WO2008152828A1 - 透過型液晶表示装置 - Google Patents
透過型液晶表示装置 Download PDFInfo
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- WO2008152828A1 WO2008152828A1 PCT/JP2008/051711 JP2008051711W WO2008152828A1 WO 2008152828 A1 WO2008152828 A1 WO 2008152828A1 JP 2008051711 W JP2008051711 W JP 2008051711W WO 2008152828 A1 WO2008152828 A1 WO 2008152828A1
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- liquid crystal
- anisotropic layer
- optically anisotropic
- display device
- refractive index
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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
- G02F1/1335—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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials
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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
- G02F1/133637—Birefringent elements, e.g. for optical compensation characterised by the wavelength dispersion
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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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133738—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homogeneous alignment
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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
- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/139—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
- G02F1/1393—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent the birefringence of the liquid crystal being electrically controlled, e.g. ECB-, DAP-, HAN-, PI-LC cells
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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
- G02F2202/00—Materials and properties
- G02F2202/40—Materials having a particular birefringence, retardation
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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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/02—Number of plates being 2
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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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/10—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with refractive index ellipsoid inclined, or tilted, relative to the LC-layer surface O plate
- G02F2413/105—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with refractive index ellipsoid inclined, or tilted, relative to the LC-layer surface O plate with varying inclination in thickness direction, e.g. hybrid oriented discotic LC
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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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/13—Positive birefingence
Definitions
- the present invention relates to a transmission type liquid crystal display device used for office automation equipment such as a word processor and a personal computer, portable information equipment such as an electronic notebook and a mobile phone, or a camera-integrated type VR provided with a liquid crystal monitor.
- a liquid crystal display device is usually composed of a liquid crystal cell, a polarizing plate, and an optical compensation sheet (retardation plate).
- a liquid crystal cell is sandwiched between a pair of polarizing plates, and one or a plurality of optical compensation sheets are disposed between the liquid crystal cell and the polarizing plate.
- the liquid crystal cell is composed of a rod-like liquid crystal molecule, two substrates for enclosing it, and an electrode layer for applying a voltage to the rod-like liquid crystal molecule.
- T N As the liquid crystal cell system, T N
- the transmissive liquid crystal display device has a viewing angle such as a decrease in display contrast, a change in display color, or an inversion of gradation when viewed from an oblique direction due to the refractive index anisotropy of liquid crystal molecules. Problems cannot be avoided and improvements are desired.
- the area where the contrast spreads is improved, but the range where the gradation is reversed is wide, and the viewing angle characteristics are not necessarily sufficient. This is because the liquid crystal layer is twisted 90 degrees, the tilted portion of the liquid crystal molecules in the liquid crystal cell when a voltage is applied spreads to the 90 degree orientation, and the range of gradation inversion is expanded. caused by.
- the liquid crystal cell is preferably a display method using the ECB method in which the twist angle of the liquid crystal molecules is 0 degree and the orientation is homogeneous.
- Patent Document 4 In order to improve the viewing angle of the ECB system, there has been proposed a configuration in which two optical compensation films and uniaxial retardation films that are nematically aligned on the upper and lower sides of a homogeneous liquid crystal cell are arranged (Patent Document 4).
- Patent Document 1 Japanese Patent No. 2 6 4 0 8 3
- Patent Document 2 Japanese Patent Laid-Open No. 1 1 1 9 4 3 2 5
- Patent Document 3 Japanese Patent Laid-Open No. 1 1 1 9 4 3 7 1
- Patent Document 4 Japanese Patent Laid-Open No. 2 0205-2 0 2 0 1 0 1
- the present invention improves the above-described problems, and provides a transmissive liquid crystal display device with little variation in display characteristics, bright display, high contrast, and low viewing angle dependency. Objective.
- a polarizing plate In the first aspect of the present invention, a polarizing plate, a second optically anisotropic layer, a first optically anisotropic layer, and a liquid crystal layer between an upper substrate and a lower substrate disposed opposite to each other in order from the backlight side.
- birefringence wavelength dispersion of the liquid crystal film of the second optically anisotropic layer D2 birefringence wavelength dispersion DLC of the liquid crystal cell
- the retardation values of the first optical anisotropic layer and the second optical anisotropic layer at nm are represented by Re1, Re2, and the retardation Re (LC) when the black display voltage is applied to the liquid crystal cell. ,
- Re 2 50 nm to 1 80 nm
- a transmissive liquid crystal display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- a display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- the second aspect of the present invention includes, in order from the backlight side, a polarizing plate, a homogeneous alignment liquid crystal cell in which a liquid crystal layer is sandwiched between an upper substrate and a lower substrate that are arranged to face each other, and a first optically anisotropic layer.
