybdenum are arranged so as to overlap a part of the pattern of the semiconductor film 116, and a protective insulating film 108 made of silicon nitride is formed so as to cover all of them. Is formed.

  An organic protective film 112 is disposed on the protective insulating film 108. The organic protective film 112 is made of a transparent material such as acrylic resin.

  The pixel electrode 105 is composed of a transparent electrode such as ITO (In2O3: Sn).

  The common electrode 103 is connected to the common electrode wiring 120 through a through hole 118 that penetrates the gate insulating film 107, the protective insulating film 108, and the organic protective film 112.

  When an electric field for driving the liquid crystal is applied, the common electrode 103 that forms a pair with the pixel electrode 105 is formed so as to surround a region of one pixel in a plane.

  The common electrode 103 is disposed on the organic protective film (overcoat layer) 112. The common electrode 103 is arranged so as to hide the drain electrode 106, the scanning signal wiring 104, and the thin film transistor (TFT) which is an active element when viewed from above, and shields the semiconductor film 116. Also serves as a light shielding layer.

  The surface of the glass substrate 101 constituting the active matrix substrate in which the unit pixels (one pixel) configured as described above are arranged in a matrix, that is, on the organic protective film 112 and the common electrode 103 formed thereon. An alignment control film 109 is formed thereon.

  On the other hand, the color filter layer 111, the organic protective film 112 formed thereon, and the orientation control film 109 are also formed on the glass 102 constituting the counter substrate.

  Similarly to the first embodiment, these alignment control films 109 have a liquid crystal alignment ability by irradiation with ultraviolet linearly polarized light extracted using a pile polarizer with a quartz plate laminated using a high-pressure mercury lamp as a light source. Has been granted.

  The glass substrate 101 and the counter substrate 102 are arranged so as to face each other on the formation surface of the alignment control film 109, and the liquid crystal composition layer 110 ′ composed of the liquid crystal molecules 110 is arranged therebetween. Yes. A polarizing plate 114 is formed on each of the outer surfaces of the glass substrate 101 and the counter substrate 102.

  As described above, also in the second embodiment of the present invention, the pixel electrode 105 is disposed below the organic protective film 112 and the protective insulating film 108 as in the first embodiment described above. The common electrode 103 is disposed on the electrode 105 and the organic protective film 112.

  Further, when the electric resistance of the common electrode 103 is sufficiently low, the common electrode 103 can also serve as the common electrode wiring 120 formed in the lowermost layer. In that case, the formation of the common electrode wiring 120 arranged in the lowermost layer and the processing of the through hole associated therewith can be omitted.

  In the second embodiment, as shown in FIG. 4A, one pixel is formed in a region surrounded by the common electrode 103 formed in a lattice shape, and four pixels are combined with the pixel electrode 105. It is arranged so as to be divided into areas.

  In addition, the pixel electrode 105 and the common electrode 103 facing the pixel electrode 105 have a zigzag bent structure in which the pixel electrode 105 and the common electrode 103 are arranged in parallel to each other, and one pixel forms two or more subpixels. As a result, the color tone change in the plane is offset.

  FIG. 5 is a schematic cross-sectional view of the vicinity of one pixel for explaining a third embodiment of the liquid crystal display device according to the present invention. In the drawing, the same reference numerals as those in the drawings of the respective embodiments described above correspond to the same functional parts.

  As shown in FIG. 5, in this embodiment mode, the pixel electrode 105 disposed under the protective insulating film 108 is pulled up on the organic protective film 112 through the through hole 118 and disposed in the same layer as the common electrode 103. . In this configuration, the voltage for driving the liquid crystal can be further reduced.

  In the TFT liquid crystal display device configured as described above, when no electric field is applied, the liquid crystal molecules 110 constituting the liquid crystal composition layer 110 ′ are in a state substantially parallel to the surfaces of the glass substrates 101 and 102 disposed opposite to each other. Homogeneous alignment is performed in the initial alignment direction defined by the photo-alignment treatment.

  Here, when a voltage is applied to the gate electrode 104 to turn on the thin film transistor (TFT), an electric field 117 is applied to the liquid crystal composition layer 110 ′ due to a potential difference between the pixel electrode 105 and the common electrode 103, and the liquid crystal composition is Due to the interaction between the dielectric anisotropy and the electric field, the liquid crystal molecules 110 change the direction in the electric field direction. At this time, display can be performed by changing the light transmittance of the liquid crystal display device by the refractive anisotropy of the liquid crystal composition layer 110 ′ and the action of the polarizing plate 114.

  In each of the embodiments of the present invention described above, a plurality of display areas each including a common electrode and a pixel electrode in one pixel can be provided. By providing a plurality of sets in this manner, even when one pixel is large, the distance between the pixel electrode and the common electrode can be shortened, so that the voltage applied to drive the liquid crystal can be reduced.

  In each of the embodiments of the present invention described above, the material of the transparent conductive film constituting at least one of the pixel electrode and the common electrode is not particularly limited, but is easy to process, high in reliability, etc. Therefore, it is desirable to use a transparent conductive film ion-doped with titanium oxide such as indium-tin-oxide (ITO) or ion-doped zinc oxide.

  In general, in the IPS system, it is known that the interface tilt with the substrate surface is not necessary in principle, unlike the vertical electric field system typified by the conventional TN system, and the viewing angle characteristics are better as the interface tilt angle is smaller. Even in the photo-reactive alignment control film, a small interface tilt angle is desirable, and an angle of 1 degree or less is particularly effective.

  Next, formation of the alignment control film using the rubbing-less alignment method of the liquid crystal alignment control film in the liquid crystal display device according to the present invention will be described. The flow of the alignment control film forming process according to the present invention is as follows (1) to (4).

  (1) Coating / formation of orientation control film (forms a uniform coating over the entire display area).

  (2) Imidization firing of the orientation control film (removal of varnish solvent and promotion of polyimide with high heat resistance are promoted).

  (3) Giving liquid crystal alignment ability by applying polarized light (giving uniform alignment ability to the display area).

  (4) Promotion / stabilization of alignment ability by (heating, infrared irradiation, far infrared irradiation, electron beam irradiation, radiation irradiation).

  The alignment control film is formed through the above four-stage process, but is not limited to the order of the above processes (1) to (4). In the following cases (I) and (II) Further effects are expected.

  (I) By processing the above (3) and (4) so as to overlap in time, the alignment control film can be formed more effectively by accelerating the provision of liquid crystal alignment ability and inducing a crosslinking reaction or the like. It becomes possible.

  (II) When using the heating, infrared irradiation, far-infrared irradiation, etc. of the above (4), the above (2), (3), (4) are overlapped in time, The process can also serve as the imidization process (2), and the alignment control film can be formed in a short time.

  Next, specific examples of the manufacturing method of the liquid crystal display device according to the present invention will be described.

  The first example corresponds to the liquid crystal display device described in the first embodiment of the present invention. Hereinafter, a first embodiment of the present invention will be described in detail with reference to FIGS.

