WO2011093337A1 - 半透過型液晶表示装置用カラーフィルタ基板、その製造方法、及び半透過型液晶表示装置 - Google Patents
半透過型液晶表示装置用カラーフィルタ基板、その製造方法、及び半透過型液晶表示装置 Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133553—Reflecting elements
- G02F1/133555—Transflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133371—Cells with varying thickness of the liquid crystal layer
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133631—Birefringent elements, e.g. for optical compensation with a spatial distribution of the retardation value
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
Definitions
- the present invention relates to a color filter substrate for a liquid crystal display device, a method for manufacturing the same, and a liquid crystal display device, and in particular, a color filter substrate for a transflective liquid crystal display device that uses both a backlight on the back surface of the liquid crystal display device and external light,
- the present invention relates to a manufacturing method thereof and a transflective liquid crystal display device including the same.
- the present invention relates to a color filter substrate suitable for a liquid crystal display device of a liquid crystal driving system such as FFS or IPS.
- IPS In-Plane Switching
- VA Vertical Alignment
- HAN Hybrid Aligned br Nematic
- FFS Ringe Field Switching
- OCB Optically Compensated Bend
- liquid crystal display devices such as the IPS system in which liquid crystal is aligned parallel to the substrate surface, such as glass
- the VA system that is easy to support high-speed response
- the FFS system that is effective for a wide viewing angle
- flatness film
- Higher levels are required for electrical characteristics such as thickness uniformity (reduction of unevenness of the color filter surface) and dielectric constant.
- a technique for reducing the thickness of the liquid crystal cell has become a major issue in order to reduce coloring in viewing in an oblique direction.
- a technique for reducing the thickness of the liquid crystal cell is also a major issue for driving the liquid crystal even faster. It has become.
- Patent Document 1 In order to reduce coloration in viewing the liquid crystal display device in an oblique direction, there is a technique of using a plurality of colored layers as spacers in order to make the liquid crystal cell thickness uniform in addition to flattening of the color filter (for example, see Patent Document 1).
- a technique of using a plurality of colored layers as spacers in order to make the liquid crystal cell thickness uniform in addition to flattening of the color filter For example, see Patent Document 1).
- forming the spacers by laminating a plurality of colored layers and the like by a photolithography technique is excellent from the viewpoint of securing a uniform liquid crystal cell gap.
- Patent Document 1 does not disclose color filter characteristics and configuration appropriate for the FFS method and the IPS method, and does not describe a technique related to the light scattering layer.
- a general liquid crystal cell such as an FFS method or an IPS method is configured by arranging and attaching the color filter side of the color filter substrate and the array side of the array substrate to face each other.
- a spacer is provided between the substrates, and the thickness of the liquid crystal layer sandwiched between the two substrates is controlled.
- a transmissive liquid crystal display device is provided with a diffusion plate for diffusing light together with the above-described backlight on the back surface on the array substrate side as a liquid crystal cell.
- 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 drive a liquid crystal and formed in a comb-like pattern shape).
- TFT elements for example, TFT elements that are electrically connected to drive a liquid crystal and formed in a comb-like pattern shape.
- Transparent electrode and an array substrate provided with a common electrode.
- a common electrode usually a thin film of conductive metal oxide called ITO, also called a transparent electrode
- liquid crystal aligned in the direction parallel to the array substrate surface (horizontal) is used, and a comb-like pixel electrode as described above and an insulating layer of about 0.3 ⁇ m to 0.5 ⁇ m are provided below the pixel electrode.
- This is a system driven by an arch-shaped electric field (lines of electric force) generated between the common electrodes disposed between the electrodes.
- fluorescent and LED backlights are provided on the back and side surfaces of these FFS and IPS 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. Studies on liquid crystal display devices to be used are in progress.
- a transflective liquid crystal display device has one pixel as a transmissive portion that uses light from the back surface of the backlight as transmitted light, and a reflective portion that reflects external light or light from the front light.
- This is a liquid crystal display device used in a divided manner. Or it is a liquid crystal display device which can turn off a backlight and can visually recognize the display with bright outside light such as sunlight in a bright outdoor room.
- Patent Documents 2 and 3 Techniques for forming a light scattering film for a reflective or transflective liquid crystal display device are disclosed in Patent Documents 2 and 3, for example. These technologies do not disclose color filter characteristics suitable for the FFS method and the IPS method, and are based on a configuration in which a transparent electrode is laminated on a color filter disposed on an observer-side electrode substrate or the like. Yes.
- a technology of a phase difference element having different phase differences for each color of red, green, and blue, a technology of a phase difference layer of a continuous film laminated on a color filter, and the like are known (for example, see Patent Documents 4 and 5). .
- Patent Documents 4 and 5 A technology of a phase difference element having different phase differences for each color of red, green, and blue, a technology of a phase difference layer of a continuous film laminated on a color filter, and the like are known (for example, see Patent Documents 4 and 5). .
- Patent Documents 4 and 5 disclose color filter characteristics appropriate for the FFS method and the IPS method, and there is no description of the technology related to the light scattering layer.
- Patent Document 7 proposes a color filter having different phase differences between a reflection part and a transmission part. None of these patent documents disclose a color filter characteristic suitable for the FFS method and the IPS method, and there is no description of a technique related to the light scattering layer.
- 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 No. 3788421 JP 2009-128860 A
- a color filter member such as a light shielding layer or a black matrix is used for a liquid crystal display device such as an FFS method or an IPS method from the viewpoint of electrical characteristics and flatness.
- a liquid crystal display device such as an FFS method or an IPS method from the viewpoint of electrical characteristics and flatness.
- a problem in smooth electric field formation through the liquid crystal due to the driving voltage applied between the pixel electrode and the common electrode peculiar to the FFS method and the IPS method, and there is a problem in high-quality display. .
- phase adjustment necessary for a transflective liquid crystal display device for example, a quarter wavelength layer (usually a retardation layer having a function of converting linearly polarized light into circularly polarized light, or converting circularly polarized light into linearly polarized light.
- a retardation layer having a function of returning hereinafter, simply referred to as a retardation layer having a function of rotating the incident light from the outside, which has been linearly polarized light, by 90 degrees in the thickness direction by one reciprocation in the thickness direction.
- a quarter wavelength layer since the technique disclosed in Patent Document 7 has a configuration in which a reflective layer and a retardation layer are arranged in this order on one substrate, the reflective layer cannot be used as a light reflective electrode.
- Patent Documents 6 and 7 that disclose the installation of a retardation layer in a transflective liquid crystal display device have high intensities such as sunlight and are not supposed to use a liquid crystal display device under parallel light, and are bright. It was not intended to be a liquid crystal display device that can be used in both an environment and a dark environment. Furthermore, it is not compatible with liquid crystal display devices such as the above-described FFS method and IPS method, and there is no description of color filter characteristics necessary for these liquid crystal display devices.
- the color filter substrate proposed in the technique of Patent Document 8 has a conductive counter electrode on the color filter and conductive metal chromium as a black matrix, liquid crystal such as FFS mode and IPS mode is used. It is difficult to apply to a display device.
- the unreacted monomer of the polymerizable liquid crystal compound used for forming the quarter wavelength layer is the surface of the quarter wavelength layer.
- the unreacted monomer may contaminate the liquid crystal used in the liquid crystal display device and cause deterioration in display characteristics, or may cause a change with time in the phase difference of the quarter wavelength layer itself.
- Many of the polymerizable liquid crystal compounds are oxygen-inhibited, and the unreacted portions as described above are likely to remain even after the film hardening after exposure, leading to deterioration of the optical function.
- the layer when the quarter wavelength layer is formed as an independent pattern having a rectangular cross section on the reflection portion, the layer may be fluidized at the time of hardening by heat treatment, resulting in shape collapse.
- a 1/4 wavelength layer when a 1/4 wavelength layer is not formed for each colored pixel and is used as a solid film, a phase difference remains in a portion (transmission part) where a 1/4 wavelength phase difference is unnecessary, and display quality is increased. The adverse effect on was inevitable.
- carbon black is excellent in terms of light shielding properties and particularly preferable.
- carbon black is a colorant having a high dielectric constant, and is used for liquid crystal display devices such as FFS and IPS. Is not appropriate.
- the main coloring material (100% to 90% with respect to the total amount of pigment (weight ratio)
- the light blocking layer and the black matrix have a relative dielectric constant of about 7 to 15, and the liquid crystal of the FFS mode or IPS mode.
- the color filter constituting member is not suitable for driving.
- the relative dielectric constant of a liquid crystal material driven by an active element such as TFT is about 7 to 40 in the molecular direction where the relative dielectric constant is large.
- the relative dielectric constant thereof is 5 or less, preferably 4.5 or less.
- 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.
- 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.
- Patent Document 8 discloses a technique in which a light-shielding partition wall is provided on a substrate in advance, and a color filter or a retardation layer is formed between the partition walls by a droplet discharge method.
- a partition wall having a height for holding droplets ejected from the nozzle is an important component of this technique.
- it is a light-shielding and photosensitive material (for example, in paragraphs 0048 and 0060 of Patent Document 8).
- it is difficult to produce a thin wire suitable for a liquid crystal display device or a good cross-sectional shape with a high yield.
- the present invention has been made in view of the above circumstances, and is a color filter substrate for a transflective liquid crystal display device suitable for a liquid crystal display device such as an FFS system or an IPS system, a manufacturing method thereof, and a transflective liquid crystal display device.
- the purpose is to provide.
- the light shielding layer is arranged on the outer periphery of the effective display area on the transparent substrate, and the colored pixels including the green pixels, the spacers, and the first retardation layer are effectively displayed.
- the color filter substrate for a transflective liquid crystal display device formed in a region a concave portion is formed in each of the colored pixels, and the first retardation layer is provided in the concave portion and converted into linearly polarized light.
- a color filter substrate for a transflective liquid crystal display device having a function of rotating incident light by 90 degrees in one reciprocation in the thickness direction of the first retardation layer.
- a transflective liquid crystal display device comprising the above-described color filter substrate for a transflective liquid crystal display device.
- the light shielding layer is disposed on the outer periphery of the effective display area on the transparent substrate, and the colored pixels including the green pixel, the spacer, and the first retardation layer are effectively displayed.
- a step of forming a recess in each of the plurality of colored pixels, and an alignment film for aligning a retardation layer in the recess by an inkjet method A method of manufacturing a color filter substrate for a transflective liquid crystal display device, comprising the step of forming, is provided.
- a color filter substrate that is optimal for the FFS method and the IPS method is provided, and in particular, a transflective liquid crystal display device that is excellent in both transmissive part display and reflective part display is provided.
- a transflective liquid crystal display device is provided by disposing a retardation layer and a cell gap adjusting layer or a light scattering layer having a function of diffusing light together with a total retardation in a colored pixel.
- a color filter substrate optimal for the above can be provided.
- the cell gap adjusting layer or the light scattering layer when the cell gap adjusting layer or the light scattering layer is laminated after forming the retardation layer, the cell gap adjusting layer or the light scattering layer is effective for protecting the retardation layer, and the reason is As will be described later, a retardation layer having stable retardation characteristics can be obtained by promoting the curing of the retardation layer.
- an alignment film for the alignment treatment of the retardation layer can be selectively formed in the concave portion of the colored layer in a few steps in advance, so that high image quality can be achieved as a liquid crystal display device.
- a color filter substrate that can be obtained can be provided.
- the step of the frame portion can be eliminated, and the thickness of the stack can be reduced to that of the green pixel.
- 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.
- a color filter substrate having excellent flatness can be formed with a small number of steps with high accuracy, and a liquid crystal display device including the color filter substrate is provided.
- a color filter substrate for a high-quality liquid crystal display device and a liquid crystal display device in consideration of electrical characteristics such as relative permittivity are provided.