- the birefringence wavelength dispersion D 1 of the liquid crystal film of the first optical anisotropic layer the second Birefringence wavelength dispersion D 2 of the liquid crystal film of the optically anisotropic layer, Birefringence wavelength dispersion DLC of the liquid crystal cell
- the thickness of the first optically anisotropic layer is d 1, the in-plane main refractive indices are Nx l and N y 1, the main refractive index in the thickness direction is N z 1, and the in-plane main refractive index is N z 1
- the thickness of the second optically anisotropic layer is d 2
- the in-plane main refractive index is Nx 2 and Wavelength when Ny 2
- the main refractive index in the thickness direction is N z 2
- the phase difference values of the first optical anisotropic layer and the second optical anisotropic layer at 50 nm are represented by R e 1 and R e 2, and the phase difference R e (LC )But
- R e 1 2 O nm to l 4 O nm
- Re 2 50 nm to 1 80 nm
- a transmissive liquid crystal display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- a display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- the third aspect of the present invention is a homogenous orientation in which a polarizing plate, a first optically anisotropic layer, and a liquid crystal layer are sandwiched between an upper substrate and a lower substrate that are arranged opposite to each other in order from the backlight side.
- the retardation value of the anisotropic layer and the second optically anisotropic layer is represented by Re1, Re2, and the retardation Re (LC) when the black display voltage is applied to the liquid
- Re 1 20 nm to 140 nm
- Re 2 50 nm to 1 80 nm
- a transmissive liquid crystal display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- a display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- the fourth aspect of the present invention is a homogenous orientation in which a polarizing plate, a second optically anisotropic layer, and a liquid crystal layer are sandwiched between an upper substrate and a lower substrate disposed opposite to each other in order from the backlight side.
- the thickness of the first optically anisotropic layer is d 1, the in-plane main refractive indices are Nx l and N y 1, the main refractive index in the thickness direction is N z 1, and the in-plane main refractive index is N z 1
- the thickness of the second optically anisotropic layer is d 2
- the in-plane main refractive index is Nx 2 and Wavelength 550, where Ny 2 is the main refractive index in the thickness direction, N z 2
- the retardation values of the first optical anisotropic layer and the second optical anisotropic layer at nm are represented by Re1, Re2, and the retardation Re (LC) when the black display voltage is applied to
- a transmissive liquid crystal display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- a display device characterized in that the first optically anisotropic layer is composed of at least a liquid crystal film having a nematic hybrid alignment structure fixed thereto.
- a fifth aspect of the present invention is the transmission type liquid crystal display device according to any one of the first to fourth aspects of the present invention, wherein the second optically anisotropic layer is a polymer stretched film. is there.
- the second optically anisotropic layer is an optical film obtained by fixing a nematic alignment formed in a liquid crystal state by a liquid crystal material having optically positive uniaxiality.
- the transmissive liquid crystal display device according to any one of the first to fourth aspects of the present invention.
- an angle between a tilt direction obtained by projecting a hybrid direction of the liquid crystal film of the first optically anisotropic layer onto a substrate plane and a rubbing direction of the liquid crystal layer is within 30 °.
- an angle between a tilt direction obtained by projecting a hybrid direction of the liquid crystal film of the first optically anisotropic layer onto a substrate plane and a slow axis of the second optically anisotropic layer is 70.
- the liquid crystal film of the first optically anisotropic layer is made of a liquid crystal material exhibiting optically positive uniaxiality, and the nematic hybrid alignment formed by the liquid crystal material in a liquid crystal state.
- the transmission type according to any one of the first to eighth aspects of the present invention, wherein the liquid crystal film has a mean tilt angle of 5 to 45 degrees in the nematic hybrid alignment.
- a liquid crystal display device According to a tenth aspect of the present invention, an angle formed between an absorption axis of the polarizing plate and a tilt direction in which a hybrid direction of the liquid crystal film of the first optically anisotropic layer is projected onto a substrate plane is 30 ° or more.
- the transmission type liquid crystal display device according to any one of the first to ninth aspects of the present invention, wherein the transmission type liquid crystal display device is in a range of less than or equal to about 5 degrees.
- the phase difference when no voltage is applied to the homogeneously aligned liquid crystal cell is 200 nm to 400 nm.
- the liquid crystal display device of the present invention has features that the display is bright, the front contrast is high, and the viewing angle dependency is small.
- the transmissive liquid crystal display device of the present invention has any one of the following four configurations (1) to (4), and a light diffusion layer, a light control film, a light guide plate, a prism as necessary. A member such as a sheet is further added, but there is no particular limitation on these. Any of the configurations (1) to (4) may be used in terms of obtaining optical characteristics with little viewing angle dependency.