  When manufacturing the liquid crystal display device according to the first embodiment of the present invention, the glass substrate 101 constituting the active matrix substrate and the glass substrate 102 constituting the counter substrate (color filter substrate) have a thickness of 0.7 mm and the surface. A glass substrate polished is used.

  A thin film transistor formed on the glass substrate 101 includes a source electrode (pixel electrode) 105, a drain electrode (signal electrode) 106, a gate electrode (scanning electrode) 104, and a semiconductor film (amorphous silicon) 116.

  The scanning electrode 104, the common electrode wiring 120, the signal electrode 106, and the pixel electrode 105 were all formed by patterning a chromium film, and the distance between the pixel electrode 105 and the common electrode 103 was 7 μm.

  For the common electrode 103 and the pixel electrode 105, a chromium film having low resistance and easy patterning is used. However, a transparent electrode can be formed using an ITO film to achieve higher luminance characteristics. .

  The gate insulating film 107 and the protective insulating film 108 were made of silicon nitride, and the film thicknesses were each 0.3 μm. An acrylic resin was applied thereon, and a transparent and insulating organic protective film 112 was formed by heat treatment at 220 ° C. for 1 hour.

  Next, through holes were formed up to the common electrode wiring 120 by photolithography and etching, and the common electrode 103 connected to the common electrode wiring 120 was formed by patterning as shown in FIG.

  As a result, in the unit pixel (one pixel), as shown in FIG. 2A, the pixel electrode 105 is arranged between the three common electrodes 103, and the number of pixels is 1024 × 3 (R , G, and B), an active matrix substrate having 1024 × 3 × 768 composed of signal electrodes 106 and 768 scanning electrodes 104 was formed.

Next, as the alignment control film, 1,4-diaminopyridine represented by the following general formula [Compound 23] and 1-methyl-1,2,3,4-cyclobutanetetracarboxylic acid diester represented by the following general formula [Compound 24] are used. A polyamic acid varnish composed of an anhydride was adjusted to a resin concentration of 5% by weight, NMP 60% by weight, γ-butyllactone 20% by weight, butyl cellosolve 15% by weight, printed on the active matrix substrate at 220 ° C. Imidization is performed by heat treatment for 30 minutes to form a dense polyimide orientation control film 109 having a thickness of about 70 nm.

  Similarly, the same polyamic acid varnish is printed on the surface of the other glass substrate 102 on which ITO has been formed, heat-treated at 220 ° C. for 30 minutes, and an orientation composed of a dense polyimide film of about 70 nm. A control film 109 was formed.

In order to give the liquid crystal alignment ability to the surface, the polyimide alignment control film 109 was irradiated with polarized UV (ultraviolet) light. A high pressure mercury lamp is used as a light source, UV light in the range of 240 nm to 380 nm is taken out through an interference filter, and is converted into linearly polarized light with a polarization ratio of about 10: 1 using a pile polarizer laminated with a quartz substrate. Irradiation was performed with an irradiation energy of / cm ² .

  As a result, it was found that the alignment direction of the liquid crystal molecules on the surface of the alignment control film was orthogonal to the polarization direction of the irradiated polarized UV light.

  Next, these two glass substrates 101 and 102 are interspersed with spacers made of spherical polymer beads dispersed with their surfaces having alignment control films 109 having liquid crystal alignment ability facing each other. Then, a sealant was applied to the peripheral portion, and a liquid crystal display panel (also referred to as a cell) to be a liquid crystal display device was assembled. The liquid crystal alignment directions of the two glass substrates were substantially parallel to each other, and the angle formed with the applied electric field direction was 75 °.

  This cell has a positive dielectric anisotropy Δε, a value of 10.2 (1 kHz, 20 ° C.), a refractive index anisotropy Δn of 0.075 (wavelength 590 nm, 20 ° C.), and a torsional elastic constant. A nematic liquid crystal composition A having a K2 of 7.0 pN and a nematic-isotropic phase transition temperature T (NI) of about 76 ° C. was injected in a vacuum and sealed with a sealing material made of an ultraviolet curable resin. A liquid crystal panel having a liquid crystal layer thickness (gap) of 4.2 μm was produced.

  The retardation (Δnd) of this liquid crystal display panel is about 0.31 μm. Also, a homogeneous alignment liquid crystal display panel was prepared using the alignment control film and the liquid crystal composition used in this panel, and the pretilt angle of the liquid crystal was measured using the crystal rotation method. showed that.

  This liquid crystal display panel was sandwiched between two polarizing plates 114, and the polarizing transmission axis of one polarizing plate was set substantially parallel to the liquid crystal alignment direction, and the other was arranged so as to be orthogonal thereto.

  Thereafter, a drive circuit, a backlight, and the like were connected to form a module, and an active matrix liquid crystal display device was obtained. In this embodiment, a normally closed characteristic is obtained in which dark display is performed at a low voltage and bright display is performed at a high voltage.

  Next, when the display quality of the liquid crystal display device according to the first embodiment of the present invention was evaluated, a high quality display with a contrast ratio of 600: 1 was confirmed, and a wide viewing angle at the time of halftone display was obtained. confirmed.

  Next, in order to quantitatively measure image printing and afterimage of the liquid crystal display device according to the first embodiment of the present invention, evaluation was performed using an oscilloscope combined with a photodiode.

  First, the window pattern is displayed on the screen at the maximum brightness for 30 minutes, and then the halftone display in which the afterimage is most noticeable. Here, the entire surface is switched so that the brightness is 10% of the maximum brightness, and the pattern of the edge portion of the window pattern. The time until disappearance was evaluated as the afterimage relaxation time. However, the afterimage relaxation time allowed here is 5 minutes or less.

  As a result, in the operating temperature range (0 ° C. to 50 ° C.), the afterimage relaxation time is 1 minute or less, and even in visual image quality afterimage inspection, image burning and display unevenness due to afterimage are not seen at all. High display characteristics were obtained.

  Conventionally, although alignment of liquid crystals can be imparted by photo-alignment, it is said that anchoring energy, that is, energy for constraining aligned liquid crystal molecules to the alignment film surface is weaker than that of general rubbing alignment.

  If the anchoring energy is weak, it is said that the reliability of the liquid crystal display device is insufficient. In particular, in the case of homogeneous orientation, anchoring energy in the azimuth direction is more important than anchoring energy in the polar angle direction.

Therefore, using the same alignment film material as the liquid crystal display device thus obtained, an alignment film is formed on the glass substrate by the same process, the alignment treatment is performed, and the same liquid crystal composition is sealed to produce a liquid crystal cell. Measure the strength of torsional coupling between the liquid crystal molecules and the alignment film surface at the interface and the azimuthal anchoring energy A2 by the torque balance method (Hasegawa et al., Liquid Crystal Society Annual Meeting Lecture Collection 3B12 (2001) p.251) Then, was 7.0 × 10- ⁴ N / m. In Comparative Example 1 shown below, the A2 is 8.6 × 10- ⁵ N / m.