- the phase difference between the blue pixel, the green pixel, and the red pixel, or the phase difference obtained by adding the phase difference of the retardation layer to these colored pixels is represented by a relationship of red pixel ⁇ green pixel ⁇ blue pixel.
- 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.
- the film thickness of the colored pixel is in the relationship of red pixel ⁇ green pixel ⁇ blue pixel.
- 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.
- FIG. 6 is a sectional view showing a color filter substrate obtained in Example 3.
- FIG. It is a fragmentary sectional view which shows the liquid crystal display device which concerns on one Embodiment of this invention. It is a fragmentary sectional view which shows the liquid crystal display device of this invention, and is a schematic diagram which shows FFS drive of a liquid crystal. It is a schematic cross section of a conventional color filter substrate.
- a color filter substrate includes a light shielding layer disposed on the outer periphery of an effective display area on a transparent substrate, and a plurality of colored pixels including a green pixel, a spacer, and a first retardation layer Is formed in the effective display area, and is applied to a transflective liquid crystal display device.
- the transflective liquid crystal display device includes a reflection unit that receives and reflects light incident from the observer side such as external light and a front light, and a transmission unit that transmits light from the backlight disposed on the back surface of the liquid crystal display device.
- the colored pixel is also divided into a reflective portion and a transmissive portion for each pixel.
- 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.
- a concave portion is formed in each reflective portion of the colored pixel, and a retardation layer is provided in the concave portion.
- This retardation layer has a function of compensating for the optical path difference between the reflection portion and the transmission portion described above.
- the linearly polarized light which is incident light (external light) transmitted through the external polarizing plate of the liquid crystal display element, is converted into circularly polarized light, and the light-reflective electrode (or reflector plate) disposed inside the liquid crystal display element ) To return the reflected light to the substantially linearly polarized light and use it as outgoing light.
- the retardation layer is a reflective liquid crystal display device that uses a light-reflecting reflective electrode, and changes the phase of polarized light by a quarter wavelength or a half wavelength, and makes one round trip in the thickness direction of the liquid crystal layer. (Reflection) has a function of making linearly polarized light with 90 degrees different directions.
- the polarization layer may be rotated by 90 degrees or 270 degrees using a 1 ⁇ 2 wavelength retardation layer.
- the absorption axis of the polarizing plate and the slow axis of the retardation layer are 22.5 degrees or 67.5.
- the incident light converted to linearly polarized light can be effectively rotated by 90 degrees by using the phase difference layer of 1 ⁇ 2 wavelength shifted by the degree.
- 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.
- the spacer is a structure having a trapezoidal or columnar cross section formed in order to make the thickness of the liquid crystal layer in the transmissive portion in the effective display region uniform, and the thickness of the liquid crystal layer. And almost the same height.
- a sub-spacer having a low height can be formed in the effective display area and on the light shielding layer.
- These spacers may be formed on the color filter using, for example, an alkali-soluble photosensitive acrylic resin, but by forming a single layer to three-layer laminate of colored layers, colored pixels are formed. Since it can be formed simultaneously, the manufacturing process can be simplified.
- the liquid crystal panel is formed by adhering a color filter substrate and an array substrate on which active elements for driving the liquid crystal are formed facing each other so as to sandwich the liquid crystal layer.
- the spacer height must include the margin at this time.
- the spacer height is a height from the top of the spacer to the center of the adjacent pixel and the surface of the colored pixel.
- a colored layer is formed by simply forming a colored layer at a portion where a transmissive portion is formed, a recessed colored layer at a thin portion of a reflective portion, and a colored layer laminated as a spacer. Expressed separately from the colored layer.
- These colored layers can be manufactured by the same coating process and photolithography process.
- a coating layer applied on a transparent substrate with a photosensitive coloring composition for forming a pixel of a color filter, or a single-layer layer with a photosensitive coloring composition is used as a coloring layer, and the coloring layer is used for publicly known.
- a pattern formed by this photolithography technique is called a colored pixel.
- the thickness of the colored pixel refers to the height from the surface of the transparent substrate to the surface of the center of the colored pixel (here, the center of the pixel in the colored layer where no recess is formed).
- the ratio of the thickness of the concave colored layer to the thickness of the colored layer (the portion where no concave is formed) is preferably in the range of 1/2 to 1/4. It should be noted that the thickness of the concave colored layer having a thickness ratio of 1/2 is 1/2 within an error range of ⁇ 0.2 ⁇ m with respect to the thickness of the colored layer.
- the original color display in consideration of the optical path difference between the transmissive part and the reflective part can be obtained by setting the ratio of the thickness of the colored layer of the concave part to the thickness of the colored layer (the part where the concave part is not formed) to be approximately 1 ⁇ 2. Can do.
- the reflection part is for observation in a bright environment such as outdoors, and brightness is important. Although it is desirable that the chromaticity areas of the transmissive part and the reflective part coincide with each other, it is sufficient to recognize that the color is on when the brightness is most important.
- the reflective display has a film thickness ratio of 1/3 or 1/4 in an application in which “brightness” is more important than color matching of the transmissive portion display (for example, outdoor use where sunlight is present). Therefore, it is desirable to use a color with high brightness.
- the NTSC ratio of the reflective part is about 35 to about 1/4 when the film thickness is 1/4 (with two transmissions). It becomes about 40%. If the NTSC ratio is 35 to 40%, it can be easily recognized that the color is on, but if it is much lower than this, it becomes difficult to recognize that the color is on. Therefore, it is desirable that the film thickness of the reflection part is 1 ⁇ 4 or more that the NTSC ratio is about 35 to 40%.
- the color visibility in moving image gradation display tends to be lower than in still image display.
- the thickness of the concave colored layer that is 1/4 of the colored layer thickness is a color display when moving image gradation display is performed.
- the film thickness is almost the lower limit.
- 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 colored pixel surface at the center of the pixel.
- the colored pixels of a plurality of colors are expressed as blue pixels, red pixels, green pixels, yellow pixels, white pixels (transparent pixels), and the like.
- the 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.
- the colored layers stacked as spacers are referred to as a red stacked portion, a green stacked portion, and a blue stacked portion, respectively.
- the substantially same film thickness can be controlled by the manufacturing process in the formation of the light shielding layer and the colored layer. For example, the manufacturing margin in the color filter manufacturing process with respect to the set film thickness.
- the film thickness is within ⁇ 0.2 ⁇ m.
- the relative dielectric constant referred to in the description of the present specification is based on the assumption that measurement is performed at room temperature at a frequency of 50 Hz to 500 Hz used for liquid crystal driving.
- a cell gap adjustment layer is disposed on the retardation layer for the purpose of adjusting the thickness of the liquid crystal layer in the transmission part and the reflection part described above.
- the difference in height from the surface of the cell gap adjusting layer and the surface of the colored pixel where no recess is formed can be approximately 1 ⁇ 2 of the thickness of the liquid crystal layer when the liquid crystal display device is constructed.
- approximately 1/2 of the thickness of the liquid crystal layer may vary within a range of 10% of the thickness of the liquid crystal layer, and within ⁇ 0.2 ⁇ m that is the manufacturing margin in the manufacturing process of the color filter. It is desirable to be.
- substantially the same film thickness similarly refers to a film thickness that increases or decreases within a manufacturing margin of ⁇ 0.2 ⁇ m in the color filter manufacturing process.
- the cell gap adjusting layer may be an insulator transparent in the visible range, but is preferably a light scattering layer imparted with light scattering properties.
- the light scattering layer serves as a diffuser for imparting diffusibility to the emitted light, making the light from the liquid crystal display device that enters the observer's eyes look like paper white and displaying with good visibility.
- a pedestal and a black matrix are arranged.
- the pedestal and the black matrix are formed of the same light shielding material as that of the light shielding layer.
- the pedestal is arranged almost corresponding to the position of an active element such as a TFT when a liquid crystal display device configured by bonding a color filter substrate and an array substrate is assumed.
- the spacer is disposed on the substrate side, and a spacer for uniformizing the cell gap is disposed thereon.
- the pedestal only needs to have an area that roughly covers the active element in plan view.
- the black matrix formed as necessary refers to a light shielding pattern in a lattice shape or a stripe shape provided in the display region for the purpose of improving the contrast of the liquid crystal display device.
- the film thickness of the pedestal and the black matrix is preferably thinner than that of the light shielding layer.
- the method of forming these thinly can be adjusted by a halftone mask used for exposure, a gray tone mask, an opening shape of the mask, or the like, in addition to adjustment in a process such as a development process or a heat treatment process.
- FIG. 1 is a diagram showing a cross section of a part of a color filter substrate according to an embodiment of the present invention, and corresponds to a cross section A-A ′ of a plan view shown in FIG. 5 described later.
- a light-shielding layer 2 made mainly of an organic pigment is disposed on the outer peripheral frame portion of the display area on the transparent substrate 1, and a red pixel 3R (not shown), a green pixel 3G, and a blue pixel 3B are displayed in the display area.
- Three colored pixels (not shown) are formed.
- the colored pixel (3G in FIG. 1) is composed of a reflective portion and a transmissive portion, and a concave portion 10 is formed in the reflective portion.
- a retardation layer 11 is formed in the recess 10, and a light scattering layer (cell gap adjustment layer) 12 is formed on the retardation layer 11.
- a retardation layer 11 ′ is also disposed on the frame-shaped light shielding layer 2.
- the light scattering layer 12 is a layer in which single or plural kinds of amorphous fine particles 13 are dispersed in a matrix resin 14 having different refractive indexes.
- the cell gap adjusting layer functioning as the light scattering layer 12 is an optical functional film that scatters incident light to give the observer a paper white-like effect.
- the matrix resin 14 may be a transparent resin that has heat resistance and visible range transparency.
- the film thickness of the light scattering layer is preferably in the range of about 1.5 ⁇ m to 5 ⁇ m because of the relationship between the amorphous fine particle diameter, the light wavelength, and the suitability in the manufacturing process.
- a cell gap adjusting layer 15 made of a transparent resin is formed as a cell gap adjusting layer instead of the light scattering layer 12 shown in FIG.
- the cell gap adjustment layer 15 is disposed 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 adjusting layer 15.
- the cell gap adjustment layer 15 ′ is also disposed on the frame-shaped light shielding layer 2, and the total thickness of the cell gap adjustment layer 15 ′ and the light shielding layer 2 in this portion is as follows. It is substantially equal to the film thickness of the green pixel 3G. 2 corresponds to a C-C ′ cross section of the plan view shown in FIG. 7 described later.
- FIG. 3 is a sectional view showing another part of the color filter substrate according to the embodiment of the present invention, and corresponds to a B-B ′ section of the plan view shown in FIG. 5 described later.
- a light shielding layer 2 mainly composed of an organic pigment is provided at the outer peripheral frame portion of the display area on the transparent substrate 1, and the display area has three colors including a red pixel 3R, a green pixel 3G, and a blue pixel 3B. 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 red pixel 3R and the green pixel 3G. On the pedestal 4, a red laminated portion 5R, a green laminated portion 5G, and A spacer 5 made of a stack of blue stacked portions 5B is formed.
- a pedestal 4 'made of the same material as that of the light shielding layer 2 and having no spacer 5 formed thereon is formed on the transparent substrate 1 at the boundary between the green pixel 3G and the blue pixel 3B.
- the pedestal 4 ′ in which the spacer 5 is not formed 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.
- a sub-spacer 6 having a two-layer structure, for example, which is lower than the spacer 5 having a three-layer structure is disposed on the light shielding layer 2.
- the pedestal 4 is thinner than the light shielding layer 2 and has a film thickness of 0.4 ⁇ m or more and 1.0 ⁇ m or less.
- the film thickness of the pedestal 4 is less than 0.4 ⁇ m, it is difficult to obtain a stable film thickness when the pedestal 4 is formed by photolithography.
- the thickness exceeds 1.0 ⁇ m the thickness of the laminated portion laminated thereon becomes thin, a sudden change in film thickness occurs between the pixels, and the laminated portion becomes unstable.