- Polarizing plate / liquid crystal cell First optical anisotropic layer / second optical anisotropic layer Z polarizing plate Z knock light
- liquid crystal cell used in the present invention will be described.
- a homogeneous alignment cell is used as a liquid crystal cell system.
- a homogeneous orientation cell is a cell with a twist angle of approximately 0 degrees.
- the term “substantially 0 degree” here means a twist angle of 0 degree or more and 5 degrees or less.
- the phase difference (A nd) of the liquid crystal cell when no voltage is applied is 2 0 0 ⁇ ⁇ ! ⁇ 400 nm is preferred, more preferably 2 3 0 n n! ⁇ 3500 nm. If it is out of this range, unnecessary coloration and a decrease in brightness are caused, which is not preferable.
- the driving method of the liquid crystal cell there is no particular limitation on the driving method of the liquid crystal cell.
- Any driving method such as a plasma-mlessing method may be used.
- the liquid crystal cell has a configuration in which a liquid crystal layer is sandwiched between two transparent substrates (hereinafter, the observer side is sometimes referred to as an upper substrate and the backlight side is referred to as a lower substrate).
- the material exhibiting liquid crystallinity for forming the liquid crystal layer is not particularly limited, and examples thereof include various ordinary low-molecular liquid crystal substances, high-molecular liquid crystal substances, and mixtures thereof that can constitute various liquid crystal cells.
- pigments, chiral agents, non-liquid crystalline substances, and the like can be added to these as long as liquid crystallinity is not impaired.
- the liquid crystal cell may include various constituent elements necessary for forming liquid crystal cells of the various types described above and various constituent members described below.
- the transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction.
- a transparent substrate having the property of orienting liquid crystals by the substrate itself, a force that lacks the alignment ability of the substrate itself, a transparent substrate having an alignment film having the property of orienting liquid crystals, etc. Can also be used.
- well-known things, such as ITO, can be used for the electrode of a liquid crystal cell.
- the electrode can usually be provided on the surface of the transparent substrate with which the liquid crystal layer is in contact, and when a substrate having an alignment film is used, it can be provided between the substrate and the alignment film.
- the polarizing plate used in the present invention is not particularly limited as long as the object of the present invention can be achieved, and a normal polarizing plate used in a liquid crystal display device can be appropriately used.
- iodine and / or dichroism is applied to hydrophilic high molecular films made of PVA such as polybulal alcohol (PVA) and partially acetalized PVA, and partially saponified ethylene monoacetate butyl copolymer.
- a polarizing film composed of a polarizing film adsorbing a dye, a poly-oriented film such as a dehydrochlorinated product of polyvinyl chloride, and the like can be used.
- a reflective polarizing film can also be used.
- the polarizing plate may be used alone, or may be a polarizing film provided with a transparent protective layer or the like on one or both sides of the polarizing film for the purpose of improving strength, improving moisture resistance, improving heat resistance, etc. good.
- a transparent protective layer transparent plastic films such as polyester, triacetyl cell mouth, cyclic olefinic polymer, etc. are laminated directly or through an adhesive layer, transparent resin coating layer, acrylic or epoxy photo-curing For example, a chemical resin layer.
- transparent protective layers are coated on both sides of the polarizing film, different protective layers may be provided on both sides.
- the second optically anisotropic layer used in the present invention is not particularly limited as long as it is excellent in transparency and uniformity, but a polymer stretched film or an optical film made of liquid crystal can be preferably used.
- the stretched polymer film include uniaxial or biaxial retardation films made of cellulose, polycarbonate, polyarylate, polysulfone, polyacrylic, polyethersulfone, cyclic olefinic polymer compounds, etc. can do.
- the second optically anisotropic layer exemplified here may be composed only of a polymer stretched film, may be composed only of an optical film composed of liquid crystal, or an optical composed of a polymer stretched film and liquid crystal. Both films can be used together.
- an optical film made of liquid crystal various liquid crystal polymer compounds of main chain type and / or side chain type, for example, liquid crystal polyester, liquid crystal polycarbonate, liquid crystal polyacrylate, etc.
- An optical film made of a low molecular weight liquid crystal compound having a reactivity capable of molecular weight can be listed, and these may be a self-supporting single film or formed on a transparent support substrate.
- the positive biaxial optically anisotropic layer has a refractive index relationship of nx>nz> ny.
- a negative biaxial optically anisotropic layer has a refractive index relationship of nx>ny> nz.