The tetracarboxylic dianhydride shown in the following general formula [Compound 25] and the following general formula [Compound] as the acid dianhydride are the same as in the first example except for the orientation control film used in the second example. 26], a polyamic acid composed of 3,4-diaminothiophene was printed on the surface of the substrate, imidized by baking at 220 ° C. for 30 minutes, and a film thickness of about 40 nm was formed. Thereafter, the surface was subjected to photo-alignment treatment by light irradiation using polarized UV light having a wavelength of 248 nm of KrF excimer laser and 337 nm of nitrogen laser.

  Then, after encapsulating the nematic liquid crystal composition A in the same manner as in the first example, annealing was performed at 100 ° C. for 10 minutes, and good liquid crystal alignment was obtained in a direction substantially perpendicular to the irradiation polarization direction.

  Thus, a liquid crystal display panel having a liquid crystal layer thickness d of 4.0 μm was obtained. Further, a homogeneous alignment liquid crystal display panel was prepared using the alignment control film and the liquid crystal composition used in this liquid crystal display panel, and the pretilt angle of the liquid crystal was measured by the crystal rotation method. .5 degrees.

  Next, when the display quality of the liquid crystal display device was evaluated in the same manner as in the first example, the contrast ratio almost equivalent to that of the liquid crystal display device of the first example was high quality exceeding 500: 1 over the entire surface. The display was confirmed, and a wide viewing angle during halftone display was also confirmed.

  Similarly to the first embodiment, the image printing and afterimage relaxation time of this liquid crystal display device were quantitatively evaluated. As a result, the afterimage relaxation time was about 1 in the operating temperature range of 0 ° C. to 50 ° C. Even in visual image quality afterimage inspection, no image burning or display unevenness due to afterimage was observed, and high display characteristics equivalent to Example 1 were obtained.

[Comparative Example 1]
As a comparative example for explaining the effect of the present example, pyromellitic acid dibenzoate represented by the following general formula [Compound 27] was used as an acid dianhydride in the same manner as in the first example except for the orientation control film. A liquid crystal display panel was constructed using a polyamic acid varnish composed of m-phenylenediamine represented by the following general formula [Compound 28] as an anhydride and a diamine compound.

  When the display quality was evaluated in the same manner as in the first example, a wide viewing angle almost the same as that of the liquid crystal display device in the first example was confirmed, but the contrast ratio was 100: 1 over the entire surface. It was confirmed that the display was lower.

Further, in the same manner as in the first embodiment, when the image printing and afterimage relaxation time of this liquid crystal display device were quantitatively evaluated, the afterimage relaxation time was about 20 in the operating temperature range of 0 ° C to 50 ° C. Even in visual image quality afterimage inspection, the afterimage relaxation time was slow, and high display characteristics equivalent to Example 1 were not obtained. The value of the azimuthal orientation anchoring energy A2 was about 8.6 × 10- ⁵ N / m.

Except for the orientation control film used in the third example, the acid dianhydride was used as an acid dianhydride as shown in the following general formula [Compound 29] 1,3-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride represented by the following general formula [Compound 30] in a molar ratio of 7: 3, and a diamine compound, p-phenylene represented by the following general formula [Compound 31] A polyamic acid varnish was prepared using diamine to prepare a liquid crystal display panel. At that time, the film thickness of the orientation control film was about 50 nm.

  Next, when the display quality of the liquid crystal display device was evaluated in the same manner as in the first example, the contrast ratio almost the same as that of the liquid crystal display device of the first example was higher than 550: 1 over the entire surface. And a wide viewing angle during halftone display were also confirmed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation time of this liquid crystal display device were quantitatively evaluated, the afterimage relaxation time was 0 ° C to 50 ° C in the operating temperature range. In the visual image afterimage inspection, no image printing or display unevenness due to the afterimage was observed at all, and the same high display characteristics as in Example 1 were obtained.

  Furthermore, the composition ratio of the above two types of acid anhydrides 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride of the polyamic acid varnish used for the orientation control film Two types of polyamic acid varnishes having a ratio of 1: 1 and 3: 7 were prepared, and two types of liquid crystal display panels were produced using each. The contrast ratio of the liquid crystal display device using this liquid crystal display panel was about 450: 1 and 180: 1, respectively.

  The afterimage relaxation times were about 3 minutes and 8 minutes, respectively, and the acid anhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic acid 2 were obtained. When the composition ratio of the anhydride was 3: 7, the display characteristics were remarkably reduced as compared with the other cases.

  Next, as a specific configuration of the liquid crystal display device according to the second embodiment of the present invention, a fourth example will be described with reference to FIGS. In the case of manufacturing the liquid crystal display device according to the fourth embodiment of the present invention, as the glass substrates 101 and 102, glass substrates having a thickness of 0.7 mm and polished surfaces are used.

  The thin film transistor includes a source electrode (pixel electrode) 105, a drain electrode (signal electrode) 106, a gate electrode (scanning electrode) 104, and a semiconductor film (amorphous silicon) 116. The scan electrode 104 is formed by patterning an aluminum film, the common electrode wiring 120 and the signal electrode 106 are formed by patterning a chromium film, and the pixel electrode 105 is formed by patterning an ITO film. As shown in FIG. The electrode wiring patterns other than 104 were formed in a zigzag bent electrode wiring pattern. At that time, the angle of bending was set to 10 degrees. The gate insulating film 107 and the protective insulating film 108 were made of silicon nitride, and the film thicknesses were each 0.3 μm.

  Next, as shown in FIG. 4C, through holes 118 are formed in a cylindrical shape having a diameter of about 10 μm to the common electrode wiring 120 by photolithography and etching, and an acrylic resin is applied thereon. An interlayer insulating film 112 having a dielectric constant of about 4 having a dielectric constant of about 4 μm was formed by heat treatment at 220 ° C. for 1 hour to a thickness of about 1 μm. By this interlayer insulating film 112, the unevenness due to the step of the pixel electrode 105 in the display area and the step unevenness of the boundary portion of the color filter layer 111 between adjacent pixels are flattened.

  Thereafter, the through hole 118 was etched again to a diameter of about 7 μm, and the common electrode 103 connected to the common electrode wiring 120 was formed by patterning the ITO film thereon. At that time, the distance between the pixel electrode 105 and the common electrode 103 was set to 7 μm. Further, the common electrode 103 is formed in a lattice shape so as to cover the upper part of the video signal wiring 106, the scanning signal wiring 104, and the thin film transistor so as to surround the pixel, and also serves as a light shielding layer.

  As a result, in the unit pixel, as shown in FIG. 4A, the pixel electrode 105 is arranged between the three common electrodes 103, and the number of pixels is 1024 × 3 (R, G, B). Correspondence) A 1024 × 3 × 768 active matrix substrate composed of signal electrodes 106 and 768 scanning electrodes 104 was obtained.