- 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.
- the thickness and the height of the spacer formed on the pedestal are substantially equal.
- the height h of the spacer 5 is the thickness of the portion protruding from the surface of the colored pixels 3R, 3G, 3B in the stack of the red stack portion 5R, the green stack portion 5G, and the blue stack portion 5B.
- a height obtained by adding a margin of about 0.1 ⁇ m in the cell manufacturing process to the thickness of the liquid crystal layer is preferable.
- FIG. 4 is an enlarged view showing 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 ⁇ m or less. .
- FIG. 5 is a diagram showing a planar arrangement of the light shielding layer 2, the bases 4, 4 ', the spacer 5, the sub-spacer 6, and the light scattering layer (cell gap adjusting layer) 12 in the color filter substrate. 5 corresponds to FIG. 1 and the B-B ′ cross section corresponds to FIG. 3.
- 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 pedestal 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 or less), 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.
- the light blocking layer and the black matrix have a relative dielectric constant of about 7 to 15, which is suitable for driving FFS and IPS liquid crystals. 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.
- all of the color material can be an organic pigment.
- red pigments examples 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.
- yellow pigments examples 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, 172 173,174,175,176,177,179,180,181,182,185,187,188,
- blue pigments examples 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 preferable.
- a purple pigment for example, 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 preferable.
- green pigments examples 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 preferable.
- Pigment pigment type it may be simply abbreviated as PB (Pigment Blue), PV (Pigment Violet), PR (Pigment Red), PY (Pigment Yellow), PG (Pigment Green), or the like.
- PG58 described above 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.
- 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 ⁇ n of green pigment). Can do.
- 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.
- the value of the dielectric constant is approximately equal to the square of the refractive index.
- the dielectric constant resulting from electronic polarization is proportional to the square of the refractive index.
- the main pigment G2 of the GP-4 pigment dispersion shown in Table 4 below is PG58.
- a pigment dispersion in which the first pigment G2 of GP-4 is replaced with PG36 is denoted as GP-5.
- a spectroscopic ellipsometer M-220 manufactured by JASCO was used to measure Nx, Ny, and Nz, and ⁇ n was calculated from the following equation. The measurement wavelength was 550 nm.
- ⁇ n [(Nx + Ny) / 2] ⁇ Nz
- the relative dielectric constant of the green pigment was measured at 120, 240, and 480 Hz under the condition of a voltage of 5 V using an impedance analyzer type 1260 manufactured by Solartron.
- a measurement sample a colored layer is applied and hardened on a glass substrate on which a conductive film made of an aluminum thin film is patterned (the film thickness is the same as in Examples described later), and a conductive film made of an aluminum thin film is formed on the colored layer. A film pattern is formed.
- the relative dielectric constant was measured for three colored layers obtained by using the green composition 1 containing the green pigment 1, the green composition 2 containing the green pigment 2, and the green composition 3 containing the green pigment 3 shown below. .
- Green pigment C.I. I. Pigment Green 58 (Dai Nippon Ink Chemical Co., Ltd. “Phthalogyanine Green A1 10 ”) 10.4 parts-Yellow pigment: C.I. I. Pigment Yellow 150 (“E4GN-GT” manufactured by LANXESS)) 9.6 parts • Dispersant (“Disperbyk-163” manufactured by Big Chemie) 2 parts • 66 parts of acrylic varnish (solid content 20% by mass).
- Green pigment C.I. I. Pigment Green 58 (Dai Nippon Ink Chemical Co., Ltd. “Phthalogyanine Green A1 10 ”) 10.4 parts-Yellow pigment: C.I. I. Pigment Yellow 150 (“E4GN-GT” manufactured by LANXESS) 3.2) Yellow pigment: C.I. I. Pigment Yellow 138 7.4 parts Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts Acrylic varnish (solid content 20% by mass) 66 parts.
- Green pigment C.I. I. Pigment Green 36 ("Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.) 10.4 parts-Yellow pigment: C.I. I. Pigment Yellow 150 (“E4GN-GT” manufactured by LANXESS)) 9.6 parts • Dispersant (“Disperbyk-163” manufactured by Big Chemie) 2 parts • 66 parts of acrylic varnish (solid content 20% by mass).
- Green composition 2 was obtained by the same composition and method as green composition 1 except that green pigment 2 was used as the dispersion.
- Green composition 3 was obtained by the same composition and method as green composition 1 except that green pigment 3 was used as the dispersion.
- 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.
- 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.
- the pigment is made fine, so that the coating characteristics of the photosensitive resin composition using the pigment dispersion are improved.
- the alkali-soluble resin or the pigment derivative may be used in combination as appropriate.
- 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.
- 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.
- a zinc halide phthalocyanine pigment is preferable because its thickness direction retardation is easily brought close to zero.
- a polymer dispersant is preferably used as the pigment dispersant because it is excellent in dispersion stability over time.
- 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.
- 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.
- 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.
- a pigment derivative or the like can be used as the dispersion aid.
- the dye derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole.
- oxinophthalone derivatives are preferred.
- substituent of the dye derivative examples 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.
- the dye derivative 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
- the pigment derivatives used in the examples described later are shown in Table 3 below.
- 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.
- 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.
- thermosetting resin examples include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
- 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 resins include monomers such as (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.
- the monomers listed above can be used alone or in combination of two or more. Further, it may be a copolymer of a compound such as styrene, cyclohexylmaleimide, and phenylmaleimide copolymerizable with these monomers.
- 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.
- a photosensitive resin can 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.
- a photosensitive resin can 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.
- 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.
- the solid acid value of the acrylic resin described above is preferably 20 to 180 mgKOH / g.
- 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.
- 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.
- the double bond equivalent of the acrylic resin is preferably 100 or more, more preferably 100 to 2000, and most preferably 100 to 1000. If the double bond equivalent exceeds 2000, sufficient photocurability may not be obtained.
- photopolymerizable monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol
- 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.
- a polyfunctional urethane acrylate having a (meth) acryloyl group obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group.
- the combination of the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate is arbitrary and is not particularly limited.
- one type of polyfunctional urethane acrylate may be used alone, or two or more types may be used in combination.
- photopolymerization initiator examples 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 methyldiphen
- sensitizer It is preferable to use a polymerization initiator and a photosensitizer in combination.
- sensitizers ⁇ -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.
- 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.
- the above photopolymerizable initiator, sensitizer, and ethylenically unsaturated compound may be added to a composition containing a polymerizable liquid crystal compound used for forming a retardation layer described later.
- 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, tris (2-hydroxyethyl) isocyanurate, trimercaptopropionic acid, 1,4-d
- 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.
- the photosensitive coloring composition can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.
- storage stabilizers 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.
- 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.
- silane coupling agents include vinyl silanes such as vinyltris ( ⁇ -methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) methyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, ⁇ -glycidoxypropyltrime
- 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.
- a solvent such as water or an organic solvent
- the solvent also has a function of uniformly dispersing the pigment.
- the solvent examples 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.
- 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).
- IPS horizontal alignment, lateral electric field method
- FFS Frringe Field Switching
- the color filter of the present invention can be used as an FFS VA liquid crystal display device.
- the liquid crystal thickness cell gap
- the thinner one can increase the response speed of the liquid crystal.
- the liquid crystal thickness is in the range of about 2 ⁇ m to 4 ⁇ m.
- 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.
- 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.
- the IPS and FFS methods can reduce the liquid crystal thickness.
- the refractive index anisotropy ⁇ n of the liquid crystal to be used is desirably larger than 0.07.
- 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.
- 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 liquid crystal layer is preferably about 1 ⁇ 2 of that of the transmission part.
- One of the comb-like pixel electrodes or the common electrode in the FFS system is formed of a light-reflective metal (aluminum alloy or silver alloy) thin film, whereby a reflective liquid crystal display device can be obtained. Further, a part of the comb-like pixel electrode or the common electrode is formed of a transparent conductive thin film such as ITO, whereby a transflective liquid crystal display device can be obtained.
- the spacer pedestal according to the present invention may be formed only at least in a portion where a spacer, which will 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. Specifically, a photomask in which multiple types of patterns with different transmittances, such as gray tone (gradation mask), or an opening smaller than the pattern size of the pedestal (adjustment of the opening size is used to adjust the exposure amount).
- the light-shielding layer and the pedestal can be formed at the same time by exposure using a photomask having an opening with a specially designed opening shape and photolithography after development after exposure.
- a photomask As a photomask, a photomask having a light shielding pattern as a thin film of metal chrome, 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.
- 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 film thickness of the pedestal is 1.0 ⁇ m or less, it is easy to stably obtain the film thickness of the colored layer laminated thereon.
- FIG. 6 shows the relationship between the thickness of the pedestal and the thickness of the layered portion of the colored layer on the pedestal.
- the preferred thickness of the pedestal is 0.4 ⁇ m to 1.0 ⁇ m.
- the film thickness of the black matrix which will be described later, may be formed as thin as 0.4 ⁇ m or less, and the formation of the black matrix may be omitted.
- FIG. 6 shows the thickness of the laminated portion when the thickness of the colored layer is 4.5 ⁇ m. In the range of 1.5 ⁇ m to 5 ⁇ m, which is a practical thickness range of the colored layer, FIG. Show similar trends.
- the pattern shape of the pedestal can be used in combination as a light-shielding pattern for suppressing generation of photocurrent due to light incident on an active element such as a TFT that drives liquid crystal.
- an active element such as a TFT that drives liquid crystal.
- the optical density is 1, so the addition of the film thickness of the pedestal of 0.4 ⁇ m to 1.0 ⁇ m and the film thickness of the overlapping portion of the colored pixels is sufficient.
- the several colored layer is laminated
- 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, it can be selected so as to include a red colored layer having a light shielding property for short-wavelength light. If the rounded shape is prioritized, a blue colored layer that has less pigment content than the other two colors and has fluidity can be selected as the top layer of a three-layer stack or a two-layer stack spacer. it can.
- the color filter of 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.
- a spacer main spacer
- a sub-spacer having a low height may be provided.
- 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 of the present invention can be applied to a liquid crystal display device having a thin liquid crystal layer thickness in the near future.
- the number of spacers and the layout may be adjusted in consideration of the flow of the liquid crystal material at the time of forming a liquid crystal cell, such as changing the arrangement.
- the light shielding layer and the pedestal can be formed in the same photolithography process, as will be described later.
- the spacer is formed, for example, in the center of the pixel in the longitudinal direction (one pixel central portion or one central portion of the pixel long side) for each pixel, and the spacer is aligned with the liquid crystal alignment It can be formed as a structure that also serves as a control function.
- 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 at the center in the longitudinal direction of the pixel in accordance with the spacer position.
- the pixel electrode on the TFT substrate side surrounds the spacers in a rhombic concentric slit shape (in the shape of a square, alternating transparent electrode openings and patterns). What is necessary is just to arrange
- the configuration that combines 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.
- the alignment control structure can be formed with a high height or with a high density to improve the response of the liquid crystal.
- these techniques substantially reduce the aperture ratio of the pixel. .
- the aperture ratio is not lowered.
- 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 by covering the entire spacer with a blue colored layer as the uppermost layer, for example, having a high fluidity when the spacer is thermally cured.
- the spacer with a single color (red colored layer).
- Forming the spacer in a single color has the following advantages. That is, the technique (for example, Patent Document 1) in which two or three colored layers are stacked and independently arranged to form a spacer is more liquid crystal alignment than the technique (Patent Document 1) that uses simple color overlap as a spacer. Is advantageous. However, in order to absorb the positional deviation when the colors are superimposed twice and three times, it is necessary to form a large bottom area of the colored layered portion of the first color, which adversely affects the pixel aperture ratio.
- FIG. 7 shows a color filter substrate according to still another embodiment of the present invention, a light blocking layer 2, a pedestal 4, a black matrix 8, a red pixel 3R, a green pixel 3G, a spacer 5 formed by stacking colored layers, and a low height.