- the first optically anisotropic layer used in the present invention is a liquid crystalline polymer exhibiting optically positive uniaxiality, specifically, a liquid crystalline polymer compound exhibiting optically positive uniaxiality, or at least An optically positive uniaxial liquid crystalline polymer composition containing one kind of the liquid crystalline polymer compound, wherein the liquid crystalline polymer compound or the liquid crystalline polymer composition is a liquid crystal
- the layer includes at least a liquid crystal film in which a nematic hybrid alignment structure having an average tilt angle of 5 ° to 45 ° formed in a state is fixed.
- the nematic hybrid alignment referred to in the present invention refers to an alignment form in which the liquid crystal molecules are nematically aligned, and the angle between the director of the liquid crystal molecules and the film plane at this time is different between the upper surface and the lower surface of the film. . Therefore, the angle formed by the director and the film plane is different between the vicinity of the upper surface interface and the vicinity of the lower surface interface. Therefore, the angle continuously changes between the upper surface and the lower surface of the film. It can be said.
- the directors of the liquid crystal molecules are oriented at different angles at all positions in the film thickness direction. Therefore, the film no longer has an optical axis when viewed as a film structure.
- the average tilt angle as used in the present invention means the average value of the angle formed by the director of the liquid crystal molecule and the film plane in the film thickness direction of the liquid crystal film.
- the angle formed by the director and the film plane is usually 20 ° to 90 °, preferably 40 ° to 80 °, in the vicinity of one interface of the film, More preferably, it has an angle of 50 ° to 70 °, and on the opposite side, the absolute value is usually 0 ° to 20 °, preferably 0 ° to 10 °.
- the average tilt angle is usually 5 ° to 50 ° in absolute value, preferably 20 ° to 45 °, more preferably 25 ° to 40 °.
- the average tilt angle is out of the above range, it is not desirable because it may cause a decrease in contrast when viewed from an oblique direction.
- the average tilt angle can be obtained by applying a crystal rotation method.
- the liquid crystal film constituting the first optically anisotropic layer used in the present invention has the nematic hybrid alignment state of the liquid crystalline polymer compound or liquid crystalline polymer composition as described above fixed and specific.
- any liquid crystal may be used as long as it has nematic hybrid orientation and satisfies the range of the average tilt angle.
- a liquid crystal film obtained by forming a low-molecular liquid crystal in a nematic hybrid orientation in a liquid crystal state and then fixing it by photocrosslinking or thermal crosslinking can be used.
- the film as used in this invention, it does not ask whether or not the film itself exhibits liquid crystallinity, but means a film obtained by forming a liquid crystal substance such as a low-molecular liquid crystal or a polymer liquid crystal into a film.
- the in-plane apparent retardation value when viewed from the normal direction of the liquid crystal film constituting the first optically anisotropic layer is the refractive index in the direction parallel to the director in the case of a nematic hybrid oriented film.
- ne the refractive index in the vertical direction
- no the refractive index in the vertical direction
- the value obtained by subtracting no from ne (ne—no) is assumed to be the birefringence above. It is assumed that the apparent retardation value is given by the product of the apparent birefringence and the absolute film thickness. This retardation value can be easily obtained by polarization optical measurement such as ellipsometry.
- the specific arrangement conditions of the optically anisotropic layer in the liquid crystal display device of the present invention will be described.
- the optical anisotropy composed of a liquid crystal film will be described with reference to FIGS.
- the upper and lower layers, the tilt direction of the optically anisotropic layer, and the pretilt direction of the liquid crystal cell layer are defined below.
- the upper and lower sides of the optically anisotropic layer made of a liquid crystal film are respectively defined by the angles formed by the liquid crystal molecule director and the film plane in the vicinity of the film interface of the liquid crystal film constituting the optically anisotropic layer.
- the surface where the angle formed by the rectifier and the film plane forms an angle of 20 to 90 degrees on the acute angle side is defined as b surface, and the surface which forms the angle of 0 to 20 degrees on the acute angle side Is the c-plane.
- the angle formed between the liquid crystal molecule director and the projection component of the director on the c-plane is an acute angle and parallel to the projection component. This direction is defined as the tilt direction of the optical anisotropic element (Figs. 1 and 2).
- the driving low-molecular liquid crystal is not parallel to the cell interface but tilted at a certain angle, and this angle is generally referred to as a pretilt angle.
- the direction in which the angle formed by the projection component on the director interface is an acute angle and the direction parallel to the projection component of the director is defined as the pretilt direction of the liquid crystal cell layer (Fig. 3).
- the first and second optically anisotropic layers may be prepared by bonding each other through an adhesive layer or an adhesive layer.
- Adhesive that forms the adhesive layer has sufficient adhesion to the optically anisotropic layer.