Next, as the orientation control film 109, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 32] and the following general formula [ Using a polyamic acid varnish composed of m-phenylenediamine shown in Compound 33], an alignment control film having a film thickness of about 60 nm was prepared, and the alignment treatment method was the same as in Example 1 with irradiation of polarized UV of about 3 Jcm-2. Irradiated with energy. However, during the polarized UV irradiation, the substrate on which the alignment control film was formed was also subjected to a heat treatment at about 150 ° C. on a hot plate.

  Next, with these two glass substrates, the surfaces having the respective liquid crystal alignment films are opposed to each other, a spacer made of dispersed spherical polymer beads is interposed, and a sealant is applied to the peripheral portion, A liquid crystal display panel was assembled. The liquid crystal alignment directions of the two glass substrates were substantially parallel to each other, and the angle formed with the applied electric field direction was 75 °.

  This liquid crystal display panel has a positive dielectric anisotropy Δε, a value of 10.2 (1 kHz, 20 ° C.), a refractive index anisotropy Δn of 0.075 (wavelength 590 nm, 20 ° C.), and a twist. A nematic liquid crystal composition A having an elastic constant K2 of 7.0 pN and a nematic-isotropic phase transition temperature T (NI) of about 76 ° C. is injected in a vacuum and sealed with a sealing material made of an ultraviolet curable resin. did. A liquid crystal panel having a liquid crystal layer thickness (gap) of 4.2 μm was produced. The retardation (Δnd) of this panel is about 0.31 μm.

  Further, a homogeneous alignment liquid crystal display panel was prepared using the alignment control film and the liquid crystal composition equivalent to the liquid crystal display panel, and the pretilt angle of the liquid crystal was measured by the crystal rotation method. Showed twice.

  This panel was sandwiched between two polarizing plates 114, and the polarizing transmission axis of one polarizing plate was made substantially parallel to the liquid crystal alignment direction, and the other was arranged so as to be orthogonal thereto. Thereafter, a drive circuit, a backlight, and the like were connected to form a module, and an active matrix liquid crystal display device was obtained. In this embodiment, a normally closed characteristic is obtained in which dark display is performed at a low voltage and bright display is performed at a high voltage.

  Next, when the display quality of the liquid crystal display device according to the fourth embodiment of the present invention was evaluated, the aperture ratio was higher than that of the liquid crystal display device according to the first embodiment, and a high quality display with a contrast ratio of 600: 1. As well as a wide viewing angle during halftone display.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation time of this liquid crystal display device were quantitatively evaluated, the afterimage relaxation time was 0 ° C to 50 ° C in the operating temperature range. In the visual image afterimage inspection, no image printing or display unevenness due to the afterimage was observed at all, and the same high display characteristics as in Example 1 were obtained.

  Moreover, when the orientation control film produced on the glass substrate by the method similar to a present Example was scraped off and the glass transition temperature of the orientation control film was evaluated using the differential scanning calorimeter (DSC), 50 was measured. A clear glass transition point could not be confirmed in the temperature range from ° C to 300 ° C. Therefore, the glass transition temperature of the alignment control film of this example is considered to be 300 ° C. or more, which is the upper limit of the measurement temperature.

As an orientation control film, a polyamic acid comprising 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 34] and 2,7-diaminocarbazole represented by the following general formula [Compound 35] An alignment control film having a film thickness of about 100 nm is prepared using a varnish, and the alignment treatment method uses light from a high-pressure mercury lamp similar to that of the first embodiment using an interference filter and a quartz pile polarizer. Irradiation was performed with a polarized UV of 10: 1 in the wavelength range of 380 nm and an irradiation energy of about 5 J / cm2. Other than that was carried out similarly to 4th Example, and produced the liquid crystal display panel of 5th Example.

  When the display quality of the liquid crystal display device obtained using this liquid crystal display panel was evaluated, a high quality display equivalent to that of the liquid crystal display device of the fourth example was confirmed. Also, a wide viewing angle during halftone display was confirmed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation times of the liquid crystal display device of the fifth embodiment were quantitatively evaluated, the operating temperature range of 0 ° C. to 45 ° C. was used. The afterimage relaxation time was 1 minute or less as in the fourth embodiment, and even in visual image quality afterimage inspection, no image burn-in and display unevenness due to afterimage were observed, and high display characteristics were obtained.

  Moreover, when the orientation control film | membrane produced on the glass substrate by the method similar to 4th Example was shaved off and the glass transition temperature of the orientation control film was evaluated using the differential scanning calorimeter (DSC; Differential Scanning Calorimetry), A clear glass transition point could not be confirmed in the temperature range from 50 ° C to 300 ° C. Therefore, the glass transition temperature of the alignment control film of this example is considered to be 300 ° C. or more, which is the upper limit of the measurement temperature.

  Further, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was used as the acid anhydride, and the liquid crystal display device was produced in the same manner as in this example, with the irradiation energy set to about 3 J / cm 2. As a result of evaluation, a liquid crystal display device having display characteristics equivalent to those of this example was obtained.

  Also, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is used as the acid anhydride, and the irradiation energy is about 2 J / cm @ 2 as in the present embodiment. When a display device was produced, a liquid crystal display device having display characteristics equivalent to those of this example was obtained.

Instead of the spacers made of polymer beads used to control the cell gap of the liquid crystal display device, a negative photosensitive acrylic resin is applied, exposed and developed before forming the alignment control film on the active matrix substrate in advance. Then, patterning is performed in a column shape with a diameter of about 10 μm, and is formed on the common electrode 103 that is the upper light shielding layer of the scanning wiring 104 in the vicinity of the TFT portion of each pixel, and then as a diamine compound as an alignment control film, 1-amino-2- (4′-aminophenyl) -ethene represented by the formula [Compound 36] and 3,6-diaminoindacene represented by the following general formula [Compound 37] in a molar ratio of 1: 2. And 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 38] Adjust the mix acid varnish was formed to a thickness of about 40 nm.

  In addition, the alignment treatment method is to irradiate light from a high-pressure mercury lamp similar to that in Example 5 with polarized light UV having a polarization ratio of 10: 1 in a wavelength range of 240 nm to 310 nm using an interference filter and a quartz pile polarizer. The energy was irradiated at about 3 J / cm2. At the same time, soft X-rays were irradiated from a short distance using a soft X-ray generator.

  Except for the above steps, the liquid crystal display device according to the sixth embodiment was made in the same manner as in the fifth embodiment, and the display quality of the liquid crystal display device according to the sixth embodiment of the present invention was evaluated. A high-quality display showing a high contrast ratio as compared with the liquid crystal display device of the example was confirmed.

  Also, a wide viewing angle during halftone display was confirmed. This is considered to be because light leakage due to the disorder of the alignment of the liquid crystal around the spacer beads randomly distributed in the pixels found in the liquid crystal display device of the fifth embodiment is completely removed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation time of the liquid crystal display device of the sixth embodiment were quantitatively evaluated, the afterimage relaxation time was 1 as in the fifth embodiment. Even in visual image quality afterimage inspection, no image burn-in and display unevenness due to afterimage were observed, and high display characteristics were obtained.