- FIG. 3 is a diagram showing a planar view arrangement of sub-spacers 6 and cell gap adjustment layers 15. That is, in FIG. 7, 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.
- FIG. 2 shows a cross section taken along the line CC ′ of FIG.
- 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 a lattice-shaped light shielding pattern that is usually formed so as to surround the colored pixels for the purpose of improving contrast, but may be formed in a stripe shape in the longitudinal direction of the pixel.
- a color filter substrate without a black matrix may be used.
- the black matrix, the pedestal, and the light shielding layers having different thicknesses may be formed in two steps using different photomasks.
- 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. 8 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 8. If the film thickness of the black matrix 8 exceeds 1.1 ⁇ m, the height of the protrusion 7 becomes extremely high, which is not preferable for liquid crystal alignment. When the thickness of the black matrix is less than 1 ⁇ m, and further less than 0.8 ⁇ m, the projection height at the end of the colored pixel is 0.25 ⁇ m, and further lower than 0.2 ⁇ m.
- a color filter that can ensure good flatness, including variations in the thickness of the colored pixels, of less than ⁇ 0.15 ⁇ m, 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 ⁇ m) of green wavelength 550 nm, which has high visibility to human eyes, and can reduce coloring unevenness.
- the black matrix can be formed simultaneously with the light shielding layer by a photolithography technique using a gray-tone mask or a half-tone mask, as in the case of the pedestal.
- 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.
- FIG. 8 does not show a black matrix having a thickness of less than 0.4 ⁇ m, the present inventors have confirmed that the height of the protrusions superimposed on the thin black matrix is low. Yes.
- 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.
- FIG. 2 shows an example in which the cell gap adjusting layer 15 according to the present invention is partially disposed on the colored pixels.
- the cell gap adjustment layer 15 is stacked on the reflective portion of the colored pixel 3G and the upper part of the retardation layer 11 at the same position as the planar view reflective portion 25.
- the cell gap adjustment layer 15 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 adjustment layer.
- the cell gap adjustment layer 15 ′ is also disposed on the frame-shaped light shielding layer 2, and the total thickness of the cell gap adjustment layer 15 ′ and the light shielding layer 2 is equal to the film thickness of the green pixel. It is almost equal.
- the cell gap adjustment layer 15 is mainly intended to adjust the optical path difference between the liquid crystal transmission part and the reflection part as a liquid crystal display device.
- the cell gap adjustment layer 15 uses a photosensitive alkali-soluble resin and a part such as a gray tone mask.
- the thickness may be changed using photomasks having different transmittances. You may change thickness according to the wavelength of the light of the main transmission part of a coloring pixel.
- the cell gap adjusting layer may be formed with a thin film thickness in the transmissive portion, in addition to being formed thick in the reflective portion.
- the cell gap adjusting layer 15 can be formed of the above-described transparent resin, alkali-soluble resin, or acrylic resin. Since the cell gap adjusting layer 15 is formed in a pattern, it is preferable to use an alkali-soluble resin that can be patterned by a photolithography process as the material. Even if a thermosetting resin is used, the pattern can be formed by dry etching or lift-off techniques. In addition, as in the embodiment shown in FIG. 1, it is more preferable that the cell gap adjusting layer is constituted by the light scattering layer 12.
- the color filter substrate according to the present invention is particularly applied to 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, and a light scattering layer 12 is arranged in the reflective part of the colored pixel as shown in FIG. That is, the light scattering layer 12 is disposed at the same position in plan view on the retardation layer 11 formed in the concave portion of the reflective portion of the colored pixel.
- the light scattering layer 12 is formed by dispersing single or plural kinds of amorphous fine particles in a matrix resin 14 having different refractive indexes, and has a paper white-like effect on the eyes of an observer by scattering incident light. It is an optical functional film.
- the matrix resin 14 may be a transparent resin that is heat resistant and transparent in the visible range.
- the film thickness of the light scattering layer 12 is preferably in the range of about 1.5 ⁇ m to 5 ⁇ m because of the relationship between the diameter of the amorphous fine particles, the wavelength of light, and the suitability in the manufacturing process.
- Examples of the amorphous fine particles 13 of the light scattering layer 12 include fine particles made of an inorganic material and fine particles made of an organic polymer.
- 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.
- a method of expressing amorphous fine particles in the matrix resin by phase separation described later may be used.
- 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.
- spherical amorphous fine particles such as silica and alumina oxide
- organic polymer fine particles acrylic fine particles, styrene acrylic fine particles and their cross-linked products, melamine fine particles, melamine-formalin condensate
- Fluoropolymers such as tetrafluoroethylene), PFA (perfluoroalkoxy resin), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), PVDF (polyfluorovinylidene), ETFE (ethylene-tetrafluoroethylene copolymer), Silicon resin fine particles and the like can be exemplified.
- crosslinked acrylic resin fine particles have a refractive index of less than 1.5
- silica particles or silicon resin fine particles have a refractive index of 1.42 to 1.45 (halogen lamp D). Line 589nm) Preferred.
- These fine particles may be mainly contained as fine particles in the light scattering layer, and for example, about 70% or more of the fine particles may be contained.
- 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. May be added.
- these fine particles can be applied as the fine particles after appropriate surface treatment is performed to improve the solvent dispersibility and compatibility with the transparent resin.
- 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.
- other examples include a treatment that causes a surface reaction with alcohol, amine, organic acid, or the like.
- the shape of the amorphous fine particles 13 is not particularly limited, but is 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 12 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 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.
- the particle diameter of the fine particles is not particularly limited, but a preferable particle diameter range is an average particle diameter of about 0.8 ⁇ m to 3 ⁇ m, preferably an average particle diameter of 1 ⁇ m to 2 ⁇ m.
- the specific gravity of the fine particles does not directly affect the optical characteristics of the light scattering layer, but has a great influence on the coating characteristics when the light scattering layer 12 is formed, and is also related to the characteristics of the light scattering layer 12 itself. . Therefore, it is desirable for the stability of the coating liquid that the value is close to the specific gravity of the solution of the matrix resin 14.
- the matrix resin 14 in which the fine particles are dispersed 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.
- Epoxy-modified acrylic resins, fluorene resins, and polyimide resins can be used.
- resins having a low refractive index fluorine-modified acrylic resins and silicon-modified acrylic resins can be used.
- acrylic resin, epoxy resin, polyester resin, urethane resin, silicon resin, and the like can be used as appropriate.
- 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.
- the refractive index of the matrix resin is preferably 1.55 to 1.65.
- the matrix resin preferably has a refractive index of 1.50 to 1.60.
- the light scattering layer 12 is formed by mixing and dispersing amorphous fine particles 13 in a transparent resin 14 as a matrix resin, applying the mixture onto a transparent substrate, drying it, and then forming it into an arbitrary shape through a photolithography process.
- a coating method spin coating, flow coating, roll coating, or the like can be applied, and as an exposure method, projection exposure or proximity exposure can be applied.
- Examples of the amorphous fine particles 13 in the light scattering layer 12 include fine particles that can be formed by mixing two resins and performing phase separation.
- 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 grows when the two resins are mixed in the solution, or when the solvent is volatilized by coating and drying on the substrate, and when the coating film is dried, transparent amorphous fine particles 13 are formed. it can.
- 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. The volume increases, but grows while deforming from a spherical shape to a disk shape due to the stress from the upper surface.
- One resin is generated 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.
- 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;
- the molecular weight of A is larger than the molecular weight of B, and the magnitude of the amount is a constraint on strength.
- the amorphous fine particles When the amorphous fine particles are generated and formed by phase separation from two or more types of resin solutions having different refractive indexes, the amorphous fine particles stay 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 matrix resin 14 and the amorphous fine particles 13 formed by phase separation desirably have high visible light transmittance and sufficient resistance to heat treatment and chemical treatment during the manufacturing process of the liquid crystal display device.
- epoxy-modified acrylic resin, fluorene resin, polyimide resin, and melamine resin can be used as the resin having a high refractive index
- fluorine-modified acrylic resin and silicon-modified acrylic resin can be used as the resin having a low refractive index
- acrylic resin, epoxy resin, polyester resin, urethane resin, silicon resin, and the like can be used as appropriate.
- Aspherical fine particles are easily available in the form of spheres, 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. Applicable as high resin.
- 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.
- a surfactant for improving coating suitability a photopolymerization initiator for imparting photosensitivity, a sensitizer, and the like can be added.
- a shape different from the above two examples and a different manufacturing process can be exemplified. That is, a transparent resin is applied and dried on a substrate, and a number of fine reliefs having a film thickness of several ⁇ m and a pattern size of several ⁇ m to several tens of ⁇ m are formed using means such as photolithography, and the relief is softened by heating. Thereafter, thermal crosslinking is performed.
- a light scattering film layer can be formed by applying a transparent resin having a different refractive index thereon.
- the light scattering characteristics can be adjusted by changing the pattern shape (size, shape and density).
- 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 that is the cell gap adjusting layer is preferably formed in a pattern having the same size as that of the phase difference layer in plan view or larger than that of the phase difference layer.
- TFT Columnored pixel overlap shape
- an apparatus with high alignment accuracy in which 3 ⁇ is 1.5 ⁇ m is commercially available.
- an alignment mark attached to the metal wiring is used.
- an organic film for example, a photosensitive colored composition film such as a black matrix.
- the alignment mark is attached to the organic film, the film thickness of the organic film is 1 ⁇ m to 4 ⁇ m, which is thicker than the TFT wiring, and the pattern edge is also tapered.
- the alignment accuracy must be at least 3 ⁇ m and 4.5 ⁇ m alignment accuracy.
- the liquid crystal thickness of the IPS, VA, or FFS type liquid crystal display device is about 2 ⁇ m to 4 ⁇ m.
- 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 ⁇ m to 4 ⁇ m.
- the line width of the black matrix is about 5 ⁇ m to 30 ⁇ m, although it differs for mobile (small) liquid crystal display devices and large TVs.
- the formation of the black matrix may be omitted.
- FIG. 9 shows the pattern edge shape of the thick colored pixel 22 and FIG. 10 shows the pattern edge shape of the thin colored pixel 23.
- the length m and n of the pattern edge relating to the alignment is 4.5 ⁇ m, and the thickness of the colored layer 22 and the thickness t of the colored pixel 23 are 1.2 ⁇ m to 4.0 ⁇ m.
- 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.
- 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 ⁇ m to 0.3 ⁇ m.
- a protective film having a thickness of 1 ⁇ m or more may be formed by previously forming a high spacer.
- the protective layer may also serve as an alignment film, or may be applied and formed in advance before the pretreatment of the retardation layer described later. Or you may contain the additive (for example, ultraviolet absorber) which assists the photo-alignment of the phase difference layer or the alignment film of a liquid crystal. 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.
- a TFT element for driving a 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 it can be used as a spacer for a vertically aligned liquid crystal display and an alignment control structure. it can.
- the reflection part of the transflective liquid crystal display device has a difference in phase difference caused by liquid crystal in addition to the optical path difference as compared with the transmission part. Due to such a difference in 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 display may be normally white display, The problem of phase difference is significant.
- this problem can be solved by shifting the phase difference of the 1/4 wavelength of incident light and adding a phase difference of 1/4 wavelength by reflection at the reflection electrode (incident converted to linearly polarized light). The light is rotated by 90 degrees in one reciprocation in the thickness direction of the retardation layer).
- a polymer liquid crystal or a crosslinkable polymer liquid crystal is used as a specific method for imparting a function of changing a quarter wavelength phase or a half wavelength phase to the retardation layer.
- examples thereof include a coating formation method using a solution, a method of adding a birefringence modifier to the alkali-soluble transparent resin described above, a method of using a polymerizable liquid crystal compound, and the like.
- 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 which were listed.
- an alignment film may be formed or an alignment treatment may be performed before the retardation layer is formed.