- acrylic resin, methacrylic resin, epoxy resin, ethylene monoacetate copolymer system, rubber system examples thereof include urethane-based, polyvinyl ether-based and mixtures thereof, and various reactive types such as thermosetting type Z or photo-curing type and electron beam-curing type.
- These adhesives include those having the function of a transparent protective layer for protecting the optically anisotropic layer.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
- an acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately used. It can be selected and used.
- an acrylic adhesive having excellent optical transparency, easy adjustment of wettability, cohesiveness and adhesive properties, and excellent weather resistance and heat resistance can be preferably used.
- the adhesive and the pressure-sensitive adhesive may be collectively referred to as “sticky adhesive”
- the adhesive and the pressure-sensitive adhesive can be performed by an appropriate method.
- examples thereof include 10 to 40 weights obtained by dissolving or dispersing a base polymer or a composition thereof in a solvent composed of a single solvent or a mixture of suitable solvents such as toluene or ethyl acetate. / 0 about a tacky adhesive solution was prepared, as flow method and coating method suitable developing methods in a manner directly applied on the optically anisotropic layer of the like, or viscous on a separator according to the above, ⁇ A method of forming an adhesive layer and transferring it onto the optically anisotropic layer can be mentioned.
- the viscosity and adhesive layers include, for example, natural and synthetic resins, in particular, tackifier resins, fillers and pigments made of glass fibers, glass beads, metal powders, other inorganic powders, It may contain additives such as colorants and antioxidants. Further, it may be an adhesive layer containing fine particles and exhibiting light diffusibility.
- the surface of the optically anisotropic layer is surface-treated to improve the adhesion to the adhesive layer or the pressure-sensitive adhesive layer.
- the surface treatment means is not particularly limited, and surface treatment methods such as corona discharge treatment, sputtering treatment, low-pressure UV irradiation, and plasma treatment that can maintain the transparency of the liquid crystal layer surface can be suitably employed. Among these surface treatment methods, edge discharge treatment is good.
- Polarizing plate / second optically anisotropic layer liquid crystal cell / polarizing plate Z first optically anisotropic layer / knock light
- a transparent electrode 3 made of a material having a high transmittance such as ITO is provided on the substrate 1, and a counter electrode 4 made of a material having a high transmittance such as ITO is provided on the substrate 2.
- a liquid crystal layer 5 made of a liquid crystal material exhibiting positive dielectric anisotropy is sandwiched between the counter electrode 4.
- a polarizing plate 7 is provided on the opposite surface of the substrate 2 on the side on which the counter electrode 4 is formed, and the first optically anisotropic layer 9 on the opposite side of the surface on which the transparent electrode 3 is formed on the substrate 1, Two optically anisotropic layers 10 and a polarizing plate 8 are provided. On the back side of the polarizing plate 8, a backlight 11 is provided.
- the angle between the pretilt direction of the liquid crystal layer in the liquid crystal cell and the tilt direction of the first optically anisotropic layer composed of the liquid crystal film in which the nematic hybrid alignment structure is fixed is preferably in the range of 0 to 30 degrees. More preferably, it is in the range of 0 degrees to 20 degrees, and particularly preferably in the range of 0 degrees to 10 degrees. If the angle formed by both exceeds 30 degrees, sufficient viewing angle compensation may not be obtained.
- the angle formed by the slow axis of the second optical anisotropic layer and the tilt direction of the first optical anisotropic layer is preferably 70 degrees or more and less than 110 degrees. More preferably, it is not less than 80 degrees and less than 100 degrees. If it is 1 10 degrees or more, or less than 70 degrees, the front contrast may be lowered, which is not preferable.
- the angle between the tilt direction of the first optically anisotropic layer and the absorption axis of the polarizing plate is 30 degrees. More than 60 degrees is preferable. More preferably, it is 40 degrees or more and less than 5,0 degrees. If it is 60 degrees or more, or less than 30 degrees, the front contrast may be reduced, which is not preferable.
- the angle formed by the slow axis of the second optically anisotropic layer and the absorption axis of the polarizing plate is preferably 30 degrees or more and less than 60 degrees. More preferably, it is 40 degrees or more and less than 50 degrees. If it is 60 ° or more, or less than 30 °, the front contrast may be lowered, which is not preferable.
- the anisotropy ⁇ 2 is generally dependent on the wavelength (nm), and its characteristics generally have a negative tendency with respect to the wavelength; L.
- D is the same if the liquid crystal materials are exactly the same, but different liquid crystal materials may be the same.
- birefringence wavelength dispersions of the liquid crystal cell, the first optically anisotropic layer, and the second optically anisotropic layer are represented as DLC ;, D1, and D2, respectively.
