JP2011141486A - Color filter substrate for transreflective type liquid crystal display device, and the transreflective-type liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter substrate in which the retardation is properly adjusted and which has excellent flatness, is formed precisely with a small number of steps and is the most suitable for a transreflective-type liquid crystal display device, and to provide the transreflective-type liquid crystal display device. <P>SOLUTION: The color filter substrate for the transreflective-type liquid crystal display device, in which a light-shielding layer formed by using the mixture of a plurality of organic pigments as a main color material is arranged on the outer periphery of an effective display region on a transparent substrate and green pixel-including colored pixels of two or more colors are formed in the effective display region, includes a spacer pedestal formed in the effective display region, made of the same material as that of the light-shielding layer and has the thickness thinner than that of the light-shielding layer; a spacer which is formed above the spacer pedestal and includes a monochromatic colored layer; a plurality of light scattering layers formed in the reflection part of the transreflective-type liquid crystal display device; and a plurality of first cell gap control layers formed at the positions, corresponding to those of the light scattering layers on the colored pixels. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a color filter substrate for a liquid crystal display device and a liquid crystal display device, and more particularly, to a color filter substrate for a transflective liquid crystal display device using both a backlight on the back surface of the liquid crystal display device and external light, and a transflective provided with the same. The present invention relates to a liquid crystal display device. In particular, the present invention relates to a color filter substrate suitable for a liquid crystal driving system such as FFS or IPS.

  In recent years, there has been a demand for further higher image quality, lower cost, and lower power consumption in thin display devices such as liquid crystal displays. A color filter for a liquid crystal display device has been required to have electrical characteristics such as sufficient color purity, high contrast, flatness, and low dielectric constant that do not hinder liquid crystal driving.

  In high-quality liquid crystal displays, liquid crystal driving methods such as IPS (In-Plane Switching), VA (Vertical Aligned), HAN (Hybrid Aligned Nematic), FFS (Fringe Field Switching), OCB (Optically Compensated Bend), etc. Have been put into practical use, and a display with a wide viewing angle and a high-speed response has been put to practical use.

  In liquid crystal display devices such as an IPS system in which liquid crystals are aligned in parallel on a substrate surface made of glass, a VA that easily supports high-speed response, and an FFS system that is effective for a wide viewing angle, the flatness (film thickness) for color filters Higher level of electrical characteristics such as the uniformity of the color filter and the unevenness of the color filter surface) and the dielectric constant.

  In such a high-quality liquid crystal display, a technique for reducing the thickness of the liquid crystal cell (the thickness of the liquid crystal layer) has been a major issue in order to reduce coloring when viewed obliquely. In a vertical electric field type liquid crystal display device that applies a driving voltage in the thickness direction of the liquid crystal layer such as VA, a technique for reducing the thickness of the liquid crystal cell (the thickness of the liquid crystal layer) is a major issue in order to further increase the response speed. Yes.

  In order to reduce the coloration of the liquid crystal display device when viewed in an oblique direction, there is a technique in which a colored layer is overlapped and used as a spacer in order to make the liquid crystal cell thickness uniform in addition to flattening the color filter (for example, patents) References 1 and 2). Forming the spacers by a laminated body such as a colored layer by a photolithography technique is excellent from the viewpoint of securing a uniform liquid crystal cell gap.

  However, the patent documents disclosing these techniques do not describe color filter characteristics and configuration suitable for the FFS method and the IPS method, and do not describe a transflective liquid crystal display device including a light scattering layer. .

  A general liquid crystal cell such as the FFS method or the IPS method is configured by bonding the color filter side of the color filter substrate and the array side of the array substrate so as to face each other. Usually, a spacer for securing the liquid crystal thickness of the liquid crystal cell is provided in the color filter to control the thickness of the liquid crystal sandwiched between the color filter substrate and the array substrate.

  In many transmissive liquid crystal display devices, a diffuser plate for diffusing light is installed on the back surface of the array substrate as a liquid crystal cell together with the above-described backlight. In general, the basic configuration of a liquid crystal display device of FFS mode or IPS mode is a color filter substrate and a plurality of pixel electrodes (for example, TFT elements that are electrically connected to a liquid crystal), and in a comb-like pattern shape. The liquid crystal is sandwiched between the formed transparent electrode) and the array substrate having the common electrode. In such a configuration, since the common electrode is formed on the array substrate side, the common electrode is formed on the color filter surface of the color filter substrate (usually a thin film of conductive metal oxide called ITO, also called a transparent electrode). There is no need to form.

  The liquid crystal drive by the FFS method is a liquid crystal aligned in a parallel direction (horizontal) with the surface of the array substrate. The comb-like pixel electrode as described above and an insulating layer of about 0.3 μm to 0.5 μm below the pixel electrode This is a system driven by an arch-shaped electric field (lines of electric force) generated between the common electrode disposed via the. In many cases, a backlight using a fluorescent lamp or an LED is provided on the back or side of these FFS, IPS, and VA liquid crystal display devices.

  Recently, in the configuration of these FFS mode and IPS mode liquid crystal display devices, all or part of the common electrode is formed of a light-reflective metal thin film of an aluminum alloy or a silver alloy, so that a reflective type or a transflective type is obtained. A study on usable liquid crystal display devices is in progress. In a transflective LCD, one pixel is divided into a transmissive portion that uses light from the back surface of the backlight as transmitted light, and a reflective portion that reflects external light and light from the front light. This is a liquid crystal display device used in a divided manner. Alternatively, it is a liquid crystal display device in which the backlight can be turned off and the display can be visually recognized with bright external light such as sunlight in a bright outdoor environment.

  Techniques for forming a light scattering film for a reflective or transflective liquid crystal display device are disclosed in Patent Documents 3 and 4, for example. However, these patent documents do not disclose color filter characteristics suitable for the FFS method and the IPS method, and these techniques are transparent on the color filter disposed on the observer side electrode substrate or the like. It is assumed that the electrodes are stacked.

  A technology of a phase difference element having different phase differences for each color of red, green, and blue, a technology of a continuous phase difference layer laminated on a color filter, and the like are known (see, for example, Patent Documents 5 and 6). None of these patent documents disclose a color filter characteristic suitable for the FFS method or the IPS method, and does not describe a transflective liquid crystal display device including a light scattering layer.

  A technique (for example, refer to Patent Documents 7 and 8) in which a quarter-wave retardation layer is provided in a reflection part of a transflective liquid crystal display device for the purpose of phase difference adjustment. The technique disclosed in Patent Document 7 relates to a color filter having different phase differences between a reflection part and a transmission part. However, none of these patent documents disclose color filter characteristics suitable for the FFS method and the IPS method, and there is no description of a technique related to the light scattering layer.

  As an IPS type color liquid crystal display device, there is a technique for eliminating light leakage by increasing the optical density of a light-shielding frame outside the effective liquid crystal display area (see, for example, Patent Document 9). However, in this patent document, there is no description of a technique related to a cell gap regulating layer or a light scattering layer so as to be applied to a transflective liquid crystal display device.

  A technique of applying the FFS method to a vertical alignment (VA) liquid crystal display device is also known (see, for example, Patent Document 10).

JP-A-63-82405 JP-A-9-49914 Japanese Patent No. 3886740 Japanese Patent Laid-Open No. 2001-272675 JP 2004-191832 A JP 2005-24919 A JP 2008-165250 A Japanese Patent Application No. 9-536964 Japanese Patent Application No. 10-170958 JP 2007-34151 A

  In the above-described prior art, the technique of simply using color overlap as a spacer (Patent Document 1) is not preferable from the viewpoint of liquid crystal alignment because the film thickness at the end of the colored pixel protrudes as it is at the color overlap portion. For example, the film thickness of the colored pixels on the color filter substrate is usually around 1.5 μm to 3 μm, and in a liquid crystal display device such as an FFS method or IPS method that requires high image quality, there is a height that surrounds the colored pixels. The protrusions hinder liquid crystal alignment. Even if the spacers are not formed by color superposition, in a normal color filter, as shown in FIG. 12, a step a or a protrusion b is generated in the overlapping portion between the light shielding layer 2 or the black matrix 8 and the colored pixel 3, and the liquid crystal Disturbance of alignment occurs, causing light leakage.

  Further, in paragraph 0023 of Patent Document 2, carbon black is excellent in terms of light shielding properties and is particularly preferable. However, carbon black is a colorant having a high dielectric constant, and liquid crystal such as FFS mode and IPS mode is used. Not suitable for display devices. When carbon is used as the main coloring material (100% to 90% with respect to the total amount of pigment (weight ratio)), the relative permittivity of the light shielding layer and the black matrix is approximately 7 to 15, and the liquid crystal drive of the FFS method or IPS method is used. This is a color filter constituent member that is not suitable for.

  The relative dielectric constant of a liquid crystal material driven by an active element such as a TFT is about 7 to 40 in the molecular direction where the relative dielectric constant is large. As a constituent member of a color filter for an FFS mode or IPS mode liquid crystal display device, the relative dielectric constant thereof is 5 or less, preferably 4.5 or less. In a liquid crystal display device such as an FFS method or an IPS method, an arch-shaped electric field line formed between a comb-like pixel electrode and a common electrode has a conventional light-shielding layer containing a high dielectric constant color material such as carbon. The deformation was caused by the black matrix, which hindered the uniform response of the liquid crystal layer.

  Further, these techniques (including Patent Document 2) for disposing a black matrix using a light-shielding material do not consider the thickness of the black matrix and the colored pixels from the viewpoint of flatness, and liquid crystal that requires high image quality. It is difficult to apply to display devices. In addition, these conventional technologies improve the flatness of the green pixels and the light-shielding layer (light-shielding frame) in consideration of the visibility of the human eye, and do not increase the number of manufacturing processes. The technology used as a device is not included.

  In addition, the technology using the light scattering layer (Patent Documents 3 and 4) is suitable for liquid crystal display devices such as the FFS method and the IPS method in terms of the electrical characteristics and flatness of color filter members such as a light shielding layer and a black matrix. However, the drive voltage applied between the pixel electrode and the common electrode peculiar to the FFS method and the IPS method has a problem in smooth electric field formation through the liquid crystal, and there is a problem in high image quality display. These techniques do not consider the phase difference adjustment necessary for the transflective liquid crystal display device.

  The technique of Patent Document 7 that discloses a phase difference adjustment technique in a transflective liquid crystal display device has high intensity such as sunlight, does not assume the use of a liquid crystal display device under parallel light, and is bright and dark. It was not a liquid crystal display device that could be used with any environment. Furthermore, it does not correspond to liquid crystal display devices such as the above-described FFS method and IPS method, and there is no description about the color filter characteristics necessary for these liquid crystal display devices.

  The present invention has been made in view of the circumstances as described above, and is an optimum color filter substrate for a transflective liquid crystal display device that is appropriately adjusted for phase difference, has excellent flatness, and can be accurately formed with few steps. It is another object of the present invention to provide a transflective liquid crystal display device including such a color filter substrate.

  In order to solve the above-mentioned problem, a first aspect of the present invention includes a light-shielding layer mainly composed of a mixture of a plurality of organic pigments on a transparent substrate, and a green pixel. In a color filter substrate for a transflective liquid crystal display device in which colored pixels of a plurality of colors are formed in an effective display area, the film is formed in the effective display area and is made of the same material as the light shielding layer and is thinner than the light shielding layer A spacer pedestal having a spacer, a spacer formed of a monochromatic colored layer formed above the pedestal, a plurality of light scattering layers formed on a reflective portion of a transflective liquid crystal display device, and the light scattering on the colored pixels A color filter substrate for a transflective liquid crystal display device comprising a plurality of first cell gap regulating layers formed at positions corresponding to the layers.

  In such a color filter substrate for a transflective liquid crystal display device, the green pixel can be formed of a green color layer containing zinc halide phthalocyanine as a main color material.

  Further, the difference in height between the surface of the cell gap regulating layer and the surface of the colored pixel can be set to about ½ of the thickness of the liquid crystal layer of the liquid crystal display device.

  In addition, the color filter substrate of this aspect further includes a second cell gap regulating layer formed on the light shielding layer and having the same shape as the light shielding layer, and the light shielding layer and the second cell gap regulating layer. The total film thickness can be substantially the same as the film thickness of the green pixel.

  As the light scattering layer, a rectangular shape having a plan view size smaller than that of the colored pixel can be used.

  The adjacent portions of the colored pixels may be overlapped at the inclined portions at the end portions of the colored pixels.

  Furthermore, the color filter substrate of this aspect may further include a black matrix made of the same material as the light shielding layer, which is disposed so as to partition the colored pixels in the effective display area on the transparent substrate.