- 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 same optical alignment treatment as that for the polymerizable liquid crystal compound can be employed.
- the exposure machine can be appropriately selected from an ultra-high pressure mercury lamp, a YAG laser, a solid-state laser, a semiconductor laser and the like including the exposure wavelength.
- the alignment density and orientation 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.
- Selective exposure may be performed for each corresponding colored pixel using a plurality of photomasks. Irradiation from a plurality of directions may be performed at a time.
- 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 film thickness of the retardation layer may be adjusted in the range of about 0.5 ⁇ m to 5 ⁇ m according to the color filter constituent material alone or the birefringence of the liquid crystal applied to the liquid crystal display device.
- the difference in retardation of the retardation layer can be adjusted by the addition amount, type, and blend of the polymerizable initiator added to the polymerizable liquid crystal compound in addition to the exposure amount.
- the polymerizable liquid crystal compound is a monomer
- the crosslinking density can be increased by using a plurality of monomer reactive groups, and a highly reliable retardation layer can be obtained.
- the retardation layer can also be a retardation layer that matches the wavelength of each principal transmitted light of the colored pixel.
- a retardation layer formed on a colored pixel but also a retardation layer on a light shielding layer (frame portion) is provided with a function of changing the phase of a quarter wavelength or a half wavelength.
- the retardation layer 11 ′ is placed on the frame-shaped light shielding layer 2 so that the total thickness of the retardation layer 11 ′ and the light shielding layer 11 is substantially equal to the thickness of the green pixel.
- an alignment film may be applied and formed as a pretreatment before the retardation layer is formed, and the alignment treatment may be performed.
- 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 retardation layer can be used for liquid crystal alignment of the transmission part, and a film having a different alignment function can be separately formed on the retardation layer of the reflection part.
- Styrene / vinyl toluene copolymer chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, polyamide, polyvinyl alcohol, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer And polymers such as carboxymethylcellulose, polyethylene, polypropylene and polycarbonate, and compounds such as silane coupling agents.
- preferable polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol, and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).
- Alignment effect can also be obtained by rubbing the colored pixel surface of the color filter.
- commercially available alignment film materials can be applied, for example, alignment film material (Sunever) manufactured by Nissan Chemical Co., Ltd., alignment film material (QL, LX series) manufactured by Hitachi Chemical DuPont Microsystems, and alignment film material manufactured by JSR ( AL series) and an orientation agent (Rixon aligner) manufactured by Chisso Corporation.
- These alignment film materials can be added by adding an organic solvent such as gamma-butyrolactone, diethylene glycol monoethyl acetate, diethylene glycol monobutyl acetate, or cyclohexanone when the viscosity is adjusted as an inkjet ink.
- the same method as the alignment method of the liquid crystal alignment film used as the liquid crystal display device can be employed.
- 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.
- pattern formation is performed by a photolithography technique using a photosensitive alignment film material that can be developed. You can go.
- 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.
- the area ratio of the transmission part and the reflection part of the color filter substrate according to the present invention can be adjusted depending on the purpose and conditions of use of the liquid crystal display device.
- 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 were 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 Azisper 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.
- Black composition A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 ⁇ m filter to obtain a black composition.
- the black composition is used to form a light shielding layer and a pedestal in a later example.
- the black composition obtained as described above was coated After the formation, the cured film thickness is 1 ⁇ m, and the optical density (OD value) is approximately 1.8. The film thickness can be adjusted depending on the application conditions. It is also possible to adjust the optical density of the coating film by adjusting the component ratio of the resin solid ratio (resin solution). In addition, in the said black composition, since the green organic pigment has bad light-shielding property, it is not added.
- 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 mathematical 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, and the optical density (OD) was calculated using Equation 1.
- Optical density (OD) ⁇ log (Y / 100) (1) (Y is the tristimulus value Y with the C light source)
- a black composition Blk diluted with an organic solvent and adjusted in concentration was applied on a glass substrate to a thickness of 1 ⁇ m 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 oven at 230 degreeC 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 according to 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 to 5 ⁇ m with the above black composition, it is possible to increase the blending amount of the resin solution and the solvent (cyclohexanone, etc.) and to set 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.
- the resin solid ratio and the solvent amount of the black composition were adjusted so that the optical density was about 3 at a film thickness of 1.6 ⁇ m.
- a photosensitive resin composition for a light scattering layer was prepared with the following composition.
- 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: Cyclohexanone 21 parts by weight Photopolymerization monomer E: M400 (manufactured by Toagosei Co., Ltd.) 2 parts by weight A2, C and E are mixed, applied and dried. The refractive index of the transparent resin after exposure (200 mJ / cm 2 ), development, and hardening at 230 ° C. for 60 minutes was 1.58 (D line 589 nm).
- a resin composition for a light scattering layer was obtained.
- the viscosity of the composition at this time was 14 cp / 25 ° C.
- 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).
- 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).
- the reaction mixture was cooled to room temperature, 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 was continued at 20 ° C. for 6 hours.
- the obtained 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).
- 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.
- 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).
- 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.
- 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).
- Example 1 (Production of color filter substrate) The production of the color filter substrate according to the first embodiment will be described with reference to FIGS.
- the frame-shaped light shielding layer 2 and the pedestal 4 shown in FIGS. 1, 3 and 5 were formed on the transparent substrate 1 made of glass using the black composition described above.
- the thickness of the light shielding layer 2 was 1.6 ⁇ m, and the thickness of the base 4 was 0.6 ⁇ m.
- 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.
- spacers 5 were formed by stacking red pixels R, green pixels G, blue pixels B, red stacked portions 5R, green stacked portions 5G, and blue stacked portions 5B.
- a gray-tone photomask was used as an exposure mask for forming colored pixels and spacers including the colored pixels in the reflective portion shown in FIG. As a result, a concave portion was formed in the reflective portion of the colored pixel.
- the film thickness of the colored layer (red pixel 3R, green pixel 3G, blue pixel 3B) formed directly on the transparent substrate 1 was 3.2 ⁇ m ⁇ 0.2 ⁇ m.
- the film thickness of the colored pixel in the reflective part (concave part) was 1.6 ⁇ m ⁇ 0.2 ⁇ m.
- the alignment film can be formed by applying ink droplets without flowing out of the recess.
- an alignment treatment was performed as follows. That is, as a pretreatment of the colored pixel surface for forming the retardation layer 11, a viscosity-adjusted alignment film material Sunever manufactured by Nissan Chemical Industries, Ltd. is used, and selectively applied to the reflective portion colored pixels by the inkjet coating apparatus. Were discharged so that the dry film thickness was 0.1 ⁇ m.
- the rheological properties of the ink ejected into the ink jet have excellent discharge properties.
- the initial value of the complex viscosity of the ink at 23 to 25 ° C. when the frequency is changed from 100 to 0.1 Hz is 20 mPa ⁇ s or less.
- the maximum value is 1000 mPa or less, and the tangent loss at a frequency of 10 Hz to 50 Hz is 1 to 20.
- the ejection amount from the inkjet nozzle was one ejection per pixel within a range of 2 to 10 pl (picoliter).
- the film was baked at 260 ° C. for 40 minutes in a clean oven to be hardened. Subsequently, a rubbing process was performed on the substrate in a certain direction to make a pretreatment.
- a phase difference layer 11 having a phase difference function for changing a quarter wavelength was formed with a film thickness of 1.6 ⁇ m ⁇ 0.1 ⁇ m on the pre-treated reflective portion colored pixels. That is, a dry film is formed on a colored pixel that is a retardation layer and is a mixture of the following composition that is stirred and mixed so as to be uniform and filtered through a 0.6 ⁇ m filter and pre-treated with a polymerizable liquid crystal compound. The film was applied to a thickness of 1.6 ⁇ m 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
- the substrate coated with the polymerizable liquid crystal compound was exposed to ultraviolet rays for each colored pixel area of the reflection part through a photomask using an exposure machine using a semiconductor laser 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, a blue pixel regions respectively exposed as 5 mJ / cm 2, at further development A retardation layer pattern was formed.
- the substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to obtain a color filter substrate on which a retardation layer as a quarter wavelength layer was formed.
- the red pixel portion was 166 nm for light of wavelength 630 nm
- the green pixel portion was 136 nm for light of wavelength 550 nm
- the blue pixel portion was wavelength 112 nm in 450 nm light.
- the retardation layer 11 ′ was also formed on the frame-shaped light shielding layer 2 with the same frame-shaped pattern.
- the total film thickness of the light shielding layer 2 and the retardation layer 11 ′ on the light shielding layer is about 3.2 ⁇ m, which is substantially the same as the film thickness of the green pixel 3 ⁇ / b> G.
- a light scattering layer (cell gap adjusting layer) 12 was formed to a thickness of 1.9 ⁇ m using the light scattering layer composition.
- the forming method used the photomask which has the pattern of the light-scattering layer 12, performed 200 mJ / cm ⁇ 2 > ultraviolet exposure, developed with the alkali developing solution, and hardened
- the oxygen inhibition of the retardation layer is eliminated and the film can be stabilized again by a hardening process including ultraviolet exposure.
- the color pixels were previously provided with recesses and then hardened by heat treatment of the retardation layer, so that the retardation layer could be well formed regardless of the difference in exposure amount.
- the protrusion height d on the pedestal 4 shown in FIG. 4 was as low as 0.1 ⁇ m on the blue pixel side and 0.14 ⁇ m on the green pixel side, and the flatness was good.
- the size of the bottom side of the spacer 5 shown in FIG. 3 was 25 ⁇ m, and the overall height of the laminated colored layer constituting the spacer 5 was about 3.9 ⁇ m.
- the liquid crystal thickness of the target liquid crystal display device is 3.8 ⁇ m.
- the thickness of the liquid crystal layer on the reflecting portion shown in FIG. 12 described later was 1.8 ⁇ m.
- Example 2 (Production of color filter substrate) First, based on FIG. 7 which is a schematic plan view of a color filter substrate, an embodiment will be described with reference to FIGS. 2 and 3 which are partial sectional views thereof.
- the present embodiment is different from the first embodiment in that a black matrix is formed and a transparent resin is used as a cell gap adjusting layer instead of a light scattering layer.
- the light shielding layer 2 and the pedestal 4 shown in FIGS. 7 and 2 were formed on the transparent substrate 1 made of glass using the black composition described above.
- the thickness of the light shielding layer 2 was 1.6 ⁇ m, and the thicknesses of the black matrix 8 and the base 4 were 0.6 ⁇ m.
- the light-shielding layer 2 and the black matrix 8 and the pedestal 4 are coated with the above-described black composition and dried, and then a gray-tone photomask (a photomask with 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 one exposure / development and heat treatment.
- a light shielding layer 11 As shown in FIG. 3, on the transparent substrate 1, a light shielding layer 11, a red pixel R, a green pixel G, a blue image B, and a spacer 5 and a sub-spacer 6 formed by stacking colored layers were formed.
- a gray-tone photomask As an exposure mask for forming the spacer 5 and the sub-spacer 6, a gray-tone photomask whose pattern portion has low transmittance was used.
- the thickness of the colored layer (red pixel R, green pixel, blue pixel B) portion directly formed on the transparent substrate 1 made of glass was 3.2 ⁇ m ⁇ 0.2 ⁇ m.
- a retardation layer 11 having a retardation function that changes a quarter wavelength is formed with a film thickness of 1.6 ⁇ m ⁇ 0.1 ⁇ m.
- the pretreatment of the colored pixel surface for aligning the retardation layer 11 to impart a retardation function, the formation of the retardation layer 11 and the materials used for these were the same as in Example 1.
- a cell gap adjusting layer 15 having a film thickness of 1.9 ⁇ m was formed on the retardation layer 11 using an acrylic photosensitive resin that can be developed with an alkali.
- the cell gap adjusting layer 15 ′ was also formed on the frame-shaped light shielding layer 11 with the same frame-shaped pattern.