- the light emitted from the backlight 11 passes through the polarizing plate 8 and is incident on the second optically anisotropic layer 10.
- the slow axis of the first optically anisotropic layer 9 is used. Is substantially parallel to the rubbing direction of the liquid crystal cell 6 and the slow axis of the second optically anisotropic layer 10 is substantially perpendicular thereto.
- the thickness of the first optically anisotropic layer is d 1
- the main refractive indices in the plane are Nx 1 and N y 1
- the main refractive index in the thickness direction is N z 1
- the in-plane retardation value R e 1 (Nx 1 -Ny 1) X d 1 [nm]
- the thickness of the second optical anisotropic layer is d 2
- the in-plane main refractive indices are Nx 2 and Ny 2
- the wavelength is 550 nm.
- phase difference value R e 1 of the first optical anisotropic layer The phase difference value R e 1 of the first optical anisotropic layer, the phase difference value R e 2 of the second optical anisotropic layer, and the phase difference R e (LC ) IR e 1 + R e (LC) -R e 2
- the optical anisotropy of the second optical anisotropic layer is canceled by the optical anisotropy of the first optical anisotropic layer and the liquid crystal cell.
- the light passing through the polarizing plate 8 is incident on the polarizing plate 7 almost without being affected by the phase difference, so that a black display can be obtained.
- R e l, R e 2 and R e (LC) are out of the range of equation (1), the front contrast may be lowered, which is not preferable.
- R e 1 is out of the range of equation (2), a sufficient viewing angle expansion effect may not be obtained, and unnecessary coloration may occur in the liquid crystal display device when viewed from an oblique direction.
- R e 2 is out of the range of equation (3), a sufficient compensation effect may not be obtained.
- the birefringence wavelength dispersion D 2 of the second optical anisotropic layer, the birefringence wavelength dispersion D 1 of the first optical anisotropic layer, and the birefringence wavelength of the liquid crystal cell Distributed DLC In order to obtain a good black display, the birefringence wavelength dispersion D 2 of the second optical anisotropic layer, the birefringence wavelength dispersion D 1 of the first optical anisotropic layer, and the birefringence wavelength of the liquid crystal cell Distributed DLC
- each optically anisotropic layer and the liquid crystal cell By adjusting the dispersion of each optically anisotropic layer and the liquid crystal cell so as to satisfy the above formula, light in a wide range of wavelengths of visible light satisfies the above formula (1), and the second optically anisotropic layer, The optical anisotropy of the first optical anisotropic layer and the liquid crystal cell can be canceled, and as a result, a good black display can be obtained. If the dispersion of each optically anisotropic layer and the liquid crystal cell is out of the above range, it is not preferable because the contrast may be lowered and the display on the display device may be unnecessarily colored.
- the light diffusion layer, the backlight, the light control film, the light guide plate, and the prism sheet are not particularly limited, and known materials can be used.
- the liquid crystal display device of the present invention can be provided with other constituent members in addition to the constituent members described above.
- a color filter to the liquid crystal display device of the present invention, a powerful liquid crystal display device capable of performing multicolor or full color display with high color purity can be manufactured.
- phase difference value ( ⁇ d) in this example is a value at a wavelength of 550 nm unless otherwise specified.
- a transparent electrode 3 made of a material having a high transmittance such as ITO is provided on the substrate 1, and a counter electrode 4 made of a material having a high transmittance such as ITO is provided on the substrate 2.
- a liquid crystal layer 5 made of a liquid crystal material exhibiting positive dielectric anisotropy is sandwiched between 3 and the counter electrode 4.
- a polarizing plate 7 is provided on the opposite surface of the substrate 2 on the side on which the counter electrode 4 is formed, and the first optically anisotropic layer 9 on the opposite side of the surface on which the transparent electrode 3 is formed on the substrate 1, Two optically anisotropic layers 10 and a polarizing plate 8 are provided. On the back side of the polarizing plate 8, a backlight 11 is provided.
- a first optically anisotropic layer 9 comprising a liquid crystal film of each film thickness in which a nematic hybrid alignment with an average tilt angle in the film thickness direction of 28 degrees is fixed. 10 to 160 nm), and a liquid crystal display device with an axial arrangement as shown in Fig. 5 was produced.
- the liquid crystal cell 6 used was ZLI-1 6 9 5 (manufactured by Merck) as the liquid crystal material, and the liquid crystal layer thickness was 4.9 ⁇ .
- the pretilt angle at the substrate interface of the liquid crystal layer is 3 degrees.
- the liquid crystal cell has an nd of about 320 nm and a dispersion DLC of about 1.0.