  The film thickness of the pedestal can be 0.4 μm to 1.0 μm.

  The first cell gap regulating layer may have a function of rotating the incident light converted into linearly polarized light by 90 degrees in one round trip in the thickness direction of the cell gap regulating layer.

  The plurality of colored pixels may include at least a red pixel, a green pixel, and a blue pixel, and a phase difference between these colored pixels may be in a relationship of red pixel ≧ green pixel ≧ blue pixel.

  The plurality of colored pixels include at least a red pixel, a green pixel, and a blue pixel, and a phase difference between each of the colored pixels and a phase difference between each of the first cell gap regulation layers stacked on the colored pixel. The total may be in the relationship of red pixel ≧ green pixel ≧ blue pixel.

  The spacer can also serve as a liquid crystal alignment control and can be disposed at the center in the longitudinal direction of the colored pixel.

  According to a second aspect of the present invention, there is provided a transflective liquid crystal display device comprising the above color filter substrate for a transflective liquid crystal display device.

  According to the present invention, a color filter substrate that is suitable for a transflective liquid crystal display device that has been subjected to appropriate phase difference adjustment, has excellent flatness, and can be accurately formed with few processes, and such a color filter substrate are provided. A transflective liquid crystal display device is provided.

It is a figure which shows the one part cross section of the color filter board | substrate which concerns on one Embodiment of this invention. It is a figure which expands and shows the part enclosed with the circle of the broken line of the color filter board | substrate shown in FIG. It is a figure which shows the cross section of the other part of the color filter board | substrate which concerns on one Embodiment of this invention. It is a figure which shows the planar arrangement | positioning of the light shielding layer, a base, and a spacer in the color filter substrate which concerns on one Embodiment of this invention. It is a characteristic view which shows the relationship between the film thickness of a base, and the film thickness of the laminated part of the colored layer on a base. It is a figure which shows the planar view arrangement | positioning of the light shielding layer, a base, a black matrix, a light-scattering layer, and a spacer in the color filter substrate which concerns on other embodiment of this invention. It is a characteristic view showing the relationship between the film thickness of the black matrix and the height of the protrusion of the colored pixel end portion superimposed on the black matrix. It is sectional drawing which shows the shape and inclination | tilt angle of the pattern edge of the colored pixel of a thick film thickness. It is sectional drawing which shows the shape and inclination | tilt angle of the pattern edge of the colored pixel of a thin film thickness. It is sectional drawing of the liquid crystal display device provided with the color filter substrate shown in FIG. It is a figure which expands and shows a part of liquid crystal display device shown in FIG. It is a figure which shows the level | step difference or protrusion which arises between the colored pixel and the light shielding layer or black matrix in the conventional color filter substrate.

  Hereinafter, embodiments of the present invention will be described.

  Before describing embodiments of the present invention, the meanings of terms used in this specification will be described.

  In the present specification, the light shielding layer and the frame portion are synonymous and mean a frame-shaped light shielding pattern on the outer periphery of the effective display area.

  Usually, a liquid crystal display panel is obtained by bonding a color filter substrate and a TFT substrate on which an active element for driving liquid crystal is formed facing each other so as to sandwich a liquid crystal layer. The pedestal corresponds to the position of an active element such as a TFT when such a liquid crystal display panel is assumed, and is arranged on the color filter substrate side for the purpose of shielding the light. In plan view, an area that roughly covers the active element is sufficient.

  In the present invention, in addition to the base, a black matrix may be formed as necessary. The black matrix refers to a light shielding pattern in a lattice shape or a stripe shape that is formed in a display region for the purpose of improving the contrast of a liquid crystal display device.

  The spacer is a member for maintaining the cell thickness (liquid crystal thickness) of the liquid crystal display device targeted by the present invention, and the spacer height is substantially the same as the liquid crystal thickness. As described above, the liquid crystal display element is made into a panel because the color filter substrate and the array substrate on which the active element for driving the liquid crystal is formed face each other so as to sandwich the liquid crystal. Must include the margin at this time. For example, the height is obtained by adding a margin of about 0.1 μm to the liquid crystal thickness. The height of the spacer is the height from the top of the spacer to the surface of the colored pixel at the center between adjacent pixels.

  The thickness of the pedestal and the black matrix is preferably thinner than the thickness of the light shielding layer. The method of forming these thinly can be adjusted by adjusting the halftone mask used for exposure, the graytone mask, the opening shape of the mask, etc. in addition to the adjustment in the process such as the development step and the heat treatment step.

  A colored pixel is formed by applying a photosensitive coloring composition on a transparent substrate to form a colored layer, and patterning the colored layer by a known photolithography technique. The film thickness of the colored pixel refers to the height from the surface of the transparent substrate to the center surface of each pixel. The height of the overlapping portion (hereinafter referred to as a protrusion) of adjacent colored pixels is the height from the top of the protrusion to the surface of the colored pixel at the center of the pixel. The colored pixels of a plurality of colors are blue pixels, red pixels, green pixels, yellow pixels, white pixels (transparent pixels), and the like.

  In the present invention, a configuration of a plurality of colored pixels including a light shielding layer is referred to as a color filter, and a color filter formed on a transparent substrate such as glass is referred to as a color filter substrate. In the present invention, the substantially same film thickness means that the film thickness difference can be controlled by the manufacturing process in the formation of the light shielding layer and the colored layer, for example, ± 0.2 μm with respect to the set film thickness, or ± The case where it exists in the range of 0.15 micrometer is said.

  In addition, the colored pixel according to the present invention includes a reflection unit that targets light incident from the observer side such as outside light and front light, and a transmission unit that uses light from the backlight on the back surface of the liquid crystal display device. Divided into The cell gap regulating layer according to the present invention is disposed in the reflective part of one pixel for the purpose of adjusting the optical path difference of the liquid crystal. In addition to adjusting the optical path difference, the cell gap regulating layer according to the present invention has a phase difference function of 1/4 wavelength or 1/2 wavelength in order to eliminate the difference between the transmissive part display and the reflective part display. It is particularly preferred.

  The relative dielectric constant referred to in the present specification is premised on measurement at a frequency of 50 Hz to 500 Hz used for liquid crystal driving at room temperature.

  FIG. 1 is a diagram showing a partial cross section of a color filter substrate according to an embodiment of the present invention.

  In FIG. 1, a light-shielding layer 2 made mainly of an organic pigment at the outer peripheral frame portion of the display area on the transparent substrate 1 has three colors consisting of a red pixel 3R, a green pixel 3G, and a blue pixel 3B in the display area. Each colored pixel is formed. The thickness of the light shielding layer 2 and the thickness of the colored pixels are substantially the same. A pedestal 4 made of the same material as the light shielding layer 2 is formed on the transparent substrate 1 at the boundary between the green pixel 3G and the blue pixel 3B, and a spacer 5 made of a red colored layer is formed above the pedestal 4. ing. The height h of the spacer 5 is the thickness of the portion protruding from the surface of the colored pixels 3R, 3G, 3B, and is substantially equal to the thickness of the colored layer.

  On the transparent substrate 1 at the boundary between the red pixel 3R and the green pixel 3G, a pedestal 4 'made of the same material as that of the light shielding layer 2 is formed above which the spacer 5 is not formed. The pedestal 4 ′ in which the spacer 5 is not formed is provided for the purpose of adjusting the aperture ratio of the red pixel R, the green pixel G, and the blue pixel B and shielding the active elements such as TFTs. A sub-spacer 6 having a height lower than that of the spacer 5 is disposed on the light shielding layer 2.

  The pedestal 4 is desirably thinner than the light shielding layer 2 and has a thickness of 0.4 μm or more and 1.0 μm or less. When the film thickness of the pedestal 4 is less than 0.4 μm, it is difficult to obtain a stable film thickness when the pedestal 4 is formed by photolithography. On the other hand, when the thickness exceeds 1.0 μm, the thickness of the colored layer laminated thereon becomes thin, a sudden change in film thickness occurs, and the thickness of the colored layer becomes unstable.

  In one embodiment of the present invention, the light shielding layer and the pedestal can be formed in the same photolithography process, as will be described later.

  A TFT substrate is disposed opposite to the color filter substrate configured as described above, and a liquid crystal display device is configured by interposing a liquid crystal layer between the color filter substrate and the TFT substrate. Is thicker than the thickness of the liquid crystal layer.

  FIG. 2 is an enlarged view of a portion surrounded by a broken-line circle of the color filter substrate shown in FIG. A portion surrounded by a broken-line circle is an overlapping portion of the blue pixel 3B and the green pixel 3G. The overlapping portion is a protrusion 7 protruding from the surface of the pixel. If the height d of the protrusion 7 is too high, the flatness of the pixel is impaired. Therefore, it is desirable that the overlapping portion be 0.25 μm or less. .

  FIG. 3 is a view showing a cross section of another part of the color filter substrate according to the embodiment of the present invention.

  In FIG. 3, a light scattering layer 11 is formed at a position below the colored pixel 3 in the reflecting portion on the transparent substrate 1, and a cell gap restriction is formed above the light scattering layer 11 and above the colored pixel 3. Layer 12 is formed.

  The light scattering layer 11 is formed by dispersing single or plural kinds of amorphous fine particles 13 in a matrix resin 16 having different refractive indexes. The light scattering layer 11 scatters incident light to make a paper white-like effect in the eyes of an observer. Is an optical functional film having The matrix resin 16 may be a transparent resin having heat resistance and visible range transparency. The film thickness of the light scattering layer 11 is preferably in the range of about 1.5 μm to 5 μm because of the relationship between the amorphous fine particle diameter, the light wavelength, and the suitability in the manufacturing process.

  FIG. 4 is a diagram showing a planar arrangement of the light shielding layer 2, the pedestals 4, 4 ', the spacer 5, and the light scattering layer 11 in the color filter substrate. 4 corresponds to FIG. 1, and the C-C ′ section corresponds to FIG. 3. The pedestal 4 ′ not formed with the spacer 5 is disposed for the purpose of adjusting the aperture ratio of the red pixel 3 </ b> R, the green pixel 3 </ b> G, and the blue pixel 3 </ b> B and shielding light from active elements such as TFTs. Further, as shown in FIG. 1, a sub-spacer 6 having a height lower than that of the spacer 5 provided in the effective display area can be provided in the frame portion. In FIG. 1, the cell gap regulating layer 12 is not shown.

  According to one embodiment of the present invention described above, a color filter substrate that is excellent in flatness and can be formed with high accuracy with few processes, and a liquid crystal display device including the color filter substrate are provided.

  The cell gap regulating layer 12 shown in FIG. 3 is disposed for the purpose of adjusting the thickness of the liquid crystal layers of the transmissive part and the reflective part in the transflective liquid crystal display device. In the present invention, the height difference H between the surface of the cell gap regulating layer and the colored pixel surface where the light scattering layer 11 is not formed is approximately ½ of the thickness of the liquid crystal layer when the liquid crystal display device is constructed. It is desirable. The height H is desirably a value within ± 10% in addition to 1/2 of the thickness of the liquid crystal layer. In the case of a hybrid alignment liquid crystal display device in which the liquid crystal alignment of the transmission part is horizontal alignment (IPS) and the liquid crystal alignment of the reflection part is TN (twisted nematic), the thickness of the cell gap regulating layer is set to be less than −10%. Also good. In the following description of the present specification, the film thickness of the cell gap regulating layer or the like refers to a film thickness within a range obtained by adding ± 0.2 μm as a manufacturing margin in the color filter manufacturing process. The film thickness of approximately ½ is a film thickness including such a margin.

  The cell gap regulation layer may be made of an insulating material that is transparent in the visible range, but it is preferable to provide a function of forming a phase difference as will be described later. Providing a color filter substrate that is optimal for a transflective liquid crystal display device by placing a cell gap regulating layer on a colored pixel with the function of changing the phase of linearly polarized light by 1/4 wavelength or 1/2 wavelength. can do.

  In other words, the cell gap regulating layer can be provided with a function of rotating the polarization of incident light converted to linearly polarized light by 90 degrees in one round trip in the thickness direction of the same liquid crystal layer. Specifically, in a configuration of a reflective liquid crystal display device using a light-reflecting reflective electrode, a function of changing the phase of the polarized light by a quarter wavelength or a half wavelength is provided so that the liquid crystal layer can be used once in the thickness direction. This is a function of making the linearly polarized light different in the direction of 90 degrees by reciprocation (reflection).