- the total film thickness of the light shielding layer 2 and the cell gap adjusting layer 15 ′ on the light shielding layer is about 3.2 ⁇ m, which is substantially the same as the film thickness of the green pixel 3 ⁇ / b> G.
- the size of the bottom side of the spacer 5 shown in FIG. 3 is 25 ⁇ m
- the height of the color layer stacking portion constituting the spacer 5 is about 3.9 ⁇ m
- the liquid crystal thickness of the target liquid crystal display device is 3.8 ⁇ m. is there.
- Example 3 (Production of color filter substrate) An embodiment will be described based on FIG. 7 which is a schematic plan view of a color filter substrate of the present invention, and also using FIGS. 2 and 3 which are partial sectional views thereof.
- the light shielding layer 2 and the pedestal 4 shown in FIGS. 7 and 2 were formed on the transparent substrate 1 made of glass using the black composition described above.
- the thickness of the light shielding layer 2 was 1.6 ⁇ m, and the thicknesses of the black matrix 8 and the base 4 were 0.6 ⁇ m.
- the light shielding layer 2, the black matrix 8 and the pedestal 4 are coated with the above-described black composition, dried, and then a gray-tone photomask (a photomask in which the light shielding layer pattern and the pedestal pattern have different transmittances).
- the film was formed on the transparent substrate 1 by a film hardening process by one exposure / development and heat treatment.
- a light blocking layer 2 As shown in FIG. 3, on the transparent substrate 1, a light blocking layer 2, a red pixel 3R, a green pixel 3G, a blue pixel 3B, and a spacer 5 and a sub-spacer 6 formed by stacking colored layers were formed.
- a gray-tone photomask As an exposure mask for forming the spacer 5 and the sub-spacer 6, a gray-tone photomask whose pattern portion has a low transmittance was used.
- the film thickness of the colored layer (red pixel 3R, green pixel 3G, blue pixel 3B) formed directly on the transparent substrate 1 was 3.2 ⁇ m ⁇ 0.2 ⁇ m.
- the pretreatment of the colored pixel surface for orienting the retardation layer 11 and imparting a retardation function was the same as in Example 1.
- the phase difference amount corresponding to each colored pixel was adjusted by the exposure amount.
- the polymerizable liquid crystal composition to be the retardation layer 11 has the following composition.
- a cell gap adjusting layer 15 having a film thickness of 0.9 ⁇ m was formed using an acrylic photosensitive resin capable of alkali development.
- a cell gap adjusting layer 15 ′ was also formed in the same pattern on the frame-shaped light shielding layer 2 shown in FIG. 2. The height and shape of the spacer are the same as in Example 1.
- the thickness of the retardation layer 11 is 2.6 ⁇ m, and is formed in the concave portion of a colored pixel (for example, the green pixel 3G) having a thickness of 3.2 ⁇ m. And protrudes from the surface of the colored pixel, so that the actual configuration is as shown in FIG.
- Example 4 A liquid crystal display device having the structure shown in FIG. 12 was produced.
- the color filter substrate 31 manufactured in Example 3 and the TFT substrate 32 are arranged to face each other, and a horizontal alignment (IPS) type liquid crystal layer 33 that is aligned in parallel with the substrate surface is sandwiched between them to provide a liquid crystal display.
- IPS horizontal alignment
- 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 through an insulating layer.
- the thickness of the liquid crystal layer 33 was set to 3.8 ⁇ m.
- Example 5 (Production of liquid crystal display device)
- the color filter substrate 31 and the TFT substrate 32 produced in Example 1 are arranged to face each other, and a vertical alignment (VA) type liquid crystal layer 33 that is aligned in parallel with the substrate surface is sandwiched between them, thereby providing a liquid crystal display device It was.
- illustration of the polarizing film, retardation film, and alignment film was abbreviate
- the color filter substrate 31 has the same thickness as that of the colored layer 3G, which is a green pixel, combined with the light shielding layer and the cell gap regulating layer, and has no excessive protrusion structure, so that it is smooth and uniform. 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.
- FIG. 13 A partially enlarged view of the liquid crystal display device in the vicinity of the TFT element 34 shown in FIG. 12 is shown in FIG. 13 (the light scattering layer and the cell gap regulating layer are not shown).
- 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.
- the present embodiment since there is a retardation layer provided in the reflection portion, there is no difference in display quality between the reflection portion and the transmission portion, and a high transmittance liquid crystal display device can be obtained.
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Abstract
Description
赤色顔料としては、例えば、C.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、264、272、279等を用いることができる。
周知のように、誘電率の値は、屈折率の自乗とほぼ等しい。換言すれば、電子分極に起因する誘電率は屈折率の自乗に比例する。
下記表1より、ハロゲン化銅フタロシアニン(PG36)を主たる顔料とする緑色顔料分散体GP-5よりも、ハロゲン化亜鉛フタロシアニン(PG58)を主たる顔料とする緑色顔料分散体GP-4の塗膜の方が、Δnの絶対値が小さく、分極が小さいことが理解できる。
緑色顔料の比誘電率は、Solartron社製インピーダンスアナライザ1260型を用い、電圧5Vの条件にて、120、240、480Hzの周波数で測定した。測定試料は、アルミニウム薄膜からなる導電膜をパターン形成したガラス基板上に着色層を塗布・硬膜し(膜厚は後述の実施例と同じ)、更にこの着色層の上にアルミニウム薄膜からなる導電膜パターンを形成したものである。
下記組成の混合物を均一に攪拌混合した後、直径1mmのガラスビースを用いて、サンドミルで5時間分散した後、5μmのフィルタで濾過して赤色顔料1の分散体を作製した。
(大日本インキ化学工業(株)製「Phthalocyanine Green A1
10」) 10.4部
・黄色顔料:C.I. Pigment Yellow 150
(ランクセス社製「E4GN-GT」)) 9.6部
・分散剤(ビックケミー社製「Disperbyk-163」) 2部
・アクリルワニス(固形分20質量%) 66部。
下記組成の混合物を用い、緑色顔料1と同様の方法で緑色顔料2の分散体を作製した。
(大日本インキ化学工業(株)製「Phthalocyanine Green A1
10」) 10.4部
・黄色顔料:C.I. Pigment Yellow 150
(ランクセス社製「E4GN-GT」)) 3.2部
・黄色顔料:C.I. Pigment Yellow 138 7.4部
・分散剤(ビックケミー社製「Disperbyk-163」) 2部
・アクリルワニス(固形分20質量% ) 66部。
下記組成の混合物を用い、緑色顔料1と同様の方法で緑色顔料3の分散体を作製した。
(東洋インキ製造(株)製「リオノールグリーン 6YK」) 10.4部
・黄色顔料:C.I. Pigment Yellow 150
(ランクセス社製「E4GN-GT」)) 9.6部
・分散剤(ビックケミー社製「Disperbyk-163」) 2部
・アクリルワニス(固形分20質量%) 66部。
その後、下記組成の混合物を均一になるように攪拌混合した後、5μmのフィルタで
濾過して赤色着色組成物を得た。
・アクリル樹脂溶液 8部
・ジペンタエリスリトールペンタおよびヘキサーアクリレート
(東亜合成(株)製「M-402」) 4部
・光重合開始剤(チバガイギー社製「IRGACURE OXE 02」)
1.2部
・光重合開始剤(チバ・スペシャルティ・ケミカルズ社製「イルガキュアー907」)
3.5部
・増感剤(保土ヶ谷化学工業(株)製「EAB-F」) 1.5部
・シクロヘキサノン 5.8部
・プロピレングリコールモノメチルエーテルアセテート 30部。
分散体として、緑色顔料2を使用した以外は、緑色組成物1と同様の組成、方法で緑色組成物2を得た。
分散体として、緑色顔料3を使用した以外は、緑色組成物1と同様の組成、方法で緑色組成物3を得た。
有機顔料の分散体の製造方法としては種々の方法を採用することができるが、以下にその一例を示す。
着色画素は、特に厚み方向位相差の観点でその位相差を微調整できる。用いる顔料種、顔料の分散方法、分散剤、顔料の微細化、また、リタデーション調整剤として添加するメラミン樹脂、スチレン樹脂、ベンジル基を有する有機化合物など、種々の方法で位相差を大きくあるいは小さくすることができる。メラミン樹脂は位相差を増加させる方向で調整でき、スチレン樹脂は位相差を減少させるために用いることができる。緑色画素 において、ハロゲン化亜鉛フタロシアニン顔料が、その厚み方向位相差をゼロに近づけやすく、好ましい。