- a polarizing plate 7 (thickness: about 100 m; 3 ⁇ 3 ⁇ -062 manufactured by Sumitomo Chemical Co., Ltd.) was placed on the viewer side (upper side of the figure) of the liquid crystal cell 6.
- the dispersion of the Zeonor film was about 1.02, and the dispersion of the first optically anisotropic layer was about 1.16.
- Figure 6 shows the white display 0 V, black when the backlight is lit (transmission mode) when ⁇ nd of the first optically anisotropic layer 9 is 90 nm and ⁇ d of the zenoah film is 140 nm.
- the contrast ratio from all directions is shown with the contrast ratio (CR) as the 5 V transmittance ratio (white display) / (black display).
- Figure 6 shows that it has good viewing angle characteristics.
- the concentric circles in Fig. 6 are drawn at 20 ° intervals. Therefore, the outermost circle shows 80 ° from the center (the same applies to the following figures).
- Example 1 Using the configuration of Example 1, the same measurement was performed when the phase difference of the first optically anisotropic layer was changed, and the front CR and viewing angle characteristics at that time are summarized in Table 1.
- the symbol at the viewing angle means “good ⁇ ⁇ > X bad”.
- FIG. 7 shows a comparative example in which ⁇ nd of the first optically anisotropic layer is 10 nm, which is outside the range of the present invention, and ⁇ nd of the second optically anisotropic layer is 60 nm.
- the contrast ratio from all directions is shown with the transmittance ratio (white display) / (black display) of white display 0V, black display 5V as the contrast ratio. .
- ⁇ nd of the first optically anisotropic layer of the present invention is preferably adjusted in the range of ⁇ 140 nm. table 1
- the first optical anisotropic layer 9, the second optical anisotropic layer 10, and the polarizing plate are provided on the opposite surface of the substrate 2 on the side where the counter electrode 4 is formed. 7 is provided, and a polarizing plate 8 is provided on the opposite side of the surface of the substrate 1 on which the transparent electrode 3 is formed. A backlight 11 is provided on the back side of the polarizing plate 8.
- the polarizing plates 7 and 8, the first optically anisotropic layer 9, and the second optically anisotropic layer 10 were the same as those in Example 1.
- the absorption axes of the polarizing plates 7 and 8, the pretilt direction of both interfaces of the liquid crystal cell 6, the tilt direction of the liquid crystal film 9, and the slow axis of the polymer stretched film 10 were arranged under the conditions described in FIG.
- Fig. 10 shows the contrast ratio from all directions, with the ratio of the transmittance of white display OV and black display 5 V (white display) Z (black display) when the backlight is lit (transmission mode). Is shown.
- the second optically anisotropic layer 10 and the polarizing plate 7 are provided on the opposite surface of the substrate 2 on the side where the counter electrode 4 is formed.
- a first optically anisotropic layer 9 and a polarizing plate 8 are provided on the opposite side of the surface on which the transparent electrode 3 is formed.
- a backlight 11 is provided on the back side of the polarizing plate 8.
- Figure 13 shows contrast from all directions with the contrast ratio of the transmittance ratio of white display 0 V and black display 5 V (white display) / (black display) when the backlight is lit (transmission mode). The ratio is shown.
- Example 3 In the liquid crystal display device used in Example 3, produced in the same manner as in Example 3 except that the position of the second optically anisotropic layer 10 was replaced with the position of the first optically anisotropic layer 9. did.
- Figure 16 shows the contrast ratio from all directions when the backlight ratio (transmission mode) is used, with the contrast ratio of the white display 0 V and black display 5 V transmittance ratio (white display) Z (black display). The ratio is shown.
- Figure 16 shows that it has good viewing angle characteristics.
- the experiment was performed without a color filter.
- a color filter is provided in the liquid crystal cell, a good multi-color or full-color display can be achieved.
- FIG. 1 is a conceptual diagram for explaining the tilt angle and twist angle of liquid crystal molecules.
- FIG. 2 is a conceptual diagram of the alignment structure of the liquid crystalline film constituting the second optical anisotropic element.
- FIG. 3 is a conceptual diagram illustrating the pretilt direction of the liquid crystal cell.
- FIG. 4 is a cross-sectional view schematically showing the liquid crystal display device of Example 1.
- FIG. 5 is a plan view showing an angular relationship among the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, the slow axis of the polymer stretched film, and the tilt direction of the liquid crystal film in Example 1.
- FIG. 6 is a graph showing the contrast ratio when the liquid crystal display device in Example 1 is viewed from all directions.
- FIG. 7 is a diagram showing the contrast ratio when the liquid crystal display device in the comparative example is viewed from all directions.