Except for the alignment control film used in the seventh example and the alignment treatment conditions, 2,7-diaminodibenzothiophene as the diamine compound represented by the following general formula [Compound 39] and A polyamic acid composed of 1,2,3-trimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride as the acid dianhydride represented by the formula [Compound 40] is printed on the surface of the substrate. The film was baked at ° C for 30 minutes for imidization to form a film having a thickness of about 30 nm.

Then, photoirradiation processing was performed by irradiating the surface with far-infrared rays and irradiating polarized UV of 337 nm of a nitrogen laser with an irradiation energy of about 4 J / cm ² . The temperature of the orientation control film at that time was about 200 ° C.

  Then, after encapsulating the nematic liquid crystal composition A in the same manner as in the fourth example, annealing was performed at 100 ° C. for 10 minutes, and good liquid crystal alignment was obtained in a direction substantially perpendicular to the irradiation polarization direction.

  Thus, a liquid crystal display device having a liquid crystal layer thickness d of 4.0 μm was obtained. In addition, a homogeneous alignment cell was prepared using the alignment control film and the liquid crystal composition used for this panel, and the pretilt angle of the liquid crystal was measured using the crystal rotation method. It was.

  Next, when the display quality of the liquid crystal display device according to the seventh embodiment of the present invention was evaluated in the same manner as in the first embodiment, the contrast ratio almost the same as that of the liquid crystal display device of the first embodiment was obtained. In addition, high-quality display exceeding 600: 1 was confirmed, and a wide viewing angle during halftone display was also confirmed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation time of the liquid crystal display device of the seventh embodiment were quantitatively evaluated, the afterimage relaxation time was 1 minute or less and Even in the image quality afterimage inspection, no image burning or display unevenness due to the afterimage was observed, and high display characteristics were obtained.

Except for the alignment control film used in the eighth example and the alignment treatment conditions, in the same manner as in the fourth example, 2,7-diaminophenazine represented by the following general formula [Compound 41], and diacid As an anhydride, a polyamic acid composed of 1-methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 42] was printed on a substrate surface, and 230 ° C., Baking for 30 minutes and imidization were performed to form a film having a thickness of about 20 nm.

  Thereafter, a photo-alignment treatment was performed by irradiating the surface with far-infrared rays using light irradiation using polarized UV light of 337 nm of a nitrogen laser. The temperature of the orientation control film at that time was about 200 ° C. Then, after encapsulating the nematic liquid crystal composition A in the same manner as in the fourth example, annealing was performed at 100 ° C. for 10 minutes, and good liquid crystal alignment was obtained in a direction substantially perpendicular to the irradiation polarization direction.

  Thus, a liquid crystal display device having a liquid crystal layer thickness d of 4.0 μm was obtained. In addition, a homogeneous alignment cell was prepared using the alignment control film and the liquid crystal composition used for this panel, and the pretilt angle of the liquid crystal was measured using the crystal rotation method. It was.

  Next, when the display quality of the liquid crystal display device according to the eighth embodiment of the present invention was evaluated in the same manner as in the first embodiment, the contrast ratio almost the same as that of the liquid crystal display device of the fourth embodiment was observed on the entire surface. A high-quality display exceeding 600: 1 was confirmed, and a wide viewing angle during halftone display was also confirmed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation time of the liquid crystal display device of the eighth embodiment were quantitatively evaluated, the afterimage relaxation time was 2 minutes or less and Even in the image quality afterimage inspection, no image burning or display unevenness due to the afterimage was observed, and high display characteristics were obtained.

In addition to the combination of far infrared irradiation and polarized UV irradiation of a nitrogen laser, the alignment control film used in this example is not limited to 300 nm to light from an high pressure mercury lamp, for example, via an interference filter and a quartz pile polarizer. It has been found that the above high display characteristics can be obtained even when polarized UV light having a wavelength range of 380 nm is irradiated at an irradiation energy of about 3 J / cm ² .

  Furthermore, it was found that the same high display characteristics as above were obtained when the polarized UV of 300 to 380 nm was irradiated while irradiating the carbon dioxide laser of 10.5 μm with 200 mJ.

  The ninth embodiment of the present invention will be described below with reference to FIG. In manufacturing the liquid crystal display device according to the ninth embodiment of the present invention, glass substrates whose thickness is 0.7 mm and whose surface is polished are used as the substrates 101 and 102.

  The thin film transistor includes a source electrode (pixel electrode) 105, a drain electrode (signal electrode) 106, a gate electrode (scanning electrode) 104, and a semiconductor film (amorphous silicon) 116. The scanning electrode 104 was formed by patterning an aluminum film, and the common electrode wiring 120, the signal electrode 106, and the pixel electrode 105 were formed by patterning a chromium film.

  The gate insulating film 107 and the protective insulating film 108 were made of silicon nitride, and the film thicknesses were each 0.3 μm. An acrylic resin was applied thereon, and a transparent and insulating organic protective film 112 having a dielectric constant of about 4 was formed to a thickness of about 1.0 μm by heat treatment at 220 ° C. for 1 hour. With this organic protective film 112, the unevenness due to the step of the pixel electrode 105 in the display region and the unevenness between the adjacent pixels are flattened.

  Next, through holes 118 are formed in a cylindrical shape with a diameter of about 10 μm up to the pixel electrode 105 by photolithography and etching, as shown in FIG. 5, and the pixel electrode 105 connected to the source electrode 105 is formed thereon from the ITO film. Was formed by patterning.

  The common electrode wiring 120 was also formed with a through hole 118 in a cylindrical shape having a diameter of about 10 μm, and the ITO film was patterned thereon to form the common electrode 103. At that time, the distance between the pixel electrode 105 and the common electrode 103 was 7 μm, and the electrode wiring pattern other than the scanning electrode 104 was formed in a zigzag bent electrode wiring pattern. At that time, the angle of bending was set to 10 degrees.

  Further, the common electrode 103 is formed in a lattice shape so as to cover the upper part of the video signal wiring 106, the scanning signal wiring 104, and the thin film transistor so as to surround the pixel, and also serves as a light shielding layer.

  As a result, the pixel electrode 105 is arranged between the three common electrodes 103 in substantially the same manner as in Example 4 except that two types of through-holes 118 are formed in the unit pixel. Formed 1024 × 3 × 768 active matrix substrates composed of 1024 × 3 (corresponding to R, G, and B) signal electrodes 106 and 768 scanning electrodes 104.

  As described above, the liquid crystal display device of the ninth example was manufactured as shown in FIG. 5 in the same manner as in the fourth example except for the pixel structure and the alignment control film to be used.

The alignment control film used in this example is diamine, 1,4-diamino-2-vinylbenzene represented by the following general formula [Compound 43], and 4,4 ′ diamino represented by the following general formula [Compound 44]. Diphenylamine was used in a molar ratio of 2: 1, and as the acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 45] and the following general formula [Compound 46 An alignment control film having a film thickness of about 30 nm is produced using a polyamic acid varnish obtained by synthesizing 1-amino-1,2,3,4-cyclobutanetetracarboxylic dianhydride shown in the above formula at a molar ratio of 1: 2. did.