  Further, after adjusting the absorption axis of the polarizing plate and the slow axis of the retardation layer, a half-wave retardation layer may be used to rotate the polarization by 90 degrees or 270 degrees. For example, in an IPS mode liquid crystal display device that is aligned parallel to the substrate surface and rotated in the substrate surface direction, the absorption axis of the polarizing plate and the slow axis of the retardation layer are shifted by 22.5 degrees or 67.5 degrees, By using a half-wave retardation layer, incident light converted into linearly polarized light can be effectively rotated by 90 degrees. By applying the retardation layer to the reflective portion of the transflective liquid crystal display device with the above-described configuration, the optical path difference between the reflective portion and the transmissive portion can be adjusted and the phase can be compensated.

  Assuming liquid crystal alignment in the VA mode or TN mode liquid crystal display mode, the angle formed by the slow axis of the quarter-wave retardation layer and the absorption axis of the polarizing plate can be about 45 degrees.

  A liquid crystal display device in which a cell gap regulating layer (second cell gap regulating layer) is laminated on the frame-shaped light shielding layer 2 and made substantially the same as the green pixel 3G, thereby eliminating light leakage due to disorder of liquid crystal alignment. Can be provided. Green is an important color with high visibility to the human eye, and light easily leaks due to its spectral characteristics. The thickness of the liquid crystal such as the frame is preferably based on the green pixel. In addition, a high-quality liquid crystal display device can be provided by using a light-shielding layer having a plurality of organic pigments as a main color material and zinc halide phthalocyanine having excellent electrical and optical characteristics as a main color material for a green pixel.

  Furthermore, according to the present embodiment, the phase difference between the blue pixel, the green pixel, and the red pixel as the color filter pixel, or the phase difference obtained by adding the cell gap restriction layer to these colored pixels is set to red pixel ≧ green pixel ≧ blue pixel. By using the relationship, it is possible to compensate for wavelength dispersion that is not sufficient only by the cell gap regulating layer or the cell gap regulating layer provided with a phase difference function. At least, it is possible to eliminate the undesirable relationship that the phase difference is red pixel <green pixel <blue pixel, and light leakage in black display and coloring in display can be reduced.

  In particular, in the IPS system, the phase difference of the reflection portion of the blue pixel and the blue pixel is made smaller than the phase difference of the other colored pixels while maintaining the wavelength relationship (wavelength magnitude relationship) of the transmission peaks of the other colored pixels. Thus, it is possible to reduce the leakage of blue light in black display.

  In addition, the film thickness of the colored pixel is in the relationship of red pixel ≦ green pixel ≦ blue pixel. In other words, the film thickness of the liquid crystal layer on each color pixel is red display portion ≧ green display portion ≧ blue display portion. The effect can be imparted and the image quality of the liquid crystal display device in the entire visible range can be improved.

  Next, the light shielding layer 2, the red pixel 3R, the green pixel 3G, the blue pixel 3B, the pedestal 4, the spacer 5, the light scattering layer 11, and the cell gap regulating layer 12 of the color filter substrate having the above configuration are configured. The material will be described.

  First, organic pigments that can be used for the light shielding layer 2, the red pixel 3R, the green pixel 3G, the blue pixel 3B, the base 4, and the spacer 5 are listed below. The organic pigment to be contained in the light shielding layer is a mixture of various organic pigments, but the green pigment described below may be omitted, and the relative dielectric constant of the light shielding layer is not increased (for example, relative dielectric constant 5 In the following, carbon may be added. The carbon that can be added is more preferably carbon particles subjected to resin coating or surface treatment in order to lower the relative dielectric constant. The carbon that can be added is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total amount of the pigment.

  When carbon is used as the main coloring material (100% to 90% by mass with respect to the total amount of pigment), the light blocking layer and the black matrix have a relative dielectric constant of about 7 to 15, which can be used for liquid crystal driving in the FFS mode and IPS mode. Becomes an unsuitable color filter component.

  The amount of the organic pigment used is preferably 90% by mass or more, particularly preferably 95% by mass or more, based on the total amount of the pigment. In the light shielding layer in the color filter substrate of the present invention, all of the color material can be an organic pigment.

(Organic pigment)
Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, H.264, 272, 279, etc. can be used.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 1 73, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and the like.

  Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc., among which C.I. I. Pigment Blue 15: 6 is preferred.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used. I. Pigment Violet 23 is preferred.

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, etc. can be used. In C.I. I. Pigment Green 58 is preferred.

  Hereinafter, C.I. I. In the description of Pigment pigment types, it may be simply abbreviated as PB (Pigment Blue), PV (Pigment Violet), PR (Pigment Red), PY (Pigment Yellow), PG (Pigment Green), or the like.

  The above-described PG58 is called zinc halide phthalocyanine, and its production example is shown in [Pigment production example G2] described later. PG58 has a smaller dielectric constant than the halogenated copper phthalocyanine, which is PG36, and can form a green pixel with high brightness. PG58 and PG36 are organic pigments having substantially the same structure except that the central metal is zinc and copper, but PG58 tends to be smaller in electrical characteristics including variations in dielectric constant.

  Despite the similarity in structure, the reason why PG58 is suitable for the present invention, according to the knowledge of the present inventors, is demonstrated from the following optical measurement (measurement of birefringence Δn of green pigment). Can do. In addition, the one where the solid ratio of organic pigments, such as a halogenated zinc phthalocyanine in a coloring composition, has a tendency to reduce a dielectric constant is preferable.

  In order to reduce the stray capacitance caused by the color filter that hinders the liquid crystal drive, it is preferable to decrease the pigment ratio and increase the resin ratio. Therefore, it is preferable to increase the thickness of the light shielding layer and the colored pixels as in the embodiment of the present invention.

[Measurement of birefringence Δn of green pigment]
As is well known, the value of the dielectric constant is approximately equal to the square of the refractive index. In other words, the dielectric constant resulting from electronic polarization is proportional to the square of the refractive index.

  From this point of view, the difference in polarization between PG58 and PG36 was clarified by measuring refractive indexes Nx, Ny, and Nz on the orthogonal coordinate system X-axis, Y-axis, and Z-axis, respectively. In order to make the measurement sample have a configuration close to the green coloring layer actually used, a pigment dispersion (for example, GP-4) shown in Table 3 below was applied on a glass substrate to a thickness of 1 μm and dried at 230 ° C. Things were used.

  The main pigment G2 of the pigment dispersion of GP-4 shown in Table 3 below is PG58. A pigment dispersion in which the first pigment G2 of GP-4 is replaced with PG36 is denoted as GP-5. For the measurement, a spectroscopic ellipsometer M-220 (manufactured by JASCO) was used to measure Nx, Ny, and Nz, and Δn was calculated from the following equation. The measurement wavelength was 550 nm.

Δn = [(Nx + Ny) / 2] −Nz
From Table 1 below, the coating film of the green pigment dispersion GP-4 mainly containing the halogenated zinc phthalocyanine (PG58) rather than the green pigment dispersion GP-5 mainly containing the halogenated copper phthalocyanine (PG36). It can be understood that the absolute value of Δn is smaller and the polarization is smaller.

(Manufacture of organic pigment dispersion)
Various methods can be adopted as a method for producing a dispersion of an organic pigment, and an example is shown below.

  First, pigments, solvents, pigment dispersants (including dye derivatives) and / or dispersion aids, surfactants, and in some cases, polymers and monomers are weighed in predetermined amounts, and subjected to a dispersion treatment step to disperse the pigments. A pigment dispersion is obtained. In this dispersion treatment step, for example, a paint conditioner, a bead mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the pigment is made fine, so that the coating characteristics of the photosensitive resin composition using the pigment dispersion are improved.

  When dispersing the pigment, the alkali-soluble resin, the pigment derivative, or the like may be used in combination as appropriate. For example, when the dispersion treatment is performed using a bead mill, glass beads or zirconia beads having a diameter of 0.1 mm to several mm are preferably used. The temperature during the dispersion treatment is usually 0 ° C. or higher, preferably room temperature or higher, and is usually set to 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion (pigment, solvent, dispersant, etc.) and the size of the apparatus such as the bead mill.

(Adjusting the phase difference of colored pixels)
The colored pixel can finely adjust the phase difference particularly from the viewpoint of the thickness direction phase difference. Increase or decrease the phase difference by various methods such as pigment type, pigment dispersion method, dispersant, finer pigment, and melamine resin, styrene resin, organic compound having benzyl group added as a retardation modifier. be able to. Melamine resin can be adjusted in the direction of increasing the phase difference, and styrene resin can be used to decrease the phase difference. In a green pixel, a zinc halide phthalocyanine pigment is preferable because its thickness direction phase difference tends to approach zero.

  In order to adjust the phase difference of the colored pixels, for example, the technique described in Japanese Patent No. 43066736 can be applied.

(Dispersant / dispersant aid)
A polymer dispersant is preferably used as the pigment dispersant because it is excellent in dispersion stability over time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Among these, a dispersant composed of a graft copolymer containing a nitrogen atom is particularly preferable from the viewpoint of developability as the light-shielding photosensitive resin composition of the present invention containing a large amount of pigment.

  Specific examples of these dispersants are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbik (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (Manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. 1 type may be used for these dispersing agents, and 2 or more types can be used together by arbitrary combinations and a ratio.

  As the dispersion aid, for example, a pigment derivative or the like can be used. Examples of the dye derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole. And oxinophthalone derivatives are preferred.

  Examples of the substituent of the dye derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group and an aryl group. And those bonded via a heterocyclic group or the like. Of these, sulfonic acid groups are preferred. In addition, a plurality of these substituents may be substituted on one pigment skeleton.

  Specific examples of the dye derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. .

1 type may be used for the above dispersion adjuvant and pigment | dye derivative | guide_body, and 2 or more types may be used together by arbitrary combinations and a ratio. The pigment derivatives used in Examples described later are shown in Table 2 below.

(Transparent resin)
The photosensitive coloring composition used as the light-shielding layer or the colored layer further contains a polyfunctional monomer, a photosensitive resin or a non-photosensitive resin, a polymerization initiator, a solvent and the like in addition to the pigment dispersion. Highly transparent organic resins that can be used in the present invention, such as photosensitive resins and non-photosensitive resins, are collectively referred to as transparent resins.

  The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. As the thermosetting resin, a resin obtained by reacting the following melamine resin with an isocyanate group-containing compound may be used.

(Alkali-soluble resin)
For the light shielding layer, light scattering layer, colored layer, and cell gap regulating layer used in the present invention, it is preferable to use a photosensitive resin composition capable of forming a pattern by photolithography. These transparent resins are desirably resins imparted with alkali solubility. The alkali-soluble resin is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group. Examples include epoxy acrylate resins, novolac resins, polyvinyl phenol resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, and the like. Of these, epoxy acrylate resins, novolak resins, and acrylic resins are preferable, and epoxy acrylate resins and novolak resins are particularly preferable.

(acrylic resin)
Examples of the transparent resin that can be used in the present invention include the following acrylic resins.

  Acrylic resin is, for example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate pencil Alkyl (meth) acrylates such as (meth) acrylate and lauryl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; ethoxyethyl (meth) acrylate and glycidyl (meta ) Ether group-containing (meth) acrylates such as acrylates; and alicyclic (meth) acrylates such as cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentenyl (meth) acrylates, etc. Polymers.

  In addition, the monomer mentioned above can be used individually or in combination of 2 or more types. Further, it may be a copolymer of a compound such as styrene, cyclohexylmaleimide, and phenylmaleimide copolymerizable with these monomers.

  Further, for example, a copolymer obtained by copolymerizing a carboxylic acid having an ethylenically unsaturated group such as (meth) acrylic acid, and a compound containing an epoxy group and an unsaturated double bond such as glycidyl methacrylate are obtained. Reacting or adding a carboxylic acid-containing compound such as (meth) acrylic acid to a polymer of an epoxy group-containing (meth) acrylate such as glycidyl methacrylate or a copolymer thereof with other (meth) acrylate Thus, a resin having photosensitivity can be obtained.

  Furthermore, a resin having photosensitivity can also be obtained by reacting a polymer having a hydroxyl group of a monomer such as hydroxyethyl methacrylate with a compound having an isocyanate group such as methacryloyloxyethyl isocyanate and an ethylenically unsaturated group. Obtainable.

  In addition, as described above, it is possible to react a copolymer such as hydroxyethyl methacrylate having a plurality of hydroxyl groups with a polybasic acid anhydride to introduce a carboxyl group into the copolymer to obtain a resin having a carboxyl group. I can do it. The manufacturing method is not limited to the method described above.

  Examples of acid anhydrides used in the above reaction include, for example, malonic acid anhydride, succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride , Methyltetrahydrophthalic anhydride, trimellitic anhydride and the like.