- FIG. 8 is a cross-sectional view schematically showing the liquid crystal display device of Example 2.
- FIG. 9 is a plan view showing an angular relationship among the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, the slow axis of the polymer stretched film, and the tilt direction of the liquid crystal film in Example 2.
- FIG. 10 is a diagram showing the contrast ratio when the liquid crystal display device in Example 2 is viewed from all directions.
- FIG. 11 is a cross-sectional view schematically showing the liquid crystal display device of Example 3.
- FIG. 12 is a plan view showing the angular relationship among the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, the slow axis of the polymer stretched film, and the tilt direction of the liquid crystal film in Example 3.
- FIG. 13 is a diagram showing the contrast ratio when the liquid crystal display device in Example 3 is viewed from all directions.
- FIG. 14 is a cross-sectional view schematically showing the liquid crystal display device of Example 4.
- FIG. 15 is a plan view showing the angular relationship between the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, the slow axis of the polymer stretched film, and the tilt direction of the liquid crystal film in Example 4.
- FIG. 16 is a graph showing the contrast ratio when the liquid crystal display device in Example 4 is viewed from all directions.
- Substrate 1 and 2: Substrate, 3: Transparent electrode, 4: Counter electrode, 5: Liquid crystal layer, 6: Liquid crystal cell, 7 and 8: Polarizing plate, 9: First optical anisotropic layer, 10: Second Optically anisotropic layer,
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Abstract
Description
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CN2008800199573A CN101681062B (zh) | 2007-06-13 | 2008-01-29 | 透射式液晶显示装置 |
US12/602,584 US8018552B2 (en) | 2007-06-13 | 2008-01-29 | Transmissive liquid crystal display device |
EP08704390A EP2157475A4 (en) | 2007-06-13 | 2008-01-29 | TRANSMISSIVE LIQUID CRYSTAL DISPLAY DEVICE |
KR1020097026886A KR101426577B1 (ko) | 2007-06-13 | 2008-01-29 | 투과형 액정 표시장치 |
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JP2007-156623 | 2007-06-13 | ||
JP2007156623A JP2008309957A (ja) | 2007-06-13 | 2007-06-13 | 透過型液晶表示装置 |
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US (1) | US8018552B2 (ja) |
EP (1) | EP2157475A4 (ja) |
JP (1) | JP2008309957A (ja) |
KR (1) | KR101426577B1 (ja) |
CN (1) | CN101681062B (ja) |
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JP2007199257A (ja) * | 2006-01-25 | 2007-08-09 | Nippon Oil Corp | 液晶表示装置 |
JP4228004B2 (ja) * | 2006-05-24 | 2009-02-25 | 新日本石油株式会社 | 透過型液晶表示装置 |
JP4975415B2 (ja) * | 2006-11-17 | 2012-07-11 | Jx日鉱日石エネルギー株式会社 | 透過型液晶表示装置 |
EP2083290A4 (en) * | 2006-11-17 | 2012-02-08 | Nippon Oil Corp | ELLIPTIC POLARIZING PLATE AND VERTICALLY ALIGNED LIQUID CRYSTAL DISPLAY |
JP5072520B2 (ja) * | 2006-12-19 | 2012-11-14 | 株式会社ジャパンディスプレイセントラル | 液晶表示装置 |
JP2009075533A (ja) * | 2007-08-31 | 2009-04-09 | Nippon Oil Corp | 楕円偏光板および液晶表示装置 |
JP2009300760A (ja) * | 2008-06-13 | 2009-12-24 | Nippon Oil Corp | 楕円偏光板およびそれを用いた垂直配向型液晶表示装置 |
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CN103493120B (zh) * | 2011-04-28 | 2016-03-09 | 夏普株式会社 | 显示装置的制造方法、显示装置以及多显示器系统 |
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WO2015046983A1 (ko) * | 2013-09-27 | 2015-04-02 | 주식회사 엘지화학 | 광학 필름 |
TWI547719B (zh) * | 2013-09-27 | 2016-09-01 | Lg化學股份有限公司 | 光學膜 |
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Also Published As
Publication number | Publication date |
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US8018552B2 (en) | 2011-09-13 |
EP2157475A4 (en) | 2010-07-28 |
US20100182544A1 (en) | 2010-07-22 |
TWI396009B (zh) | 2013-05-11 |
KR20100031690A (ko) | 2010-03-24 |
KR101426577B1 (ko) | 2014-08-05 |
JP2008309957A (ja) | 2008-12-25 |
CN101681062B (zh) | 2011-10-12 |
TW200912458A (en) | 2009-03-16 |
EP2157475A1 (en) | 2010-02-24 |
CN101681062A (zh) | 2010-03-24 |
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