  Next, when the display quality of the liquid crystal display device of this example was evaluated, a high-quality display equivalent to that of the liquid crystal display device of the first example was confirmed, and a wide viewing angle during halftone display was also confirmed. It was.

  Next, in the same manner as in the first embodiment of the present invention, when the image printing and afterimage relaxation time of the liquid crystal display device of this embodiment were quantitatively evaluated, the afterimage relaxation time was 1 minute or less, which was visually observed. Even in the image quality afterimage inspection, no image burning or display unevenness due to the afterimage was observed, and high display characteristics were obtained.

  As shown in FIG. 5, when a pixel electrode directly connected to the TFT is formed on the outermost surface of the substrate and a thin alignment control film is formed thereon, a normal rubbing alignment process causes friction. Charging occurs, and in some cases, the TFT element may be damaged through the pixel electrode near the surface. In such a case, the rubbing-less photo-alignment treatment as in this embodiment is very effective.

  FIG. 6 is a schematic sectional view of the vicinity of one pixel for explaining a fourth embodiment of the liquid crystal display device according to the present invention. In the case of manufacturing the liquid crystal display device of this embodiment, glass substrates 101 and 102 are glass substrates whose thickness is 0.7 mm and whose surface is polished.

  The thin film transistor includes a source electrode (pixel electrode) 105, a drain electrode (signal electrode) 106, a gate electrode (scanning electrode) 104, and a semiconductor film (amorphous silicon) 116. The scanning electrode 104, the common electrode wiring 120 and the signal electrode 106, the pixel electrode 105, and the common electrode 103 were all formed by patterning a chromium film, and the distance between the pixel electrode 105 and the common electrode 103 was 7 μm.

The gate insulating film 107 and the protective insulating film 108 were made of silicon nitride, and the film thicknesses were each 0.3 μm. On top of that, a diamine compound as an alignment control film, 2,5-diaminopyrrole represented by the following general formula [Compound 47], and 1,2,2 represented by the following general formula [Compound 48] as an acid dianhydride. A polyamic acid varnish composed of 3,4-cyclobutanetetracarboxylic dianhydride was printed on the substrate surface, and baked and imidized at 230 ° C. for 30 minutes to form a film having a thickness of about 50 nm.

Then, while irradiating the surface with an electron beam of 5 eV and about 0.5 μC / cm ^{2 in} a vacuum, the light from the high-pressure mercury lamp passes through an interference filter and a quartz pile polarizer in the wavelength range of 220 nm to 380 nm. Polarization UV was irradiated at an irradiation energy of about 3 J / cm 2 to perform photo-alignment treatment.

  As a result, an active matrix substrate having 1024 × 3 × 768 pixels composed of 1024 × 3 (corresponding to R, G, B) signal electrodes 106 and 768 scan electrodes 104 was formed.

  As described above, a liquid crystal display device of this example as shown in FIG. 6 was manufactured in the same manner as Example 1 except for the pixel structure.

  When the display quality of the liquid crystal display device of this example was evaluated, high-quality display equivalent to that of the liquid crystal display device of the first example was confirmed, and a wide viewing angle during halftone display was also confirmed.

  Next, in the same manner as in the first embodiment of the present invention, when the image printing and afterimage relaxation time of the liquid crystal display device of this embodiment were quantitatively evaluated, the afterimage relaxation time was 2 minutes or less and In the image quality afterimage inspection by, no image burn-in or display failure due to afterimage was found.

Further, a polyamic acid varnish synthesized by introducing 50% by mole of 2,5-diamino-3-vinylpyrrole represented by the following general formula [Compound 49], which is a derivative of the diamine compound used in this example, was used. In this case, the same high display characteristics were obtained when the irradiation energy of polarized UV was about 2 J / cm 2.

Except for the composition of the alignment control film used in the eleventh example, the formation of the alignment control film, and the alignment treatment method, the same process as in the tenth example was carried out. As the diamine compound of the alignment control film of this example, And a 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 51] as an acid dianhydride A polyamic acid varnish was printed on the substrate surface and leveled by heat treatment at 90 ° C. for 2 minutes to form a film with a thickness of about 35 nm.

Thereafter, the surface is irradiated with far-infrared rays, and the light from the high-pressure mercury lamp is polarized in the wavelength range of 220 to 380 nm through an interference filter and a quartz pile polarizer while maintaining the film surface at about 230 ° C. Was irradiated at an irradiation energy of about 5 J / cm ² to give a photo-alignment treatment. The film thickness of the orientation control film after the treatment was about 25 nm.

  Thereafter, a liquid crystal display device of this example as shown in FIG. 6 was prepared in the same manner as the tenth example, and after nematic liquid crystal composition A was sealed, annealing was performed at 100 ° C. for 10 minutes, and the above-mentioned irradiation polarized light was applied. Good liquid crystal alignment was obtained in a direction substantially perpendicular to the direction. Thus, a liquid crystal display device having a liquid crystal layer thickness d of 4.0 μm was obtained.

  In addition, a homogeneous alignment cell was prepared using the alignment control film and the liquid crystal composition used in this panel, and the pretilt angle of the liquid crystal was measured using the crystal rotation method. It was.

  Next, when the display quality of the liquid crystal display device of this example was evaluated in the same manner as in the first example, there was no light leakage due to misalignment in the vicinity of the electrode step generally seen in the rubbing alignment process. A high-quality display with a contrast ratio almost equal to that of the liquid crystal display device of the example exceeding 600: 1 over the entire surface was confirmed, and a wide viewing angle during halftone display was also confirmed.

  Further, in the same manner as in the first embodiment of the present invention, when the image printing and afterimage relaxation time of the liquid crystal display device of the eleventh embodiment were quantitatively evaluated, the afterimage relaxation time was 1 minute or less. Even in the image quality afterimage inspection, no image burning or display unevenness due to the afterimage was observed, and high display characteristics were obtained.

Further, a liquid crystal display device was produced in the same manner as in this example, except that polarized ultraviolet rays having a wavelength range of 220 to 260 nm were irradiated with 3 J / cm ² and unpolarized ultraviolet rays having a wavelength of 260 to 400 nm were irradiated with 5 J / cm ² from another light source. As a result of evaluation, a liquid crystal display device having display characteristics equivalent to those of the present example was obtained.

Except for the composition of the alignment control film and the alignment control film formation and alignment treatment method used in the twelfth example, the diamine compound of the alignment control film of this example is represented by the following general formula [Compound 52] as in Example 9. A polyamic acid varnish comprising 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 53] is printed on the substrate surface as the cinnamate derivative shown and acid dianhydride. After forming, leveling by heat treatment at 90 ° C. for 2 minutes was performed to form a film having a thickness of about 40 nm.