  It is preferable that the solid content acid value of the acrylic resin described above is 20 to 180 mgKOH / g. When the acid value is less than 20 mgKOH / g, the development speed of the photosensitive resin composition is too slow, and the time required for development increases, and the productivity tends to be inferior. On the other hand, when the solid content acid value is larger than 180 mgKOH / g, on the contrary, the development speed is too high, and there is a tendency that pattern peeling or pattern chipping after development occurs.

  Furthermore, when the said acrylic resin has photosensitivity, it is preferable that the double bond equivalent of this acrylic resin is 100 or more, More preferably, it is 100-2000, Most preferably, it is 100-1000. If the double bond equivalent exceeds 2000, sufficient photocurability may not be obtained.

(Photopolymerizable monomer)
Examples of photopolymerizable monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol Various acrylic and methacrylic acid esters such as propane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (meth) Examples include acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.

  Moreover, it is preferable to use the polyfunctional urethane acrylate which has the (meth) acryloyl group obtained by making polyfunctional isocyanate react with the (meth) acrylate which has a hydroxyl group. The combination of the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate is arbitrary and is not particularly limited. Moreover, one type of polyfunctional urethane acrylate may be used alone, or two or more types may be used in combination.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 ' Benzophenone compounds such as methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6- Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-tri Gin, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloro Triazine compounds such as methyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) Oxime ester compounds such as -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2, Phosphine compounds such as 4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone,
Examples include quinone compounds such as camphorquinone and ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like. Oxime derivatives (oxime compounds) are effective in improving sensitivity. These can be used singly or in combination of two or more.

(Sensitizer)
It is preferable to use a polymerization initiator and a photosensitizer in combination. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, A compound such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone may be used in combination.

  The sensitizer can be contained in an amount of 0.1 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

(Ethylenically unsaturated compounds)
The photopolymerization initiator is preferably used together with an ethylenically unsaturated compound. The ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule. Among them, it is a compound having two or more ethylenically unsaturated bonds in the molecule from the viewpoints of polymerizability, crosslinkability, and the accompanying difference in developer solubility between exposed and non-exposed areas. Is preferred. The unsaturated bond is more preferably a (meth) acrylate compound derived from a (meth) acryloyloxy group.

  Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like. Typical examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meta ) Urethane (meth) acrylates of acrylate compounds and polyisocyanate compounds, and epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds.

(Multifunctional thiol)
The photosensitive coloring composition can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.

  These polyfunctional thiols can be used alone or in combination. The polyfunctional thiol can be used in an amount of 0.2 to 150 parts by mass, preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the pigment in the photosensitive coloring composition.

(Storage stabilizer)
The photosensitive coloring composition can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the pigment in the photosensitive coloring composition.

(Adhesion improver)
The photosensitive coloring composition may contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the substrate. Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be contained in an amount of 0.01 to 100 parts by mass with respect to 100 parts by mass of the pigment in the photosensitive coloring composition.

(solvent)
The photosensitive coloring composition is mixed with a solvent such as water or an organic solvent in order to enable uniform coating on the substrate. When the composition of the present invention is a colored layer of a color filter, the solvent also has a function of uniformly dispersing the pigment. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be contained in an amount of 800 to 4000 parts by mass, preferably 1000 to 2500 parts by mass with respect to 100 parts by mass of the pigment in the coloring composition.

(Thickness of light shielding film, colored layer, and liquid crystal layer)
As described above, the technology according to the present invention is suitable for a liquid crystal driving method such as IPS (horizontal alignment, lateral electric field method) and FFS (Fringe Field Switching). By applying the technique described in Patent Document 10, the color filter of the present invention can be used as an FFS VA liquid crystal display device. Alternatively, it can be applied to a vertical electric field type VA liquid crystal display device by forming a transparent electrode on a color filter. In the method of applying a driving voltage of liquid crystal between the transparent electrode on the color filter and the pixel electrode of the array substrate on which the liquid crystal driving element (TFT), which is the opposite substrate, is formed, usually the liquid crystal thickness (cell gap) The thinner one can increase the response speed of the liquid crystal.

  In the main liquid crystal driving method described above, the liquid crystal thickness is in the range of about 2 μm to 4 μm. In addition, since the color (color change) when viewed from an oblique direction is smaller when the liquid crystal thickness is reduced, the liquid crystal thickness is from the viewpoint of improving responsiveness and coloring, and from the viewpoint of the amount of liquid crystal material used. Thinner is better. In addition, the film thickness of a colored pixel means the thickness from the surface of a colored pixel center to the transparent substrate surface which the said colored pixel touches.

  However, the thinner the liquid crystal is, or the larger the liquid crystal display screen is, the greater the influence of dust and foreign matter at the time of forming the liquid crystal cell. Therefore, the lower limit of the liquid crystal thickness in the vertical electric field method is about 3 μm. In the IPS and FFS systems, since it is not necessary to form a transparent electrode on the color filter side, an opposing short circuit (electrical short circuit) due to mixed conductive dust hardly occurs. From the viewpoint of conductive dust, the IPS and FFS methods can reduce the liquid crystal thickness. In order to reduce the thickness of the liquid crystal layer, it is desirable to use a liquid crystal having a refractive index anisotropy Δn larger than 0.07.

  In an FFS mode or IPS mode liquid crystal display device, the responsiveness and transmission of liquid crystal can be achieved by reducing the pitch of comb teeth (stripe pattern) of comb-like pixel electrodes (usually called conductive metal oxide thin film called ITO). Since the rate can be improved, the influence of the liquid crystal thickness is small compared to the vertical electric field method. Note that the pitch of the comb teeth may be adjusted so as to be proportional to the wavelength of each main transmittance peak of the colored pixels.

  In the transflective liquid crystal display device, the liquid crystal of the reflective part is related to the optical path difference between the transmissive part and the reflective part (in the reflective part, incident light is reflected by a light reflective electrode described later and passes through the liquid crystal layer twice). The thickness of the layer is preferably about ½ of that of the transmission part.

(Pedestal and spacer)
The spacer pedestal according to the present invention may be formed only at least in a portion where a spacer to be described later is formed and a portion necessary for shielding an active element such as a TFT. Moreover, it is desirable that the spacer base according to the present invention is simultaneously formed of the same material as the light shielding layer that is the frame portion. More specifically, a photomask in which multiple types of patterns with different transmittances such as gray tone (gradation mask) are formed, or an opening smaller than the pattern size of the pedestal (exposure amount by adjusting the size of the opening) The light-shielding layer and the pedestal can be formed simultaneously by exposure using a photomask having an opening with a specially designed opening shape and photolithography after development after exposure.

  As a photomask, a photomask having a light-shielding pattern as a thin film of metal chromium, a semi-transmissive portion as a metal oxide film such as ITO, and a transmissive portion without formation of these films may be used. The metal oxide film has an advantage that the transmittance can be adjusted by the film forming conditions and the film thickness.

  Further, the present inventors have confirmed that in a pedestal made of the same material as the frame portion (light-shielding layer) and a black matrix described later, reducing the thickness of the pedestal or black matrix is effective in improving flatness. . According to the detailed examination results of the present inventors, if the thickness of the pedestal is 1.0 μm or less, it is easy to stably obtain the thickness of the colored layer laminated thereon.

  As shown in FIG. 5, when the pedestal film thickness exceeds 1.2 μm, the film thickness of the colored layer laminated thereon becomes thin and suddenly changes, and becomes unstable. Conversely, when the film thickness is as small as 0.3 μm or less, it is difficult to obtain a stable film thickness in the photolithography process. Therefore, the thickness of the pedestal is preferably in the range of 0.4 μm to 1.0 μm. Note that the film thickness of the black matrix, which will be described later, may be formed as thin as 0.4 μm or less, and the formation of the black matrix may be omitted.

  The pattern shape of the pedestal can be used in combination as a light shielding pattern for suppressing the generation of photocurrent due to light incident on an active element such as a TFT for driving liquid crystal. For the light shielding of active elements such as TFTs, it is sufficient that the optical density is 1, so the addition of the film thickness of the pedestal of 0.4 μm to 1.0 μm and the film thickness of the overlapping portion of the colored pixels is sufficient. Moreover, in the structure which concerns on this invention, a single colored layer is laminated | stacked as a spacer on a base, and can further add light-shielding property.

  The color of the colored layer forming the spacer can be appropriately selected according to the purpose and specifications. For example, if priority is given to the light shielding property to an active element such as a TFT, a red colored layer capable of shielding light of a short wavelength can be selected. If priority is given to a rounded shape, a blue colored layer having less pigment content and fluidity compared to the other two colors can be selected as the uppermost layer of a three-layer stack or a two-layer stack spacer.

  The color filter substrate according to the present invention may be a color filter of four or more colors provided with colored pixels of complementary colors such as yellow pixels or white (transparent) pixels in addition to blue pixels, red pixels, and green pixels.

  In addition to a spacer having a height corresponding to the thickness of the liquid crystal (main spacer), a sub-spacer having a low height may be provided. When the main spacer is a three-layer stack, for example, a two-layer stack sub-spacer may be provided only in the frame portion. Each of the main spacer and the sub-spacer may be a single colored layer. The sub-spacer can be a low-height spacer by using a photomask having openings with different transmittances, such as a gray-tone mask, or using a photomask having small-diameter openings.

  The technology according to the present invention can be applied to a liquid crystal display device having a thin liquid crystal thickness in the near future. However, in the case of a thin liquid crystal thickness with poor liquid crystal fluidity, for example, the arrangement of spacer formation near the liquid crystal sealing port is changed. For example, the number of spacers and the layout may be adjusted in consideration of the flow of the liquid crystal material when forming a liquid crystal cell.

  In the color filter substrate according to the present invention, the light shielding layer and the pedestal can be formed in the same photolithography process as described later.

  Further, it is possible to form the spacer as a structure that also functions as a liquid crystal alignment control function by forming the colored pixel unit at the center in the longitudinal direction of the pixel (the center of the pixel or one central portion of the long side of the pixel). In a transflective liquid crystal display device in which one pixel is divided into a reflective portion and a transmissive portion, the structure may be formed at the center of the reflective portion of the pixel. A circular shape, a diamond shape, a polygonal shape, or the like can be adopted as the planar view shape of the structure. The TFT element for driving the liquid crystal can also be formed in the center in the longitudinal direction of the pixel in accordance with the spacer position. For example, when a liquid crystal alignment control structure having a rhombic shape in a plan view is used, the pixel electrode on the TFT substrate side has a rhombic concentric slit shape (a cross-sectional shape of the transparent electrode and an alternating pattern of the transparent electrode) so as to surround the spacer. What is necessary is just to arrange | position. This is particularly effective when a vertically aligned liquid crystal is driven by the FFS method.

  The structure combining the spacer and the alignment control structure proposed by the present inventors can substantially increase the aperture ratio of the liquid crystal display device and improve the brightness. In general, the alignment control structure can be formed with a high height or with a high density to improve the response of the liquid crystal. However, these techniques substantially reduce the aperture ratio of the pixel. In the proposed technique of the present invention, since the spacer and the alignment control structure can be used together, the aperture ratio does not decrease.

  The spacer formed in the center of the pixel can be used as a structure as a multi-domain alignment section when a liquid crystal display device adopts, for example, a photo-alignment film using ultraviolet light. The spacer used in the present invention can be formed with a smooth cross-sectional shape, for example, by covering the entire spacer with a blue colored layer as the uppermost layer, which has high fluidity when the spacer is thermally cured.

  In the embodiments of the present invention to be described later, a single color (red colored layer) spacer is shown. Forming the spacer in a single color has the following advantages. That is, the technique (described in Patent Document 2) in which two or three colored layers are stacked to form a spacer in an independent arrangement (for example, described in Patent Document 2) is a technique that uses simple color overlap as a spacer (described in Patent Document 1). This is advantageous in terms of liquid crystal alignment. However, in order to absorb the positional deviation when the colors are superimposed twice and three times, it is necessary to increase the bottom area of the colored layered portion of the first color, which adversely affects the aperture ratio of the pixel. In addition, when an independent thin and tall spacer is formed by stacking colored layers, the first color, the second color, and the third color are stacked with a thin film thickness separated from the film thickness of the colored pixels. There are difficulties in checking the conditions in the height design and manufacturing process. The technique of forming the spacers by independently arranging the two or three layers of the colored layers has been problematic because the above-described confirmation work is required for each type of color resist to be used and each type of color filter to be manufactured. Such a problem can be solved by forming the spacer in a single color.