顔料分散剤として高分子分散剤を用いると、経時の分散安定性に優れるので好ましい。高分子分散剤としては、例えば、ウレタン系分散剤、ポリエチレンイミン系分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレングリコールジエステル系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤等を挙げることができる。中でも、特に窒素原子を含有するグラフト共重合体からなる分散剤が、顔料を多く含む本発明の遮光性感光性樹脂組成物としては、現像性の点で好ましい。
遮光層あるいは着色層として用いる感光性着色組成物は、上記顔料分散体に加え、さらに、多官能モノマー、感光性樹脂ないし非感光性樹脂、重合開始剤、溶剤等を含有する。感光性樹脂及び非感光性樹脂など、本発明に用いることの可能な透明性の高い有機樹脂を総称して透明樹脂と呼ぶ。
本発明に用いる遮光層、光散乱層、着色層、セルギャップ規制層には、フォトリソグラフィによるパターン形成可能な感光性樹脂組成物を用いることが好ましい。これらの透明樹脂は、アルカリ可溶性を付与された樹脂であることが望ましい。アルカリ可溶性樹脂としては、カルボキシル基又は水酸基を含む樹脂であれば特に限定はない。例えば、エポキシアクリレート系樹脂、ノボラック系樹脂、ポリビニルフェノール系樹脂、アクリル系樹脂、カルボキシル基含有エポキシ樹脂、カルボキシル基含有ウレタン樹脂等が挙げられる。中でもエポキシアクリレート系樹脂、ノボラック系樹脂、アクリル系樹脂が好ましく、特に、エポキシアクリレート系樹脂やノボラック系樹脂が好ましい。
本発明に採用可能な透明樹脂の代表として、以下のアクリル系樹脂が例示できる。
光重合性モノマーの例として、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、メラミン(メタ)アクリレート、エポキシ(メタ)アクリレート等の各種アクリル酸エステルおよびメタクリル酸エステル、(メタ)アクリル酸、スチレン、酢酸ビニル、(メタ)アクリルアミド、N-ヒドロキシメチル(メタ)アクリルアミド、アクリロニトリル等が挙げられる。
光重合開始剤としては、4-フェノキシジクロロアセトフェノン、4-t-ブチル-ジクロロアセトフェノン、ジエトキシアセトフェノン、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1-オン等のアセトフェノン系化合物、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチルケタール等のベンゾイン系化合物、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、4-ベンゾイル-4’-メチルジフェニルサルファイド等のベンゾフェノン系化合物、チオキサンソン、2-クロルチオキサンソン、2-メチルチオキサンソン、イソプロピルチオキサンソン、2,4-ジイソプロピルチオキサンソン等のチオキサンソン系化合物、2,4,6-トリクロロ-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ピペニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4-ビス(トリクロロメチル)-6-スチリルs-トリアジン、2-(ナフト-1-イル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-メトキシ-ナフト-1-イル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4-トリクロロメチル-(ピペロニル)-6-トリアジン、2,4-トリクロロメチル(4’-メトキシスチリル)-6-トリアジン等のトリアジン系化合物、1,2-オクタンジオン,1-〔4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)〕、O-(アセチル)-N-(1-フェニル-2-オキソ-2-(4’-メトキシ-ナフチル)エチリデン)ヒドロキシルアミン等のオキシムエステル系化合物、ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド等のホスフィン系化合物、9,10-フェナンスレンキノン、
カンファーキノン、エチルアントラキノン等のキノン系化合物、ボレート系化合物、カルバゾール系化合物、イミダゾール系化合物、チタノセン系化合物等が挙げられる。 感度向上にオキシム誘導体類(オキシム系化合物)が有効である。これらは1種を単独であるいは2種以上を組み合わせて用いることができる。
重合開始剤と光増感剤とを併用することが好ましい。増感剤として、α-アシロキシエステル、アシルフォスフィンオキサイド、メチルフェニルグリオキシレート、ベンジル、9,10-フェナンスレンキノン、カンファーキノン、エチルアンスラキノン、4,4’-ジエチルイソフタロフェノン、3,3’,4,4’-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノン、4,4’-ジエチルアミノベンゾフェノン等の化合物を併用することもできる。
上記の光重合開始剤は、エチレン性不飽和化合物と共に用いることが好ましい。エチレン性不飽和化合物としては、エチレン性不飽和結合を分子内に1個以上有する化合物を意味する。中でも、重合性、架橋性、及びそれに伴う露光部と非露光部との現像液溶解性の差異を拡大できる等の点から、エチレン性不飽和結合を分子内に2個以上有する化合物であることが好ましい。また、その不飽和結合は(メタ)アクリロイルオキシ基に由来する(メタ)アクリレート化合物が更に好ましい。
感光性着色組成物には、連鎖移動剤としての働きをする多官能チオールを含有させることができる。多官能チオールは、チオール基を2個以上有する化合物であればよく、例えば、ヘキサンジチオール、デカンジチオール、1,4-ブタンジオールビスチオプロピオネート、1,4-ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、エチレングリコールビスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリス(3-メルカプトブチレート)、ペンタエリスリトールテトラキスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、トリメルカプトプロピオン酸トリス(2-ヒドロキシエチル)イソシアヌレート、1,4-ジメチルメルカプトベンゼン、2、4、6-トリメルカプト-s-トリアジン、2-(N,N-ジブチルアミノ)-4,6-ジメルカプト-s-トリアジン等が挙げられる。
感光性着色組成物には、組成物の経時粘度を安定化させるために貯蔵安定剤を含有させることができる。貯蔵安定剤としては、例えばベンジルトリメチルクロライド、ジエチルヒドロキシアミンなどの4級アンモニウムクロライド、乳酸、シュウ酸などの有機酸およびそのメチルエーテル、t-ブチルピロカテコール、トリエチルホスフィン、トリフェニルフォスフィンなどの有機ホスフィン、亜リン酸塩等が挙げられる。貯蔵安定剤は、感光性着色組成物中の顔料100質量部に対して、0.1質量部から10質量部の量で含有させることができる。
感光性着色組成物には、基板との密着性を高めるためにシランカップリング剤等の密着向上剤を含有させることもできる。シランカップリング剤としては、ビニルトリス(β-メトキシエトキシ)シラン、ビニルエトキシシラン、ビニルトリメトキシシラン等のビニルシラン類、γ-メタクリロキシプロピルトリメトキシシラン等の(メタ)アクリルシラン類、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)メチルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、β-(3,4-エポキシシクロヘキシル)メチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン等のエポキシシラン類、N-β(アミノエチル)γ-アミノプロピルトリメトキシシラン、N-β(アミノエチル)γ-アミノプロピルトリエトキシシラン、N-β(アミノエチル)γ-アミノプロピルメチルジエトキシシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリエトキシシラン等のアミノシラン類、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルトリエトキシシラン等のチオシラン類等が挙げられる。シランカップリング剤は、感光性着色組成物中の顔料100質量部に対して、0.01質量部から100質量部で含有させることができる。
前記感光性着色組成物には、基板上への均一な塗布を可能とするために、水や有機溶剤等の溶剤が配合される。また、本発明の組成物がカラーフィルタの着色層である場合、溶剤は、顔料を均一に分散させる機能も有する。溶剤としては、例えばシクロヘキサノン、エチルセロソルブアセテート、ブチルセロソルブアセテート、1-メトキシ-2-プロピルアセテート、ジエチレングリコールジメチルエーテル、エチルベンゼン、エチレングリコールジエチルエーテル、キシレン、エチルセロソルブ、メチル-nアミルケトン、プロピレングリコールモノメチルエーテル、トルエン、メチルエチルケトン、酢酸エチル、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルケトン、石油系溶剤等が挙げられ、これらを単独でもしくは混合して用いる。溶剤は、着色組成物中の顔料100質量部に対して、800質量部から4000質量部、好ましくは1000質量部から2500質量部で含有させることができる。
本発明に係る技術は、上述したように、IPS(水平配向、横電界方式)やFFS(Fringe Field Switching)といった液晶駆動方式に好適である。特許文献10に記載されている技術などを適用することで、FFS方式でのVA液晶表示装置として本発明のカラーフィルタを用いることができる。カラーフィルタ上の透明電極と、対向する基板である液晶駆動素子(TFT)の形成されたアレイ基板の画素電極との間で液晶の駆動電圧を印加する方式では、通常、液晶厚み(セルギャップ)は薄い方が液晶の応答速度を高めることができる。
本発明に係るスペーサ用台座は、少なくとも、後述するスペーサの形成される部分とTFTなどアクティブ素子の遮光に必要な部分にのみ形成すればよい。また、本発明に係るスペーサ用台座は、額縁部である遮光層と同一材料で同時に形成することが望ましい。具体的には、グレートーン(階調マスク)の類の複数種の透過率の異なるパターンを形成したフォトマスク、あるいは、台座のパターンサイズより小さな開口部(開口部の大きさ調整で露光量を調節する)や開口形状を工夫した開口部を形成したフォトマスクを用いた露光及び露光後の現像以降のフォトリソグラフィの手法により、遮光層と台座を同時に形成することができる。
図7は、本発明の更に他の実施形態に係るカラーフィルタ基板における、遮光層2、台座4、ブラックマトリクス8、赤色画素3R、緑色画素3G、着色層の積層によるスペーサ5、高さの低いサブスペーサ6、セルギャップ調整層15の平面視配置を示す図である。即ち、図7には、赤色画素3R、緑色画素3G、及び青色画素3Bからなる3色の着色画素を区分するブラックマトリクス8が設けられている。なお、図7のC-C’断面を図2に示す。
本発明に係るセルギャップ調整層15を、着色画素上に部分的に配設される例として、図2に示した。この例では、セルギャップ調整層15は、平面視反射部25と同じ位置の、着色画素3Gの反射部及び位相差層11の上部に積層される。上述したように、セルギャップ調整層15は、透過部と反射部の光路差を調整する目的で配設する。そのため、少なくとも可視光の高い透過性と液晶パネル工程で必要な耐熱性のある樹脂材料をセルギャップ調整層に用いることができる。図2に示すように、額縁状の遮光層2上にもセルギャップ調整層15’が配設され、セルギャップ調整層15’と遮光層2の膜厚の合計は、緑色画素の膜厚と略等しくなっている。
例えば、無機物微粒子であればシリカやアルミナの酸化物等の球状の非晶質微粒子、有機ポリマー微粒子としては、アクリル微粒子やスチレンアクリル微粒子及びその架橋体、メラミン微粒子、メラミン-ホルマリン縮合物、(ポリテトラフルオロエチレン)やPFA(ペルフルオロアルコキシ樹脂)、FEP(テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体)、PVDF(ポリフルオロビニリデン)、ETFE(エチレン-テトラフルオロエチレン共重合体)等の含フッ素ポリマー、シリコン樹脂微粒子等を例示できるが、そのなかでも、架橋アクリル樹脂微粒子は屈折率が1.5未満であり、更にシリカ粒子あるいはシリコン樹脂微粒子は屈折率が1.42~1.45(ハロゲンランプD線589nm)と小さいため、特に好ましい。
1)Aの量がBの量より少ないこと、
2)A溶液の表面張力がB溶液の表面張力より大きいこと、
3)A溶液の蒸発速度がB溶液の蒸発速度より大きいこと、
4)Aの分子量がBの分子量より大きいこと
等があげられるが、特に量の大小は強度の制約条件である。
TFT用露光装置は、3σが1.5μmの高いアライメント精度の装置が市販されている。TFTの場合には、金属配線に付されたアライメントマークが用いられているが、カラーフィルタの場合には、それと異なり、有機物膜(例えばブラックマトリクスなどの感光性着色組成物膜)に付されたアライメントマークを用いる。また、積層していく着色層も同様に、アライメントマークは有機物膜に付され、有機物膜の膜厚も1μmから4μmとTFTの配線と比較して厚く、パターンエッヂにもテーパが形成されるため、そのアライメント精度は、3σで4.5μmのアライメント精度が少なくとも必要となる。
半透過型液晶表示装置の反射部は、透過部と比較して光路差のほかに液晶に起因する位相差の差が生じる。このような反射部と透過部の位相差の違いにより、反射部の反射光や黒表示に着色を生じたり、あるいはノーマリブラック表示であるはずの表示がノーマリホワイト表示となることがあり、位相差の問題は大きい。
(顔料分散体RD1)
着色剤としてC.I.ピグメントレッド254/C.I.ピグメントレッド177=80/20(重量比)混合物20部、分散剤としてBYK-2001を5部(固形分換算)、溶媒としてプロピレングリコールモノメチルエーテルアセテート75部を、ビーズミルにより処理して、顔料分散体(RD1)を調製した。
着色剤としてC.I.ピグメントイエロー150を20部、分散剤としてソルスパース24000を5部(固形分換算)、溶媒としてプロピレングリコールモノメチルエーテルアセテート75部を、ビーズミルにより処理して、顔料分散体(YD1)を調製した。
着色剤としてC.I.ピグメントブルー15:6を20部、分散剤としてアジスパーPB-821を5部(固形分換算)、溶媒としてプロピレングリコールモノメチルエーテルアセテート75部を、ビーズミルにより処理して、顔料分散体(BD1)を調製した。