Thereafter, the surface is irradiated with far-infrared rays, and the light from the high-pressure mercury lamp is polarized UV in the wavelength range of 220 to 280 nm through an interference filter and a quartz pile polarizer while maintaining the film surface at about 250 ° C. Was irradiated at an irradiation energy of about 3 J / cm ² to perform imidization baking treatment and photo-alignment treatment. The film thickness of the orientation control film after the treatment was about 25 nm.

  Thereafter, a liquid crystal display device of Example 12 as shown in FIG. 5 was prepared in the same manner as Example 9, and after nematic liquid crystal composition A was sealed, it was annealed at 100 ° C. for 10 minutes, and the above-mentioned irradiation polarized light was applied. Good liquid crystal alignment was obtained in a direction substantially parallel to the direction. Thus, a liquid crystal display device having a liquid crystal layer thickness d of 4.0 μm was obtained.

  In addition, a homogeneous alignment cell was prepared using the alignment control film and the liquid crystal composition used in this panel, and the pretilt angle of the liquid crystal was measured using the crystal rotation method. It was.

Next, when the display quality of the liquid crystal display device according to the seventh embodiment of the present invention was evaluated in the same manner as in the first embodiment, light leakage due to misalignment in the vicinity of the electrode step generally observed in the rubbing alignment treatment was observed. In addition, a high-quality display having a contrast ratio almost equal to that of the liquid crystal display device of the first embodiment exceeding 600: 1 over the entire surface was confirmed, and a wide viewing angle during halftone display was also confirmed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation times of the liquid crystal display device of the twelfth embodiment were quantitatively evaluated, the operating temperature range of 0 ° C. to 50 ° C. was used. The afterimage relaxation time was 1 minute or less, and even in visual image quality afterimage inspection, no image burn-in and display unevenness due to afterimage were observed, and high display characteristics were obtained.

  Next, a thirteenth example will be described with reference to FIGS. 7 and 8 as a specific configuration of the liquid crystal display device according to the fifth embodiment of the present invention. In manufacturing the liquid crystal display device according to the thirteenth embodiment of the present invention, a glass substrate having a thickness of 0.7 mm and a polished surface is used as the substrate 101.

  FIG. 7 is a cross-sectional view taken along the line AA ′ of FIG. 8. On the substrate 101, an insulating film 107, a thin film transistor and an electrode 105 for preventing a short circuit of the electrodes 103, 105, 106, 104 are provided. A protective insulating film 108 for protecting 106 is formed to form a TFT substrate.

  FIG. 8 shows the structure of the thin film transistor and the electrodes 103, 105, and 106. The thin film transistor includes a source electrode (pixel electrode) 105, a drain electrode (signal electrode) 106, a gate electrode (scanning electrode) 104, and a semiconductor film (amorphous silicon) 116.

  The scan electrode 104 is formed by patterning an aluminum film, the signal electrode 106 is formed by patterning a chromium film, and the common electrode 103 and the pixel electrode 105 are formed by patterning ITO.

  The insulating film 107 and the protective insulating film 108 were made of silicon nitride, and the film thicknesses were set to 0.2 μm and 0.3 μm, respectively. The capacitor is formed to have a structure in which the insulating films 107 and 108 are sandwiched between the pixel electrode 105 and the common electrode 103.

  The pixel electrode 105 is arranged so as to overlap the upper layer of the solid-shaped common electrode 103. The number of pixels is 1024 × 3 × 768 including 1024 × 3 (corresponding to R, G, and B) signal electrodes 106 and 768 scanning electrodes 104.

On the substrate 102, a color filter 111 with a black matrix 113 having the same configuration as that of the liquid crystal display device according to the first embodiment of the present invention was formed to form a counter color filter substrate.

Next, as an alignment control film, 2,5-diaminopyrimidine represented by the following general formula [Compound 54] and 1,2-diaminoethene represented by the following general formula [Compound 55] are mixed in a diamine compound in a molar ratio of 3: 1. As an acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following general formula [Compound 56] and 1,2,3,4- represented by the following general formula [Compound 57] A polyamic acid varnish having a molar ratio of tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride of 2: 1, a resin concentration of 5% by weight, NMP 60% by weight, γ-butyllactone 20% by weight, butyl cellosolve Adjusted to 15% by weight, printed on the active matrix substrate, imidized by heat treatment at 220 ° C for 30 minutes, and dense polyimide orientation control of about 110 nm A film 109 is formed.

  Similarly, the same polyamic acid varnish is printed on the surface of the other glass substrate 102 on which ITO has been formed, heat-treated at 220 ° C. for 30 minutes, and an orientation composed of a dense polyimide film of about 110 nm. A control film 109 was formed.

In order to impart the liquid crystal alignment ability to the surface, the polyimide alignment control film 109 was irradiated with polarized UV (ultraviolet) light while irradiating far infrared rays. A high pressure mercury lamp is used as a light source, UV light in the range of 240 nm to 380 nm is taken out through an interference filter, and is made into linearly polarized light having a polarization ratio of about 10: 1 using a pile polarizer laminated with a quartz substrate. Irradiation was performed with an irradiation energy of / cm ² . The temperature of the orientation control film at that time was about 120 ° C.

  As a result, it was found that the alignment direction of the liquid crystal molecules on the surface of the alignment control film was orthogonal to the polarization direction of the irradiated polarized UV light.

  The alignment directions of the alignment control film 109 on the TFT substrate and the color filter substrate were substantially parallel to each other, and the angle formed with the direction of the applied electric field 117 was 15 degrees. Polymer beads having an average particle diameter of 4 μm were dispersed as spacers between these substrates, and the liquid crystal 110 was sandwiched between the TFT substrate and the color filter substrate. As the liquid crystal 110, the same liquid crystal composition A as in the first example was used.

  The two polarizing plates 114 sandwiching the TFT substrate and the color filter substrate were arranged in crossed Nicols. A normally closed characteristic that takes a dark state at a low voltage and a bright state at a high voltage is adopted.

  Since the configuration of the system for driving the liquid crystal display device according to the thirteenth embodiment of the present invention is the same as that of the first embodiment, the details of the configuration are omitted.

  Next, when the display quality of the liquid crystal display device according to the thirteenth embodiment of the present invention was evaluated, the aperture ratio was higher than that of the liquid crystal display device of the first embodiment, and a high quality display with a contrast ratio of 650: 1 was obtained. As well as being confirmed, a wide viewing angle during halftone display was also confirmed.

  Similarly to the first embodiment of the present invention, when the image printing and afterimage relaxation time of this liquid crystal display device were quantitatively evaluated, the afterimage relaxation time was 0 ° C to 50 ° C in the operating temperature range. It was about 1 minute, and even in visual image quality afterimage inspection, no image burn-in and display unevenness due to afterimage were observed, and high display characteristics equivalent to Example 1 were obtained.

  Further, when the azimuthal anchoring energy A2 at the liquid crystal alignment film interface was evaluated by the same method as in the first example, a value of about 1.0 × 10 −3 N / m or more was obtained.