(Black matrix thickness)
FIG. 6 shows a spacer 5 formed by stacking a light shielding layer 2, a pedestal 4, a black matrix 8, a red pixel 3R, a green pixel 3G, and a single colored layer in a color filter substrate according to another embodiment of the present invention. It is a figure which shows the planar view arrangement | positioning of the low subspacer 6 and the light-scattering layer 11 of low. That is, in FIG. 5, a black matrix 8 is provided that separates three colored pixels including a red pixel 3R, a green pixel 3G, and a blue pixel 3B.

  One of the features of one embodiment of the present invention is that the light shielding layer, the cell gap regulation layer laminated on the light shielding layer, the total film thickness, and the green pixel thickness are substantially the same, and the flatness suitable for the alignment of the liquid crystal is obtained. It is an object of the present invention to provide a color filter substrate having no leakage of light at the frame portion due to poor liquid crystal alignment. The present inventors have confirmed that the film thickness of the black matrix made of the same material as that of the frame portion (light shielding layer) affects the improvement of flatness. The black matrix is usually a lattice-shaped light shielding pattern formed so as to surround the colored pixels for the purpose of improving the contrast, but may be formed in a stripe shape in the longitudinal direction of the pixels. Further, in the present invention, a color filter substrate without a black matrix may be used. Alternatively, the black matrix, the pedestal, and the light shielding layers having different thicknesses may be formed in two steps using different photomasks. Alternatively, a black matrix, a pedestal, and a light shielding layer having different film thicknesses may be formed by adjusting the number of shots in laser irradiation exposure.

  FIG. 7 shows the relationship between the film thickness of the black matrix and the height above the protrusions of the end portions of the colored pixels that are superimposed on the black matrix. When the film thickness of the black matrix 10 exceeds 1.1 μm, the height of the protrusion 7 becomes remarkably high, which is not preferable for liquid crystal alignment. When the thickness of the black matrix is less than 1 μm, and further less than 0.8 μm, the projection height at the end of the colored pixel is 0.25 μm, and further lower than 0.2 μm.

  A color filter that can ensure good flatness, including variations in the thickness of the colored pixels, of less than ± 0.15 μm, and meets the high demands of high-quality liquid crystal display devices such as the IPS method and the FFS method. Can be provided. Moreover, it becomes a color filter having high flatness within a 1/4 wavelength range (± 0.15 μm) of green wavelength 550 nm, which has high visibility to human eyes, and can reduce coloring unevenness.

  Similar to the pedestal, the black matrix can be formed simultaneously with the light shielding layer by a photolithography technique using a gray tone mask, a half tone mask, or the like. Alternatively, the exposure amount of the light-shielding layer and the black matrix may be formed by changing the number of shots with a difference in film thickness by using laser exposure.

  Although FIG. 7 does not show a black matrix having a thickness of less than 0.4 μm, the present inventors have confirmed that the height of the protrusions superimposed on the thin black matrix is low. Yes. Unlike the light-shielding layer (frame portion), the black matrix is not required to have a light-shielding property. Therefore, in the present invention, the formation of the black matrix may be omitted, and the black matrix may be substituted only by overlapping the colored layers of different colors. Note that light from a light source (backlight) disposed on the back surface of the transmissive liquid crystal display device can be shielded by a scanning line or a signal line of an active element such as a TFT.

  The height of the spacer 5 in the effective display area is substantially the same as that of the effective display area, but the adjustment of the height is performed by processes such as selection of the pedestal thickness and the colored layer, application in the color filter manufacturing process, development, and hardening. Various adjustments can be made according to the spacer diameter (size). The pedestal 4 ′ not formed with the spacer 5 is disposed for the purpose of adjusting the aperture ratio of the red pixel R, the green pixel G, and the blue pixel B and shielding the active elements such as TFTs.

(Light scattering layer)
As described above, the color filter substrate according to the present invention can be suitably used particularly for a transflective liquid crystal display device. The colored pixel of the color filter of the present invention is divided into a transmissive part and a reflective part. In the reflective part, as shown in FIG. 3, a light scattering layer 11 is provided below the colored pixel 3 on the transparent substrate 1. It is arranged at the position. The cell gap regulating layer 12 is disposed at substantially the same position as the light scattering layer 11 via the colored pixels 3 and the light scattering layer 11. In FIG. 4, the cell gap restriction layer is not shown.

  The light scattering layer 11 is formed by dispersing single or plural kinds of amorphous fine particles 13 in a matrix resin 14 having different refractive indexes. The light scattering layer 11 scatters incident light to make a paper white-like effect on the eyes of an observer. Is an optical functional film having The matrix resin may be any transparent resin that has heat resistance and visible range transparency. The film thickness of the light scattering layer 11 is preferably in the range of about 1.5 μm to 5 μm because of the relationship between the amorphous fine particle diameter, the light wavelength, and the suitability in the manufacturing process.

  Examples of the amorphous fine particles 13 of the light scattering layer 11 include fine particles made of an inorganic material and fine particles made of an organic polymer. In particular, organic polymer fine particles are mainly listed because they are amorphous, but even inorganic fine particles are not problematic as long as they are amorphous. The method of forming the light scattering layer 11 may be a method of expressing amorphous fine particles in the matrix resin by phase separation described later. Amorphous fine particles may be formed by a photolithography technique, and a matrix resin (hereinafter referred to as a transparent resin) may be applied thereon.

  Examples of the amorphous fine particles 13 include spherical amorphous fine particles such as silica and alumina oxide in the case of inorganic fine particles, and examples of the organic polymer fine particles include acrylic fine particles, styrene acrylic fine particles and cross-linked products thereof, melamine fine particles, Melamine-formalin condensate, (polytetrafluoroethylene), PFA (perfluoroalkoxy resin), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), PVDF (polyfluorovinylidene), ETFE (ethylene-tetrafluoroethylene copolymer) Examples thereof include fluorine-containing polymers such as coalesced) and silicon resin fine particles. Among them, the crosslinked acrylic resin fine particles have a refractive index of less than 1.5, and the silica particles or silicon resin fine particles have a low refractive index of 1.42 to 1.45 (halogen lamp D line 589 nm). preferable.

  Moreover, these amorphous fine particles 13 should just be mainly contained as the fine particles in the light-scattering layer 11, and should just contain about 70% or more of fine particles, for example. In addition to these fine particles, non-spherical fine particles such as irregular fine particles and small amounts of crystalline fine particles of about 30% or less are used for the purpose of finely adjusting the dispersion stability of the fine particles in the coating liquid and light scattering characteristics. You can add it.

Further, these fine particles can be applied as the fine particles after appropriate surface treatment to improve the solvent dispersibility and compatibility with the transparent resin. Examples of such a surface treatment include, for example, a treatment of applying and coating SiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, a transparent resin, a coupling agent, or a surfactant. In addition to these, a treatment for causing a surface reaction with alcohol, amine, organic acid or the like can be exemplified.

  The shape of the amorphous fine particles 13 is not particularly limited, but may be a spherical shape or a shape similar to a spherical shape. The spherical fine particles can be easily controlled in size, particle size distribution, and the like, and therefore, the optical characteristics of the light scattering layer 11 can be easily controlled. The particle size of the fine particles is not particularly limited, and the allowable range varies depending on the film thickness of the target light scattering layer 11 and the presence or absence of coloring. However, it is usually not preferable to use fine particles larger than the thickness of the light scattering layer because the surface of the light scattering layer becomes very rough. As a preferable particle size range, the average particle size is about 0.8 μm to 3 μm, preferably 1 μm to 2 μm.

  The specific gravity of the fine particles does not directly affect the optical characteristics of the light scattering layer 11, but has a great influence on the coating characteristics when forming the light scattering layer 11, and is also related to the characteristics of the light scattering layer 11 itself. To do. It is desirable for the stability of the coating solution that the value is close to the specific gravity of the transparent resin solution.

  The transparent resin 14 for dispersing the fine particles preferably has a high visible light transmittance and has sufficient resistance to heat treatment and chemical treatment during the manufacturing process of the liquid crystal display device. For example, as a resin having a high refractive index, Epoxy-modified acrylic resins, fluorene resins, and polyimide resins can be used. As resins having a low refractive index, fluorine-modified acrylic resins and silicon-modified acrylic resins can be used. In addition, acrylic resin, epoxy resin, polyester resin, urethane resin, silicon resin, and the like can be used as appropriate.

  When the light scattering layer 11 is provided in a pattern by a photolithography process, an acrylic resin or an epoxy resin having photosensitivity and developability can be used. Also, these resins can be used in combination with heat curing or ultraviolet curing.

  For example, when the fine particle is a crosslinked acrylic fine particle having a refractive index of 1.49 (value using a halogen lamp D line of 589 nm), the transparent resin preferably has a refractive index of 1.55 to 1.65. In the case of silica particles or silicon resin fine particles having a refractive index of 1.42 to 1.45, the transparent resin preferably has a refractive index of 1.50 to 1.60.

  The light scattering layer 11 is formed by mixing and dispersing amorphous fine particles 13 in a transparent resin 14 that is a matrix resin, coating and drying on a transparent substrate, and then forming an arbitrary shape through a photolithography process. I can do it. Note that spin coating, flow coating, roll coating, or the like can be applied as a coating method, and projection exposure or proximity exposure can be applied as an exposure method.

  Examples of the amorphous fine particles 13 in the light scattering layer 11 include fine particles that can be formed by mixing two resins and separating the phases. Amorphous fine particles 13 can be formed by selecting an appropriate amount of two or more resins and additives having different refractive indexes and applying and drying a coating solution dissolved in a solvent on the substrate.

  Phase separation is performed when two resins are mixed in a solution or when the solvent is volatilized by coating and drying on a substrate, and when the coating film is dried, transparent amorphous fine particles 13 are formed. Can be formed. At this time, one phase-separated resin tries to grow into a spherical shape in the solution, but when coated on the substrate, the film volume decreases as the solvent in the coating film volatilizes, and the spherical shape grows. However, it grows while deforming from a spherical shape to a disk shape due to stress from the upper surface.

One resin is formed and grown as droplets from two resin solutions, and the amorphous fine particles 13 are formed under the condition that one resin is A and the other resin is B. 1) The amount of A is more than the amount of B Less,
2) The surface tension of the A solution is larger than the surface tension of the B solution,
3) The evaporation rate of solution A is greater than the evaporation rate of solution B;
4) the molecular weight of A is greater than the molecular weight of B;
In particular, the magnitude is a constraint on strength.

  When the amorphous fine particles 13 are generated and formed by phase separation from two or more kinds of resin solutions having different refractive indexes, the amorphous fine particles remain inside the film and do not come out on the surface. The surface of the layer becomes flat, and the film thickness of the color filter becomes uniform.

  The transparent resin 14 and the amorphous fine particles 13 formed by phase separation desirably have a high visible light transmittance and sufficient resistance to heat treatment and chemical treatment during the manufacturing process of the liquid crystal display device.

  For example, an epoxy-modified acrylic resin, a fluorene resin, a polyimide resin, or a melamine resin can be used as a resin having a high refractive index, and a fluorine-modified acrylic resin or a silicon-modified acrylic resin can be used as a resin having a low refractive index. In addition, acrylic resin, epoxy resin, polyester resin, urethane resin, silicon resin, and the like can be used as appropriate.

  Amorphous fine particles are easily available in spherical shape, and the refractive index of transparent silica and silicon resin is 1.43 to 1.44, and the refractive index of crosslinked acrylic resin is 1.49. It can be applied as a high resin.

  When the light scattering layer 11 is provided in a pattern by a photolithography process, an acrylic resin or an epoxy resin having photosensitivity and developability can be used. It is also possible to use a thermosetting resin or an ultraviolet curable resin.

  In addition to the above resin, a surfactant for improving coating suitability, a photopolymerization initiator for imparting photosensitivity, a sensitizer, and the like can be added.

  Examples of the amorphous fine particles 13 in the light scattering layer 11 may be different from those in the above two examples, and different manufacturing processes may be exemplified as the method for forming the light scattering layer 11. That is, a transparent resin is applied and dried on a substrate, and a number of fine reliefs having a film thickness of several μm and a pattern size of several μm to several tens of μm are formed using means such as photolithography, and the relief is softened by heating. After that, a light scattering film layer can be formed by thermal crosslinking and coating a transparent resin having a different refractive index thereon.

  When the amorphous fine particles 13 are hemispherical microlenses formed by melting and dissolving a fine resin pattern, the light scattering characteristics can be adjusted by changing the pattern shape (size, shape and density). . Alternatively, a directional light scattering layer can be obtained by making the cross-sectional shape of the microlens asymmetrical or parabolic.