着色剤としてC.I.ピグメントバイオレット23を20部、分散剤としてアジスパーPB-821を5部(固形分換算)、溶媒としてプロピレングリコールモノメチルエーテルアセテート75部を、ビーズミルにより処理して、顔料分散体(VD1)を調製した。
反応容器にシクロヘキサノン800部を入れ、容器に窒素ガスを注入しながら加熱して、下記モノマーおよび熱重合開始剤の混合物を滴下して重合反応を行った。
メタクリル酸 60部
メチルメタクリレート 65部
ブチルメタクリレート 65部
熱重合開始剤 10部
連鎖移動剤 3部
滴下後十分に加熱した後、熱重合開始剤2.0部をシクロヘキサノン50部で溶解させたものを添加し、さらに反応を続けてアクリル樹脂の溶液を得た。この樹脂溶液に不揮発分が20重量%になるようにシクロヘキサノンを添加してアクリル樹脂溶液を調製し、樹脂溶液(P1)とした。アクリル樹脂の重量平均分子量は、約10,000であった。
下記組成の混合物を均一になるように攪拌混合した後、5μmのフィルタで濾過して黒色組成物を得た。黒色組成物は、後の実施例で遮光層及び台座の形成に用いる。
上記顔料分散液(BD1) 17部
上記顔料分散液(YD1) 4部
樹脂溶液(P-1) 9部
トリメチロールプロパントリアクリレート 4.8部
光重合開始剤
(チバガイギー社製「イルガキュア-369」) 2.8部
光増感剤(保土ヶ谷化学社製「EAB-F」) 0.2部
シクロヘキサノン 36.2部
以上のようにして得た黒色組成物は、塗布形成後の硬化させた膜厚1μmで、およそ1.8の光学濃度(OD値)である。塗布条件により膜厚調整が可能である。樹脂の固形比(樹脂溶液)の成分比調整で塗膜の光学濃度の調整も可能である。なお、上記黒色組成物では、緑色有機顔料は遮光性が悪いため、添加をしていない。
光学濃度(OD値)は物質が光を吸収する程度を表わす値であり、光路長が一定のとき、OD値が大きいほど物質の濃度が高いことを示す。本発明における光学濃度(OD値)は下記数式(1)で表される。上記にて得られた黒色組成物塗布基板をオリンパス社製分光器OSP-200を用いてC光源での三刺激値Yを測定し、式1を用いて光学濃度(OD)を算出した。
光学濃度(OD)=-log(Y/100)・・・(1)
(但し、YはC光源での三刺激値Yである)
測定用試料として、有機溶剤で希釈し、濃度調整した黒色組成物Blkをガラス基板上に1μmの厚さに塗工し、自然乾燥させた。ホットプレートにて90℃で1分間加熱して、余剰の溶剤を除去乾燥させた。その後、230℃にて1時間オーブンで焼成を行って遮光層の光学濃度測定試料とした。光学濃度(OD)は、およそ1.8であった。
感光性の光散乱層用樹脂組成物を以下に示す組成で調製した。
:フルオレン骨格を有するエポキシアクリレート樹脂 4.5重量部
透明粒子B3:MX180(綜研化学社製) 2重量部
光重合開始剤C:イルガキュア819
(チバ・スペシャルティ・ケミカルズ社製) 0.45重量部
溶剤D:シクロヘキサノン 21重量部
光重合モノマーE:M400(東亞合成社製) 2重量部
A2とCとEを混合し、塗布し、乾燥し、露光(200mJ/cm2 )し、現像した後、230℃で60分間硬膜化した後の透明樹脂の屈折率は、1.58(D線589nm)であった。
[顔料製造例R2]
ジケトピロロピロール系赤色顔料PR254(チバスペシャリティケミカルズ社製「イルガフォアレッドB-CF」;R-1)100部、色素誘導体(D-1)18部、粉砕した食塩1000部、およびジエチレングリコール120部をステンレス製1ガロンニーダー(井上製作所製)に仕込み、60℃で10時間混練した。
アントラキノン系赤色顔料PR177(チバスペシャリティケミカルズ社製「クロモフタルレッドA2B」)100部、色素誘導体(D-2)8部、粉砕した食塩700部、およびジエチレングリコール180部をステンレス製1ガロンニーダー(井上製作所製)に仕込み、70℃で4時間混練した。この混合物を温水4000部に投入し、約80℃に加熱しながらハイスピードミキサーで約1時間攪拌してスラリー状とし、濾過、水洗をくりかえして食塩および溶剤を除いた後、80℃で24時間乾燥し、102部のソルトミリング処理顔料(R3)を得た。
スルホン化フラスコにtert-アミルアルコール170部を窒素雰囲気下において装填し、ナトリウム11.04部を添加し、この混合物を92~102℃に加熱した。溶融したナトリウムを激しく撹拌しながら100~107℃に一晩保持した。
塩化アルミニウム356部および塩化ナトリウム6部の200℃の溶融塩に、亜鉛フタ
ロシアニン46部を溶解し、130℃まで冷却し、1時間攪拌した。反応温度を180℃に昇温し、臭素を1時間あたり10部で10時間滴下した。その後、塩素を1時間あたり0.8部で5時間導入した。
セパラブルフラスコに水150部を仕込み、さらに攪拌しながら35%塩酸63部を仕込み、塩酸溶液を調製した。発泡に注意しながらベンゼンスルホニルヒドラジド38.7部を仕込み、液温が0℃以下になるまで氷を追加した。冷却後、30分かけて亜硝酸ナトリウム19部を仕込み、0~15℃の間で30分撹拌した後、ヨウ化カリウムでんぷん紙で着色が認められなくなるまでスルファミン酸を仕込んだ。
銅フタロシアニン系青色顔料PB15:6(東洋インキ製造社製「リオノールブルーES」)100部、粉砕した食塩800部、およびジエチレングリコール100部をステンレス製1ガロンニーダー(井上製作所製)に仕込み、70℃で12時間混練した。
LIONOGEN VIOLET RL(東洋インキ製造製)300部を96%硫酸3000部に投入し、1時間撹拌した後、5℃の水に注入した。1時間撹拌後、濾過し、温水で洗浄液が中性になるまで洗浄し、70℃で乾燥した。
反応容器にシクロヘキサノン800部を入れ、容器に窒素ガスを注入しながら100℃に加熱して、同温度で下記のモノマーおよび熱重合開始剤の混合物を1時間かけて滴下し
て重合反応を行った。
メタクリル酸 10.0部
メタクリル酸メチル 65.0部
メタクリル酸ブチル 65.0部
アゾビスイソブチロニトリル 10.0部
滴下後、さらに100℃で3時間反応させた後、アゾビスイソブチロニトリル2.0部をシクロヘキサノン50部に溶解したものを添加し、さらに100℃で1時間反応を続けて樹脂溶液を合成した。
下記表4に示す組成(重量部)の混合物を均一に撹拌混合した後、直径1mmのジルコニアビーズを用いて、サンドミルで5時間分散した後、5μmのフィルタで濾過して赤色、緑色、青色の顔料分散体を得た。
(カラーフィルタ基板の作製)
図1、3及び5を参照して、実施例1に係るカラーフィルタ基板の作製について説明する。
(BASFジャパン株式会社製「Paliocolor LC 242」)
光重合開始剤 0.3部
(チバ・スペシャリティー・ケミカルズ株式会社製「イルガキュアー907」)
界面活性剤 6.0部
(ビックケミー社製「BYK111」2%シクロヘキサノン溶液)
シクロヘキサノン 154.0部
次に、この重合性液晶化合物を塗布した基板を、半導体レーザを光源とする露光機を用い、フォトマスクを介して反射部のそれぞれ着色画素領域毎に紫外線を露光した。紫外線の照射量は、レーザのショット回数を変えて、赤色画素領域では500mJ/cm2、緑色画素領域では200mJ/cm2、青色画素領域では5mJ/cm2としてそれぞれ露光し、さらに現像処理にて位相差層のパターンを形成した。
(カラーフィルタ基板の作製)
まず、カラーフィルタ基板の模式平面図である図7に基づき、またその部分断面図である図2及び図3を併用して実施例を説明する。本実施例は、ブラックマトリクスを形成し、また、セルギャップ調整層として光散乱層ではなく透明樹脂を用いた点が実施例1と異なる。
(カラーフィルタ基板の作製)
本発明のカラーフィルタ基板の模式平面図である図7に基づき、またその部分断面図である図2及び図3を併用して実施例を説明する。
(大日本インキ化学工業株式会社製「UCL-017」)
光重合開始剤 0.5部
(チバ・スペシャリティー・ケミカルズ社製「イルガキュアーOXE01」)
界面活性剤 2.0部
(ビックケミー社製「BYK330」2%シクロヘキサノン溶液)
シクロヘキサノン 148.0部
図12に示す構成の液晶表示装置を作製した。
(液晶表示装置の作製)
実施例1で作製したカラーフィルタ基板31とTFT基板32を対向させて配置し、それらの間に基板面と平行に配向する垂直配向(VA)方式の液晶層33を挟持して、液晶表示装置とした。なお、偏光フィルム、位相差フィルム、配向膜の図示は省略した。
Claims (17)
- 透明基板上に、遮光層を有効表示領域の外周に配置するとともに、緑色画素を含む複数色の着色画素、スペーサ、及び第1の位相差層を有効表示領域に形成した半透過型液晶表示装置用カラーフィルタ基板において、
前記着色画素のそれぞれには凹部が形成され、前記第1の位相差層は、前記凹部内に設けられるとともに、直線偏光に変換した入射光を該第1の位相差層の厚み方向に1回の往復にて90度偏光回転させる機能を有することを特徴とする半透過型液晶表示装置用カラーフィルタ基板。 - 前記凹部が形成されている着色画素の膜厚と、前記凹部が形成されていない着色画素の膜厚の比が、1/2から1/4の範囲内にあることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記緑色画素が、ハロゲン化亜鉛フタロシアニンを主たる色材として含むことを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記第1の位相差層上に第1のセルギャップ調整層が形成されていることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記第1のセルギャップ規制層の表面と前記凹部が形成されていない着色画素の表面との高さの差が、液晶表示装置の液晶層の厚みの略1/2であることを特徴とする請求項4に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記第1のセルギャップ調整層が、光散乱層であることを特徴とする請求項4又は5に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記透明基板上の有効表示領域に前記着色画素を区分するように配置された、前記遮光層と同一材料からなるブラックマトリクスを更に具備することを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記遮光層の膜厚より前記ブラックマトリクスの膜厚が薄いことを特徴とする請求項7に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記遮光層は、複数の有機顔料の混合物を主たる色材とすることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記遮光層上に積層された第2の位相差層を更に具備し、前記遮光層と第2の位相差層の合計膜厚が、前記緑色画素の膜厚と略同一であることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記遮光層上に積層された第2のセルギャップ調整層を更に具備し、前記遮光層と第2のセルギャップ調整層の合計膜厚が、前記緑色画素の膜厚と略同一であること特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記複数色の着色画素が、少なくとも赤色画素と緑色画素と青色画素を含み、これら着色画素の位相差が、赤色画素≧緑色画素≧青色画素の関係にあることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記複数色の着色画素が、少なくとも赤色画素と緑色画素と青色画素を含み、これら着色画素の位相差と当該着色画素上に積層された第1の位相差層の位相差のそれぞれ色毎に合計した位相差が、赤色画素≧緑色画素≧青色画素の関係にあることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記スペーサが、複数の着色層の積層からなることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- 前記スペーサは、液晶配向制御の役割を兼ねるとともに、前記着色画素の長手方向中央に配設されていることを特徴とする請求項1に記載の半透過型液晶表示装置用カラーフィルタ基板。
- カラーフィルタ基板と、このカラーフィルタ基板に対向して配置された、液晶駆動素子を備える対向基板と、前記カラーフィルタ基板及び対向基板との間に設けられた液晶層とを具備する半透過型液晶表示装置であって、
前記カラーフィルタ基板は、透明基板上に、遮光層を有効表示領域の外周に配置するとともに、緑色画素を含む複数色の着色画素、スペーサ、及び第1の位相差層を有効表示領域に形成してなり、
前記着色画素のそれぞれには凹部が形成され、前記第1の位相差層は、前記凹部内に設けられるとともに、直線偏光に変換した入射光を該第1の位相差層の厚み方向に1回の往復にて90度偏光回転させる機能を有する
ことを特徴とする半透過型液晶表示装置。 - 透明基板上に、遮光層を有効表示領域の外周に配置するとともに、緑色画素を含む複数色の着色画素、スペーサ、及び位相差層を有効表示領域に形成した半透過型液晶表示装置用カラーフィルタ基板を製造する方法において、
前記複数の着色画素のそれぞれに凹部を形成する工程、及び
前記凹部にインクジェット方式により位相差層を配向させる配向膜を形成する工程
を具備することを特徴とする半透過型液晶表示装置用カラーフィルタ基板の製造方法。
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- 2011-01-26 EP EP11737050.2A patent/EP2530497A4/en not_active Withdrawn
- 2011-01-26 KR KR1020127019816A patent/KR101385911B1/ko not_active Expired - Fee Related
- 2011-01-26 WO PCT/JP2011/051493 patent/WO2011093337A1/ja not_active Ceased
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2011154327A (ja) | 2011-08-11 |
| CN102725662B (zh) | 2015-04-01 |
| TW201133079A (en) | 2011-10-01 |
| CN102725662A (zh) | 2012-10-10 |
| TWI470316B (zh) | 2015-01-21 |
| EP2530497A4 (en) | 2014-03-26 |
| KR101385911B1 (ko) | 2014-04-15 |
| JP5077367B2 (ja) | 2012-11-21 |
| US20120287380A1 (en) | 2012-11-15 |
| EP2530497A1 (en) | 2012-12-05 |
| KR20120106998A (ko) | 2012-09-27 |
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