  DESCRIPTION OF SYMBOLS 101,102 ... Glass substrate, 103 ... Common electrode (common electrode), 104 ... Scanning electrode (gate electrode), 105 ... Pixel electrode (source electrode), 106 ... Signal electrode (drain electrode), 107 ... Gate Insulating film 108 ... Protective insulating film 109 ... Orientation control film 110 ... Liquid crystal molecule 110 '... Liquid crystal layer (liquid crystal composition layer) 111 ... Color filter 112 ... Organic protective film (interlayer insulating film) 113 ... Light shielding film (black matrix), 114... Polarizing plate, 116... Semiconductor film, 117... Electric field direction, 118.

Claims (8)

An alignment film material used for a photo-reactive alignment control film,
The alignment film material is composed of polyamic acid or polyimide composed of cyclobutanetetracarboxylic dianhydride and its derivative and a diamine compound,
The cyclobutanetetracarboxylic dianhydride and derivatives thereof are represented by the following general formulas 1 to 3 (wherein R1, R2, R3, and R4 are independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, A phenyl group or an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a vinyl group [— (CH ₂ ) m —CH═CH ₂ , m = 0, 1, 2], or an alkynyl group [— (CH ₂ ) m — At least one compound selected from the group consisting of CH≡CH, m = 0, 1, 2]),
The diamine compound is compound 5 to compound 18, compound 21, or compound 22 represented by the following general formula (wherein R1 to R8 of compound 5 to compound 18 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a carbon atom) An alkyl group, an alkoxy group, or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0,1,2] or an alkynyl group [— (CH ₂ ) m—CH≡CH , M = 0, 1, 2] In compounds 10 to 12, X represents a —CH ₂ —, —NH—, —CO—, —O—, or —S— bonding group. R1 of compounds 21 and 22 each independently represents an alkyl group having 1 to 6 carbon atoms.) An alignment film material containing at least one compound selected from the group consisting of compounds.

The diamine compound may further be compound 19 or compound 20 represented by the following general formula (R1 and R2 of compound 19 and compound 20 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 6 carbon atoms. , An alkoxy group, or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0,1,2,], or an alkynyl group [— (CH ₂ ) m—CH≡CH, m = 0,1, 2) In addition, R3 and R4 of Compound 20 each independently represents an alkyl group having 1 to 6 carbon atoms.) The compound 20 comprises at least one compound selected from the group consisting of compounds. Alignment film material.

An alignment film material used for a photo-reactive alignment control film,
The alignment film material is composed of polyamic acid or polyimide composed of cyclobutanetetracarboxylic dianhydride and its derivative and a diamine compound,
The cyclobutanetetracarboxylic dianhydride and derivatives thereof are compounds 1 represented by the following general formula (where R1, R2, R3 and R4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group or An alkyl group having 1 to 6 carbon atoms, an alkoxy group or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0, 1, 2], or an alkynyl group [— (CH ₂ ) m—CH≡CH , M = 0, 1, 2]),
The diamine compound is a compound 7 represented by the following general formula (wherein R1 to R2 of the compound 7 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or vinyl) A group [— (CH ₂ ) m—CH═CH ₂ , m = 0,1,2] or an alkynyl group [— (CH ₂ ) m—CH≡CH, m = 0,1,2]. And Compound 19 (R1 and R2 of Compound 19 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group, alkoxy group, or vinyl group having 1 to 6 carbon atoms [— (CH ₂ ) m—CH═CH ₂ , m = 0,1,2], or an alignment film material containing an alkynyl group [— (CH ₂ ) m—CH≡CH, m = 0,1,2].

The cyclobutanetetracarboxylic dianhydride and derivatives thereof are further compound 1 represented by the following general formula (where R1, R2, R3 and R4 are independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, phenyl Group or an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0, 1, 2], or an alkynyl group [— (CH ₂ ) m—CH 2. The alignment film material according to claim 1, comprising one compound selected from the group consisting of ≡CH, m = 0, 1, 2]).

An alignment film material used for a photo-reactive alignment control film,
The alignment film material is composed of polyamic acid or polyimide composed of cyclobutanetetracarboxylic dianhydride and its derivative and a diamine compound,
The cyclobutanetetracarboxylic dianhydride and derivatives thereof are compounds 1 represented by the following general formula (where R1, R2, R3 and R4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group or An alkyl group having 1 to 6 carbon atoms, an alkoxy group or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0, 1, 2], or an alkynyl group [— (CH ₂ ) m—CH≡CH M = 0, 1, 2]),
The diamine compound is a compound 4 and a compound 44 represented by the following general formula, or a compound 16 and a compound 18 (provided that R1 to R6 of the compounds 4, 16, and 18 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, Alternatively, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0, 1, 2], or an alkynyl group [— (CH ₂ ) m—CH ≡CH, m = 0, 1, 2]) (provided that compound 1 in which R1 to R4 are all hydrogen atoms includes compound 1, and 1,3-dimethyl-1,2, Except when it contains 3,4-cyclobutanetetracarboxylic dianhydride ).

An alignment film material used for a photo-reactive alignment control film,
The photoreactive alignment control film is composed of polyamic acid or polyimide composed of cyclobutanetetracarboxylic dianhydride and its derivative and a diamine compound,
The cyclobutanetetracarboxylic dianhydride and derivatives thereof are compounds 2 or 3 represented by the following general formula (where R1, R2, R3, and R4 are independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, phenyl Group or an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a vinyl group [— (CH ₂ ) m—CH═CH ₂ , m = 0,1,2,2], or an alkynyl group [— (CH ₂ ) m—CH At least one compound selected from the group consisting of ≡CH, m = 0, 1, 2]),
The diamine compound is compound 4 to compound 22 represented by the following general formula (wherein R1 to R8 of compound 5 to compound 18 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 6 carbon atoms) , an alkoxy group or a vinyl _{group, [- (CH 2) m} -CH = CH 2, m = 0,1,2], or an alkynyl group _{[- (CH 2) m-} CH≡CH, m = 0,1, In the compounds 10 to 12, X represents a bonding group of —CH ₂ —, —NH—, —CO—, —O—, —S—, and R 1 of the compounds 21 and 22 represents Each independently represents an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 of compound 4, compound 19 and compound 20 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 6 carbon atoms, Alkoxy group or vinyl group [ _{(CH 2) m-CH-} CH 2, m = 0,1,2], or alkynyl group [-. Shows a _{(CH 2) m-CH≡CH,} m = 0,1,2] Furthermore, compound 20 R3 and R4 each independently represents an alkyl group having 1 to 6 carbon atoms.) An alignment film material comprising at least one compound selected from the group consisting of compounds consisting of:

The photoreactive alignment control film, according to claim 1 to 6, characterized in that it includes a repeating structure of a polyamic acid or a polyimide consisting cyclobutane tetracarboxylic dianhydride and its derivative and a diamine compound in which at least 50% or more The alignment film material according to any one of the above. Examples alignment film material, further, NMP, alignment film material according to any one of claims 1 to 7 including the γ-butyrolactone or butyl cellosolve.

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