  The pattern size of the light scattering layer 11 is desirably formed in a pattern smaller than the size in plan view of the colored pixels. When the pattern of the light scattering layer is larger than the colored pixels, exposure light is scattered by the light scattering layer when forming the colored pixels using a photomask, and the pattern edge shape of the colored pixels tends to be slightly disturbed.

(Colored pixel overlap shape)
As an exposure apparatus for TFT, an apparatus with high alignment accuracy in which 3σ is 1.5 μm is commercially available. In the case of TFT, an alignment mark attached to the metal wiring is used. However, in the case of a color filter, it is attached to an organic film (for example, a photosensitive colored composition film such as a black matrix). Use alignment marks. Similarly, in the colored layer to be laminated, the alignment mark is attached to the organic film, the film thickness of the organic film is 4 μm to 1 μm, which is thicker than the TFT wiring, and the pattern edge is also tapered. The alignment accuracy must be at least 3 μm and 4.5 μm alignment accuracy.

  As described above, the liquid crystal thickness of the IPS, VA, or FFS type liquid crystal display device is about 2 μm to 4 μm. The thickness of the colored layer in the color filter of the present invention is about 0.6 to 1 times the liquid crystal thickness. Therefore, the specific thickness of the colored layer is about 1.2 μm to 4 μm.

  The line width of the black matrix is about 5 μm to 30 μm, although it differs for mobile (small) liquid crystal display devices and large TVs. When giving priority to the aperture ratio of the pixel, as described above, the formation of the black matrix may be omitted.

FIG. 8 shows the pattern edge shape of the thick colored pixel 22 and FIG. 9 shows the pattern edge shape of the thin colored pixel 23. The length m and n of the pattern edge related to the alignment is 4.5 μm, and the thickness of the colored layer 22 and the thickness t of the colored pixel 23 are 1.2 μm to 4.0 μm. When the taper angles θ ₁ and θ _{2 of} the pattern edges (angles formed with the surface of the transparent substrate 1 at the end of the colored pixels) are calculated, the angle range is about 15 ° to 40 °. Therefore, although depending on the film thicknesses s and t of the colored layers 22 and 23, in order to obtain good flatness, it is desirable to form the end shape of the colored pixel at a taper angle of 15 ° to 40 °. .

  The end shape of the colored pixel can be controlled by various methods such as changing the amount of the polymerization initiator, the developing method, and the exposure amount. The planar view shape of the colored pixels is preferably a continuous stripe shape of the colored pixels.

  On the color filter substrate according to the present invention, the subtle texture of the surface of the color filter, the surface gap of 0.1 μm or less, such as the cell gap regulating layer surface described later, or the treatment (orientation treatment) before forming the cell gap regulating layer A protective layer or an insulating layer made of a transparent resin may be laminated for the purpose of covering the surface and improving the electrical insulation. The protective layer can be formed so as to ensure followability (opposite to ensure flatness) by increasing the molecular weight of the transparent resin to be used in order to ensure the height of the spacer to some extent. . The spacer height can be secured by coating and forming the protective layer with a thin film thickness of, for example, 0.05 μm to 0.3 μm. A protective layer having a thickness of 1 μm or more may be formed in advance by forming a high spacer.

  The protective layer may also serve as an alignment film, or may contain an additive (for example, an ultraviolet absorber) that assists photoalignment. Further, a transparent conductive film made of a metal oxide thin film called ITO or the like may be formed. Further, a protrusion may be formed in the pixel in advance using the same material as the light shielding layer, and a colored layer may be further stacked to be used as an alignment control structure. A spacer and an alignment control structure may be used together. For example, a TFT element for driving the liquid crystal on the TFT substrate side and a pedestal on the color filter substrate side are formed at the center of the pixel so as to face each other, so that the vertical alignment liquid crystal display spacer and the alignment control structure can be used together. Can do. The transparent conductive film may be formed in a comb-like shape, and a slit which is an opening may be formed in this for the purpose of liquid crystal alignment control.

(Cell gap regulation layer)
As shown in FIG. 3, the cell gap regulation layer 12 according to the present invention is partially formed on the colored pixels 3. As described above, the cell gap regulation layer 12 is provided for the purpose of adjusting the optical path difference between the transmission part and the reflection part. Therefore, a resin material having at least high visible light permeability and heat resistance necessary for the liquid crystal panel process can be used for the cell gap regulating layer.

  Similarly, the above-described transparent resin, alkali-soluble resin, and acrylic resin can be applied. Since the cell gap regulating layer forms a pattern on the colored pixels, it is preferable to use as the material an alkali-soluble resin that can be patterned in a photolithography process. Even if a thermosetting resin is used, the pattern can be formed by dry etching or lift-off techniques.

  It is more preferable to provide the cell gap regulating layer with a function of ¼ wavelength phase difference or ½ wavelength phase difference. The reflection part of the transflective liquid crystal has a difference in phase difference caused by the liquid crystal in addition to the optical path difference as compared with the transmission part. Due to the difference in the phase difference between the reflective part and the transmissive part, the reflected light and black display of the reflective part may be colored, or the display that should be normally black may become normally white display. The problem is big.

  This phenomenon can be eliminated by shifting the phase difference of the 1/4 wavelength of the incident light and further adding a phase difference of 1/4 wavelength by reflection at the reflection electrode (the incident light converted to linearly polarized light is converted into the cell gap regulating layer). The polarization is rotated by 90 degrees in a single reciprocation in the thickness direction). Alternatively, in an IPS liquid crystal display device, a ½ wavelength retardation layer in which the absorption axis (transmission axis) and the orientation axis (slow axis) of the observer side polarizing plate are shifted by 22.5 degrees in the cell gap regulating layer. By providing the above function, similarly, linearly polarized incident light can be rotated by 90 degrees in a single round trip in the thickness direction of the cell gap regulating layer.

  Specific methods for imparting a function of a quarter wavelength phase difference or a half wavelength phase difference to the cell gap regulating layer include a coating formation method using a polymer liquid crystal or a crosslinkable polymer liquid crystal solution, and the above-described alkali-allowable. Examples thereof include a method of forming a birefringence regulator in a soluble transparent resin and a method using a polymerizable liquid crystal compound. In the case of a polymerizable liquid crystal compound, a discotic polymerizable liquid crystal compound or a rod-shaped polymerizable liquid crystal compound having a disc-like molecular structure can be used. You may form combining these methods and materials listed.

  In addition, in order to improve the reproducibility of imparting the function of changing the phase of polarized light by 90 degrees, formation of an alignment film or alignment treatment may be performed before the formation of the cell gap regulating layer. When the alignment can be adjusted by the amount of exposure and the exposure wavelength as in the case of the polymerizable liquid crystal compound, the density and the alignment direction of the alignment can be adjusted by the color of the colored pixel.

  The exposure machine can be appropriately selected including the exposure wavelength such as an ultra-high pressure mercury lamp, a YAG laser, a solid-state laser, and a semiconductor laser. In the case of laser exposure, the alignment density and alignment direction can be adjusted by selecting the exposure wavelength, adjusting the exposure amount by the number of laser shots, the incident angle of the laser beam, and the like. The exposure may be performed with polarized light irradiation or non-polarized light irradiation. Immobilization may be performed by non-polarization irradiation while heating after polarization irradiation first. When there is oxygen inhibition, it is preferably performed in an inert gas atmosphere.

  The difference in retardation of the cell gap regulating layer can be adjusted by the addition amount, type and blend of the polymerization initiator added to the polymerizable liquid crystal compound in addition to the exposure amount. Moreover, when the polymerizable liquid crystal compound is a monomer, the crosslinking density can be increased by using a plurality of functional groups of the monomer, and a highly reliable cell gap regulating layer can be obtained. The cell gap regulating layer may be a quarter wavelength layer that matches the wavelength of the main transmitted light of the colored pixel. In the case of normally black display, not only the cell gap regulating layer formed on the colored pixels but also the cell gap regulating layer on the light shielding layer (frame portion) has a function of changing the quarter wavelength or the half wavelength. By doing so, light leakage can be eliminated. In a normally black liquid crystal display device, the cell gap regulating layer 12 is placed on the frame-shaped light shielding layer 2 so that the total film thickness of the cell gap regulating layer 12 and the light shielding layer 2 is substantially equal to the film thickness of the green pixel. By forming the film, light leakage can be eliminated and image quality can be improved.

  When a polymerizable liquid crystal compound is used as the cell gap regulating layer, an orientation film may be applied and formed as a pretreatment before the cell gap regulating layer is formed, and the orientation treatment may be performed thereon. Further, it is desirable to form an alignment film for liquid crystal alignment after forming a cell gap regulating layer to form a color filter substrate. When this alignment film is an alignment film whose alignment amount can be adjusted with an energy beam such as ultraviolet rays, the alignment amount of the transmission part and the reflection part is changed by laser exposure as described above, or the alignment for each color is made different. be able to. The alignment film used for the alignment treatment of the cell gap regulating layer can be used for liquid crystal alignment of the transmissive part, and a film having a different alignment function can be separately formed on the cell gap regulating layer of the reflecting part. .

  For the alignment treatment, which is a pretreatment of the polymerizable liquid crystal compound, the same method as the alignment method of the liquid crystal alignment film used as the liquid crystal display device can be employed. For example, in addition to a rubbing method that mechanically rubs the surface of the alignment film, a photo-alignment method using ultraviolet light may be used. The ultraviolet light source can be appropriately selected such as the wavelength, irradiation angle, and irradiation amount of the ultraviolet light to be exposed, such as an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a short arc type xenon lamp, a solid laser, a YAG laser, and a semiconductor laser. The ultraviolet light may be irradiated from a plurality of directions such as two directions and four directions.

  The cell gap regulating layer 12 may be formed independently for each colored pixel, or may be formed so as to connect adjacent colored pixels. As shown in FIG. 12, the reason is that the liquid crystal alignment unevenness due to the level difference “a” that has conventionally occurred in the colored pixels 3 and the light shielding layer 2 of the color filter is improved by improving the flatness of the color filter.

  In addition, the area ratio of the transmission part and the reflection part of the color filter substrate according to the present invention can be adjusted according to the purpose and conditions of use of the liquid crystal display device.

(Light shielding layer material / adjustment of black composition)
(Pigment dispersion RD1)
As a coloring agent, C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 = 80/20 (weight ratio) 20 parts of a mixture, 5 parts of BYK-2001 as a dispersant (in terms of solid content), and 75 parts of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill to obtain a pigment dispersion (RD1) was prepared.

(Pigment dispersion YD1)
As a coloring agent, C.I. I. A pigment dispersion (YD1) was prepared by treating 20 parts of Pigment Yellow 150, 5 parts of Solsperse 24000 as a dispersant (in terms of solid content) and 75 parts of propylene glycol monomethyl ether acetate as a solvent with a bead mill.

(Pigment dispersion BD1)
As a coloring agent, C.I. I. Pigment Blue 15: 6, 20 parts of Ajisper PB-821 as a dispersant (in terms of solid content), and 75 parts of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill to prepare a pigment dispersion (BD1) did.

(Pigment dispersion liquid VD1)
As a coloring agent, C.I. I. A pigment dispersion (VD1) was prepared by treating 20 parts of Pigment Violet 23, 5 parts of Ajisper PB-821 as a dispersant (in terms of solid content) and 75 parts of propylene glycol monomethyl ether acetate as a solvent using a bead mill.

(Synthesis of resin solution (P1))
A reaction vessel was charged with 800 parts of cyclohexanone, heated while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise to carry out a polymerization reaction.

Styrene 60 parts Methacrylic acid 60 parts Methyl methacrylate 65 parts Butyl methacrylate 65 parts Thermal polymerization initiator 10 parts Chain transfer agent 3 parts A solution in which 2.0 parts of the thermal polymerization initiator is dissolved in 50 parts of cyclohexanone after sufficient heating after dropping. Was added, and the reaction was further continued to obtain an acrylic resin solution.

  To this resin solution, cyclohexanone was added so that the nonvolatile content was 20% by weight to prepare an acrylic resin solution, which was designated as resin solution (P1). The weight average molecular weight of this acrylic resin was about 10,000.

(Black composition)
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a black composition. This black composition is used for forming a light shielding layer and a pedestal in Examples described later.

21 parts of the above pigment dispersion (RD1) 17 parts of the above pigment dispersion (BD1) 4 parts of the above pigment dispersion (YD1) 9 parts of the resin solution (P-1) 4.8 parts of trimethylolpropane triacrylate Photopolymerization initiator
(“Irgacure-369” manufactured by Ciba Geigy Co., Ltd.) 2.8 parts Photosensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Cyclohexanone 36.2 parts The above black composition was cured after coating formation. An optical density (OD value) of about 1.8 can be obtained with a thickness of 1 μm. The film thickness can be adjusted depending on the application conditions. The optical density of the coating film can also be adjusted by adjusting the component ratio of the resin solid ratio (resin solution). In the black composition, the green organic pigment is not added because of its poor light-shielding property.

(Measurement of optical density (OD))
The optical density (OD value) is a value representing the extent to which a substance absorbs light. When the optical path length is constant, the larger the OD value, the higher the concentration of the substance. The optical density (OD value) in the present invention is represented by the following formula (1). The tristimulus value Y with a C light source was measured for the black composition coated substrate obtained above using a spectroscope OSP-200 manufactured by Olympus Corporation, and the optical density (OD) was calculated using the following formula 1.

[Formula 1]
Optical density (OD) = − log (Y / 100) (1)
(Y is the tristimulus value Y with the C light source)
As a measurement sample, a black composition Blk diluted with an organic solvent and adjusted in concentration was applied on a glass substrate to a thickness of 1 μm and dried naturally. The mixture was heated on a hot plate at 90 ° C. for 1 minute to remove excess solvent and dry. Then, it baked in 230 degreeC oven for 1 hour, and was set as the optical density measurement sample of a light shielding layer. The optical density (OD) was approximately 1.8.

  The film thickness can be adjusted depending on the coating conditions. It is also possible to control the concentration by adjusting the component (solid content) ratio of the resin solution. When the film thickness is increased from 4 μm to 5 μm with the above black composition, it is possible to increase the amount of resin solution and solvent (cyclohexanone, etc.) and increase the organic pigment concentration to around 10% of the black composition. can do. The light shielding property at this time can be set in the range of 3 to 4 in terms of optical density.

  In the examples described later, the resin solid ratio and the solvent amount of the black composition were adjusted to a film thickness of 2.9 μm and the optical density was about 3.

(Adjustment of resin composition for light scattering layer)
Photosensitive resin composition for light scattering layer The following composition was prepared.

Alkali-soluble photosensitive transparent resin A2
: Epoxy acrylate resin having a fluorene skeleton 4.5 parts by weight Transparent particles B3: MX180 (manufactured by Soken Chemical Co., Ltd.) 2 parts by weight Photopolymerization initiator C: Irgacure 819
(Ciba Specialty Chemicals Co., Ltd.) 0.45 parts by weight Solvent D: 21 parts by weight of cyclohexanone Photopolymerization monomer E: M400 (manufactured by Toagosei Co., Ltd.) 2 parts by weight Alkali-soluble photosensitive transparent resin A2 , Photopolymerization initiator C, and photopolymerization monomer E were mixed, applied, dried, exposed (200 mJ / cm ² ), developed, and then hardened at 230 ° C. for 60 minutes. The refractive index was 1.58 (D line 589 nm).

  Alkali-soluble photosensitive transparent resin A2, transparent particle B3, photopolymerization initiator C, solvent D, and photopolymerization monomer (A2: B3: C: D: E = 4.5: 2: 0.45 in weight ratio) : 21: 2) was mixed and stirred with a medialess disperser for 3 hours to obtain a resin composition for a light scattering layer. The viscosity of the resin composition for a light scattering layer was 14 cp / 25 ° C.

(Adjustment of colored pixel material / colored composition)
[Pigment production example R2]
100 parts of diketopyrrolopyrrole red pigment PR254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals; R-1), 18 parts of dye derivative (D-1), 1000 parts of crushed salt, and 120 parts of diethylene glycol was charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours.

  The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. Dried to obtain 115 parts of a salt milled pigment (R2).

[Pigment production example R3]
Stainless steel 1 gallon kneader containing 100 parts of anthraquinone red pigment PR177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals), 8 parts of pigment derivative (D-2), 700 parts of crushed salt and 180 parts of diethylene glycol (Made by Inoue Seisakusho) and kneaded at 70 ° C. for 4 hours. The mixture was put into 4000 parts of warm water, heated to about 80 ° C., stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. Drying gave 102 parts of salt milled pigment (R3).

[Pigment production example R4]
A sulfonation flask is charged with 170 parts of tert-amyl alcohol under a nitrogen atmosphere. 11.04 parts of sodium are added and the mixture is heated to 92-102 ° C. The molten sodium is kept at 100-107 ° C. overnight with vigorous stirring.

  A solution prepared by dissolving 44.2 parts of 4-chlorobenzonitrile and 37.2 parts of diisopropyl succinate in 50 parts of tert-amyl alcohol at 80 to 98 ° C. was dissolved in the obtained solution. Introduce over 2 hours. After the introduction, the reaction mixture is stirred for a further 3 hours at 80 ° C. and at the same time 4.88 parts of diisopropyl succinate are added dropwise. The reaction mixture is cooled to room temperature and added to a 20 ° C. mixture of 270 parts of methanol, 200 parts of water, and 48.1 parts of concentrated sulfuric acid and stirring is continued at 20 ° C. for 6 hours. This red mixture was filtered, and the residue was washed with methanol and water and then dried at 80 ° C. to obtain 46.7 parts of a red pigment (R4).

[Pigment production example G2]
In a molten salt of 200 ° C. of 356 parts of aluminum chloride and 6 parts of sodium chloride, 46 parts of zinc phthalocyanine was dissolved, cooled to 130 ° C., and stirred for 1 hour. The reaction temperature was raised to 180 ° C., and bromine was added dropwise at 10 parts per hour for 10 hours. Thereafter, chlorine was introduced at 0.8 parts per hour for 5 hours.

  The reaction solution was gradually poured into 3200 parts of water, then filtered and washed with water to obtain 107.8 parts of a crude zinc halide phthalocyanine pigment. The average number of brominations contained in one molecule of the crude zinc halide phthalocyanine pigment was 14.1 and the average number of chlorine was 1.9. In this example, the bromination number is not limited.

  120 parts of the obtained crude zinc halide phthalocyanine pigment, 1600 parts of crushed salt and 270 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours.

  The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. Drying gave 117 parts of salt milled pigment (G2).

[Pigment production example Y2]
A separable flask was charged with 150 parts of water, and further stirred with 63 parts of 35% hydrochloric acid to prepare a hydrochloric acid solution. While paying attention to foaming, 38.7 parts of benzenesulfonyl hydrazide was charged, and ice was added until the liquid temperature became 0 ° C. or lower. After cooling, 19 parts of sodium nitrite was charged over 30 minutes, stirred for 30 minutes at 0 to 15 ° C., and then sulfamic acid was charged until no coloration was observed on the potassium iodide starch paper.

  Next, after adding 25.6 parts of barbituric acid, it heated up to 55 degreeC and stirred as it was for 2 hours. Next, 25.6 parts of barbituric acid was added, and after raising the temperature to 80 ° C., sodium hydroxide was added until the pH reached 5. After further stirring for 3 hours at 80 ° C., the temperature was lowered to 70 ° C., followed by filtration and washing with warm water.

  The obtained press cake was reslurried in 1200 parts of warm water, and then stirred at 80 ° C. for 2 hours. Thereafter, filtration was performed at the same temperature, and washing with 2000 parts of water at 80 ° C. was performed with warm water, and it was confirmed that benzenephonamide was transferred to the filtrate side. The obtained press cake was dried at 80 ° C. to obtain 61.0 parts of disodium azobarbituric acid.

  Next, 200 parts of water was charged into a separable flask, and 8.1 parts of the obtained disodium azobarbituric acid powder was added and dispersed while stirring. After uniformly dispersing, the solution was heated to 95 ° C., and 5.7 parts of melamine and 1.0 part of diallylaminomelamine were added.

  Further, a green solution obtained by dissolving 6.3 parts of cobalt (II) chloride hexahydrate in 30 parts of water was added dropwise over 30 minutes. After completion of the dropwise addition, complexation was performed at 90 ° C. for 1.5 hours.

  Thereafter, the pH was adjusted to 5.5, 20.4 parts of xylene, 0.4 part of sodium oleate, and 16 parts of water were previously stirred to add 20.4 parts of an emulsion, and further heated for 4 hours. Stir. After cooling to 70 ° C., it was quickly filtered, and washing with warm water at 70 ° C. was repeated until the inorganic salt could be washed.

  Thereafter, 14 parts of an azo yellow pigment (Y2) was obtained through drying and grinding processes.

[Pigment production example B2]
100 parts of copper phthalocyanine blue pigment PB15: 6 (“Rionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. And kneaded for 12 hours.

  The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. Dried to obtain 98 parts of salt milled pigment (B2).

[Pigment production example V2]
300 parts of LIONOGEN VIOLET RL (manufactured by Toyo Ink Manufacturing Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and poured into water at 5 ° C. After stirring for 1 hour, it was filtered, washed with warm water until the washing solution became neutral, and dried at 70 ° C.

  120 parts of the obtained acid pasting pigment, 1600 parts of sodium chloride, and 100 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It was dried at 80 ° C. for 24 hours to obtain 118 parts of a salt milled pigment (V2).

(Preparation of resin solution (P2))
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction. .

Styrene 70.0 parts Methacrylic acid 10.0 parts Methyl methacrylate 65.0 parts Butyl methacrylate 65.0 parts Azobisisobutyronitrile 10.0 parts After dropwise addition and further reacted at 100 ° C for 3 hours, A solution prepared by dissolving 2.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to synthesize a resin solution.

  After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution (P2) was prepared.

(Preparation of pigment dispersion and coloring composition)
The mixture (parts by weight) shown in Table 3 below was uniformly stirred and mixed, then dispersed with a sand mill for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter to obtain red, green, and blue A pigment dispersion was obtained.

Thereafter, as shown in Table 4 below, a mixture of a pigment dispersion, an acrylic resin solution (P2), a monomer, a polymerization initiator, a sensitizer, an organic solvent, and the like is mixed and stirred and then filtered through a 5 μm filter. , Green and blue colored compositions were obtained. In the following examples, red pixels, green pixels, and blue pixels were formed using the colored composition shown in Table 4 below.

  Hereinafter, based on Example 1, this invention is demonstrated in detail.

[Example 1]
(Production of color filter substrate)
As shown in FIG. 1, the frame-shaped light shielding layer 2, the base 4, and the black matrix 8 were formed on the transparent substrate 1 which consists of glass using the black composition mentioned above. The thickness of the light shielding layer was 2.9 μm, and the thicknesses of the black matrix 8 and the pedestal 4 were 0.6 μm. The light shielding layer 2, the pedestal 4 and the black matrix 8 are coated with the above-described black composition and dried, and then a gray-tone photomask (a photomask having a transmittance difference between the light shielding layer pattern and the pedestal and black matrix pattern, respectively). Using a mask, the film was formed on the transparent substrate 1 by a single filming process by exposure / development and heat treatment.

  Next, the light scattering layer 11 shown in FIGS. 3 and 6 (indicated by a broken line) was formed to a thickness of 2.4 μm using the above-described resin composition for a light scattering layer.

  Further, on the transparent substrate 1, a spacer 5 was formed by stacking the red pixel 3R, the green pixel 3G, the blue pixel 3B, and the red stacked portion 5R, the green stacked portion 5G, and the blue stacked portion 5B. As the exposure mask for forming colored pixels (green pixels) and spacers on the light-scattering layer 11 shown in FIG. 3, a gray-tone photomask whose pattern portion has low transmittance was used.

  The thickness of the colored layer (red pixel 3R, green pixel 3G, blue pixel 3B) formed directly on the transparent substrate 1 made of glass was 4.5 μm ± 0.2 μm. The thickness of the colored pixel 3 on the light scattering layer 11 was 2.3 μm ± 0.2 μm.

  Further, a cell gap regulating layer 12 having a film thickness of 1.6 μm was formed on the colored pixel 3 on the light scattering film 11 using an acrylic photo-sensitive resin capable of alkali development. A cell gap regulating layer 12 (not shown in FIG. 6) was formed in the same pattern on the frame-shaped light shielding layer 2 shown in FIG. The total film thickness of the light shielding layer 2 and the cell gap regulating layer 12 on the light shielding layer 2 is about 4.5 μm, which is substantially the same as the film thickness of the green pixel 3G.

  Further, the size of the bottom side of the spacer 5 shown in FIG. 1 was 30 μm, and the height of the red laminated portion constituting the spacer 5 was about 3.6 μm. The height of the protrusion of the overlapping portion of the blue pixel 3B and the green pixel 3G below the red stacked portion shown in FIG. 2 is about 0.1 μm, and the overall height of the spacer 5 is 3.7 μm. The liquid crystal thickness of the target liquid crystal display device is 3.6 μm.

  The thickness of the liquid crystal layer on the reflecting portion shown in FIG. 3 was 1.8 μm. By setting the thickness of the cell gap regulating layer 12 to be ½ or less of the thickness of the liquid crystal layer in the transmissive portion, the thickness of the liquid crystal layer in the reflective portion can be reduced to about ½. The film thickness of the cell gap regulating layer 12 shown in FIG. 3 needs to be set in consideration of the film thickness of the light scattering layer 11 and the colored laminated portion.

  The protrusion height d on the pedestal 4 shown in FIG. 2 was as low as 0.1 μm on the blue pixel side and 0.17 μm on the green pixel side, and the flatness was good. The height h of the spacer 5 is the sum of the thickness of the red laminated portion and the height d of the protrusion.

[Example 2]
(Production of color filter substrate)
The color filter substrate according to Example 2 will be described based on FIG. 4 which is a schematic plan view of the color filter substrate which is the first embodiment of the present invention, and in combination with FIGS. To do. The present embodiment is different from the color filter substrate according to the first embodiment in that a black matrix is not formed and a phase difference adjusting function is added to the cell gap regulating layer.

  On the transparent substrate 1 made of glass, the light shielding layer 2 and the pedestal 4 shown in FIGS. 1 to 4 were formed using the above-described black composition. The thickness of the light shielding layer 2 was 2.9 μm, and the thickness of the base 4 was 0.6 μm. The light shielding layer 2 and the pedestal 4 are coated with the above-described black composition, dried, and then used with a gray tone photomask (a photomask having a difference in transmittance between the light shielding layer pattern and the pedestal pattern). The film was formed on the transparent substrate 1 by a film hardening process by repeated exposure / development and heat treatment.

  Next, using the above-described resin composition for a light scattering layer, the light scattering layer 11 shown by a broken line in FIG. 4 or shown in FIG. 3 was formed to a thickness of 2.4 μm.

  Further, on the transparent substrate 1 shown in FIG. 1, a red pixel 3R, a green pixel 3G, a blue pixel 3B, and a spacer 5 and a sub-spacer 6 by forming a pattern of a red colored layer were formed. As the exposure layer mask for forming the colored laminated portion on the light scattering layer 11 and the spacers 5 and the sub-spacers 6 shown in FIG.

  The film thicknesses of the colored layers (red pixel 3R, green pixel 3G, blue pixel 3B) formed directly on the transparent substrate 1 made of glass were all 4.5 μm ± 0.2 μm.

  On the colored laminated portion of the reflective portion shown in FIG. 3, a cell gap regulating layer 12 having a phase difference function for changing a quarter wavelength, which will be described in detail below, was formed with a film thickness of 1.6 μm ± 0.1 μm. .

  As a pretreatment of the colored pixel surface for imparting a phase difference function to the cell gap regulating layer 12, an alignment film material (“SE-1410” manufactured by Nissan Chemical Industries, Ltd.) is applied on the colored pixel (color filter). The film was applied with a spin coater so that the dry film thickness was 0.1 μm, dried on a hot plate at 90 ° C. for 1 minute, and then baked at 230 ° C. for 40 minutes in a clean oven. Subsequently, this substrate was subjected to a rubbing treatment in a certain direction to be a pretreatment.

  A mixture having the composition shown below for forming the cell gap regulating layer was stirred and mixed so as to be uniform, and filtered through a 0.6 μm filter to obtain a polymerizable liquid crystal compound. This polymerizable liquid crystal compound was applied onto the pretreated colored pixels so that the dry film thickness was 1.6 μm, and dried by heating at 90 ° C. for 2 minutes on a hot plate to obtain a liquid crystal alignment substrate.

Horizontally-aligned polymerizable liquid crystal 39.7 parts (“Palocolor LC 242” manufactured by BASF Japan Ltd.)
Photopolymerization initiator 0.3 part ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 6.0 parts ("BYK111" 2% cyclohexanone solution manufactured by Big Chemie)
154.0 parts of cyclohexanone Next, the substrate coated with the polymerizable liquid crystal was exposed to ultraviolet rays for each colored pixel region of the reflecting portion through a photomask using an exposure machine using an ultrahigh pressure mercury lamp as a light source. The dose of ultraviolet rays, by changing the number of shots of the laser, 500 mJ / cm ² in the red pixel region, 200 mJ / cm ² in the green pixel region, and 5 mJ / cm ² in the blue pixel region, further cell gap regulating layer by development treatment Pattern was formed.

  Subsequently, the substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to obtain a color filter substrate provided with the cell gap regulating layer 12 provided with a ¼ phase difference function.

When the total of the phase difference between the colored pixel and the cell gap regulating layer of the obtained color filter substrate was measured, the red pixel portion was 161 nm in the light of wavelength 630 nm, the green pixel portion was 136 nm in the light of wavelength 550 nm, and the blue pixel portion was It was 112 nm in light having a wavelength of 450 nm. The results are shown in Table 5 below.

  A cell gap regulating layer (not shown in FIG. 4) was formed in the same pattern on the frame-shaped light shielding layer 2 shown in FIG. The total film thickness of the light shielding layer 2 and the cell gap regulating layer on the light shielding layer is about 4.5 μm, which is substantially the same as the film thickness of the green pixel 3G.

  Also, the size of the base of the spacer 5 shown in FIG. 2 is 30 μm, the height of the red laminated portion constituting the spacer 5 is about 3.6 μm, and the overlapping portion of the color pixel 3B and the green pixel 3G below the red laminated portion is formed. The height of the protrusion was about 0.1 μm, and the overall height of the spacer 5 was 3.7 μm. The liquid crystal thickness of the target liquid crystal display device is 3.6 μm.

  The protrusion height d on the pedestal 4 shown in FIG. 2 was as low as 0.1 μm on the blue pixel side and 0.17 μm on the green pixel side, and the flatness was good. The height h of the spacer 5 is the sum of the thickness of the red laminated portion and the height d of the protrusion.

Example 3
(Production of liquid crystal display device)
A liquid crystal display device having the structure shown in FIG. 10 was produced.

  A color filter substrate 31 and a TFT substrate 32 are arranged to face each other, and a VA liquid crystal layer 33 oriented perpendicular to the substrate surface is sandwiched between them to obtain a liquid crystal display device. In addition, illustration of the polarizing film, retardation film, and alignment film was abbreviate | omitted.

  The pixel electrode 35 electrically connected to the TFT element 34 has a comb-like pattern made of a transparent conductive film. Although not shown, a common electrode is disposed below the pixel electrode via an insulating layer. As the color filter substrate 31, the same one as obtained in Example 2 shown in FIGS. 1 to 4 was used, and the thickness of the liquid crystal layer 33 was set to 3.6 μm.

  In this embodiment, the color filter substrate 31 has the same thickness as the colored layer, which is a green pixel, and the combined thickness of the light shielding layer and the cell gap regulating layer, and there is no extra protruding structure, so that the color filter substrate 31 is smooth and uniform. The liquid crystal can be filled and the image display is very uniform and good. A high-quality liquid crystal display device free from light leakage without any disturbance of the liquid crystal alignment around the colored pixels or at the boundary between the light shielding layer and the display region was obtained.

  A partially enlarged view of the liquid crystal display device in the vicinity of the TFT element 34 shown in FIG. 10 is shown in FIG. 11 (the light scattering layer and the cell gap regulating layer are not shown). When the thickness of the insulating layer 41 is small, more efficient liquid crystal driving through the insulating layer 41 is possible by the arch-shaped electric lines of force 44 formed between the pixel electrode 42 and the common electrode 43. According to this embodiment, since there is a cell gap regulating layer provided in the reflecting portion, there is no difference in display quality between the reflecting portion and the transmitting portion, and a liquid crystal display device with high transmittance can be obtained.

  As described above, the present invention is not limited to the VA method for the liquid crystal alignment method. Compatible with IPS and various FFS liquid crystal display devices by forming a cell gap regulating layer having a phase difference function thick or using a material having a large birefringence for the cell gap regulating layer. can do.

  The IPS-type transflective liquid crystal display device requires a half-wave retardation layer in the reflection part, but the cell provided with the quarter-wave retardation function used in Example 2 By doubling the film thickness of the gap regulating layer 12, the cell gap regulating layer 12 to which a 1/2 wavelength phase difference forming function is imparted can be obtained.

  Further, by using a retardation material having a double birefringence without changing the film thickness, it is possible to obtain a cell gap regulating layer to which a half-wave retardation forming function is imparted.

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 11 ... Light-shielding layer 3 ... Colored pixel 3R ... Red pixel 3G ... Green pixel 3B ... Blue pixel 4 ... Base 5 ... Spacer 6 ... Subspacer 7 ... Protrusion 8 ... Black matrix 11 ... Light scattering layer 12 ... Cell gap regulating layer 13 ... Amorphous fine particles 14 ... Matrix resin (transparent resin)
22 ... thick colored pixels 23 ... thin colored pixels 31 ... color filter substrate 32 ... TFT substrate 33 ... liquid crystal layer 34 ... TFT elements 35, 42 ... pixel electrodes 41 ... -Insulating layer 43 ... Common electrode 44 ... Electric field lines.

Claims (13)

A transflective liquid crystal in which a light shielding layer mainly composed of a mixture of a plurality of organic pigments is disposed on the outer periphery of an effective display area on a transparent substrate and a plurality of colored pixels including green pixels are formed in the effective display area In color filter substrates for display devices,
A spacer pedestal made of the same material as the light shielding layer formed in the effective display area and having a film thickness thinner than the light shielding layer, a spacer made of a single colored layer formed above the pedestal, semi-transmissive A plurality of light scattering layers formed on the reflective portion of the liquid crystal display device, and a plurality of first cell gap regulation layers formed at positions corresponding to the light scattering layers on the colored pixels. A color filter substrate for a transflective liquid crystal display device.   2. The color filter substrate for a transflective liquid crystal display device according to claim 1, wherein the green pixel is composed of a green colored layer mainly composed of zinc halide phthalocyanine.   3. The half according to claim 1, wherein a difference in height between the surface of the cell gap regulating layer and the surface of the colored pixel is approximately ½ of the thickness of the liquid crystal layer of the liquid crystal display device. Color filter substrate for transmissive liquid crystal display devices.   A second cell gap regulating layer formed on the light shielding layer and having the same shape as the light shielding layer is further provided, and a total film thickness of the light shielding layer and the second cell gap regulating layer is a film thickness of the green pixel. The color filter substrate for a transflective liquid crystal display device according to claim 1, wherein the color filter substrate is substantially the same.   5. The transflective liquid crystal according to claim 1, wherein the light scattering layer has a rectangular shape and a size in plan view is smaller than a size in plan view of the colored pixel. Color filter substrate for display devices.   The color filter substrate for a transflective liquid crystal display device according to any one of claims 1 to 5, wherein adjacent portions of the colored pixels overlap each other at an inclined portion of an end portion of the colored pixel.   The black matrix made of the same material as that of the light shielding layer, further arranged to divide the colored pixels in an effective display area on the transparent substrate. Color filter substrate for transflective liquid crystal display devices.   The color filter substrate for a transflective liquid crystal display device according to claim 1, wherein the pedestal has a film thickness of 0.4 μm to 1.0 μm.   The first cell gap regulating layer has a function of rotating incident light that is converted into linearly polarized light by 90 degrees in one round-trip in the thickness direction of the cell gap regulating layer. The color filter substrate for a transflective liquid crystal display device according to any one of 8.   The plurality of colored pixels include at least a red pixel, a green pixel, and a blue pixel, and a phase difference between these colored pixels has a relationship of red pixel ≧ green pixel ≧ blue pixel. A color filter substrate for a transflective liquid crystal display device according to any one of the above.   The plurality of colored pixels include at least a red pixel, a green pixel, and a blue pixel, and a phase difference between each of the colored pixels and a phase difference between each of the first cell gap regulation layers stacked on the colored pixel. 11. The color filter substrate for a transflective liquid crystal display device according to claim 1, wherein the total is in a relationship of red pixel ≧ green pixel ≧ blue pixel.   12. The color for a transflective liquid crystal display device according to claim 1, wherein the spacer also serves as a liquid crystal alignment control and is disposed at a center in a longitudinal direction of the colored pixel. Filter substrate.   A transflective liquid crystal display device comprising the color filter substrate for a transflective liquid crystal display device according to claim 1.

Images