WO2009150779A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2009150779A1 WO2009150779A1 PCT/JP2009/001797 JP2009001797W WO2009150779A1 WO 2009150779 A1 WO2009150779 A1 WO 2009150779A1 JP 2009001797 W JP2009001797 W JP 2009001797W WO 2009150779 A1 WO2009150779 A1 WO 2009150779A1
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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
- G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
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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
- G02B5/3016—Polarising elements involving passive liquid crystal 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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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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
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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
- 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
- G02F2413/04—Number of plates greater than or equal to 4
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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
- G02F2413/08—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 a particular optical axis orientation
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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
- G02F2413/12—Biaxial compensators
Definitions
- the present invention relates to an elliptically polarizing plate and a liquid crystal display device excellent in viewing angle characteristics, and more particularly to a vertical alignment type liquid crystal display device in which liquid crystal molecules are aligned perpendicular to a substrate when no voltage is applied.
- the liquid crystal display device there is a vertical alignment mode in which liquid crystal molecules in the liquid crystal cell are aligned perpendicularly to the substrate surface in the initial state. When no voltage is applied, the liquid crystal molecules are aligned perpendicular to the substrate surface, and a black display is obtained by arranging linear polarizers orthogonally on both sides of the liquid crystal cell.
- the optical characteristics in the liquid crystal cell are isotropic in the in-plane direction, and ideal viewing angle compensation is easily possible.
- an optical element having negative uniaxial optical anisotropy in the thickness direction is inserted between one or both surfaces of the liquid crystal cell and the linear polarizer.
- Patent Document 1 a configuration is proposed in which linear polarizers arranged on both sides of a liquid crystal element having a liquid crystal layer including a randomly aligned state are replaced with circularly polarizing plates.
- a circularly polarizing plate that combines a linear polarizer and a quarter-wave plate By replacing the linear polarizer with a circularly polarizing plate that combines a linear polarizer and a quarter-wave plate, a dark region at the time of voltage application can be eliminated, and a liquid crystal display device with high transmittance can be realized.
- a vertical alignment type liquid crystal display device using a circularly polarizing plate has a problem that viewing angle characteristics are narrower than a vertical alignment type liquid crystal display device using a linear polarizer.
- an optical anisotropic element having a negative uniaxial optical anisotropy or a biaxial optical anisotropic material is proposed as a viewing angle compensation of a vertical alignment type liquid crystal display device using a circularly polarizing plate. ing. However, it can compensate for the positive uniaxial optical anisotropy in the thickness direction of the liquid crystal cell by an optical anisotropic element having negative uniaxial optical anisotropy. A viewing angle characteristic cannot be obtained.
- the in-plane main refractive index of the obtained retardation plate is nx, ny
- the refractive index in the thickness direction is nz
- nx> ny Nz defined by Nz (nx ⁇ nz) / (nx ⁇ ny) is ⁇ 1.0 ⁇ Nz ⁇ 1.0
- Nz (nx ⁇ nz) / (nx ⁇ ny)
- stretched in the thickness direction thickness of the obtained phase difference plate increases rather than a elongate film.
- the thickness of the retardation plate obtained by the manufacturing method is about 50 to 100 ⁇ m, which is not sufficient for the thinning required for a liquid crystal display device or the like.
- Patent Documents 3 and 4 as a viewing angle compensation of a vertical alignment type liquid crystal display device using a circularly polarizing plate, an optical anisotropic element having negative uniaxial optical anisotropy as a compensation of a liquid crystal cell, 1/4
- a configuration combining a compensation layer having a large refractive index in the thickness direction and a polarizer compensation film has been proposed.
- these three types of films are used on both sides of the vertical alignment type liquid crystal display device, so that a total of six films are used, and further, a ⁇ / 4 plate is used on both sides to provide a circularly polarizing plate function. For this reason, a total of 8 films are used, and although the viewing angle is greatly improved, it is not realistic in terms of both price and thickness.
- An object of the present invention is to provide an elliptically polarizing plate for a vertical alignment type liquid crystal display device and a vertical alignment type liquid crystal display device which can be reduced in price and have excellent viewing angle characteristics.
- the present inventors have found that the object can be achieved by the elliptically polarizing plate shown below and a vertical alignment type liquid crystal display device using the same, thereby completing the present invention. It came. That is, the present invention is as follows.
- An elliptically polarizing plate in which at least a first polarizer, a first optical anisotropic layer, a second optical anisotropic layer, and a third optical anisotropic layer are laminated in this order,
- the first optically anisotropic layer satisfies the following [1] to [3], [1] 50 ⁇ Re1 ⁇ 500 [2] 30 ⁇ Rth1 ⁇ 750 [3] 0.6 ⁇ Rth1 / Re1 ⁇ 1.5 (Here, Re1 means an in-plane retardation value of the first optically anisotropic layer, and Rth1 means a retardation value in the thickness direction of the first optically anisotropic layer.
- the second optically anisotropic layer satisfies the following [4] and [5], [4] 0 ⁇ Re2 ⁇ 20 [5] ⁇ 500 ⁇ Rth2 ⁇ ⁇ 30 (Here, Re2 means an in-plane retardation value of the second optically anisotropic layer, and Rth2 means a retardation value in the thickness direction of the second optically anisotropic layer.
- ny2 are main refractive indexes in the second optical anisotropic layer surface for light having a wavelength of 550 nm
- nz2 is a main refractive index in the thickness direction for light having a wavelength of 550 nm
- Re3 means an in-plane retardation value of the third optical anisotropic layer
- Rth3 means a retardation value in the thickness direction of the third optical anisotropic layer.
- ny3 is the main refractive index in the third optical anisotropic layer surface for light with a wavelength of 550 nm
- nz3 is the main refractive index in the thickness direction for light with a wavelength of 550 nm
- the second optically anisotropic layer is composed of a homeotropic alignment liquid crystal film in which a liquid crystalline composition exhibiting positive uniaxial property is homeotropically aligned in a liquid crystal state and then fixed in alignment.
- liquid crystalline composition exhibiting positive uniaxiality includes a side chain type liquid crystalline polymer having an oxetanyl group.
- the second optically anisotropic layer satisfies the following [4] and [5], [4] 0 ⁇ Re2 ⁇ 20 [5] ⁇ 500 ⁇ Rth2 ⁇ ⁇ 30 (Here, Re2 means an in-plane retardation value of the second optically anisotropic layer, and Rth2 means a retardation value in the thickness direction of the second optically anisotropic layer.
- ny2 are main refractive indexes in the second optical anisotropic layer surface for light having a wavelength of 550 nm
- nz2 is a main refractive index in the thickness direction for light having a wavelength of 550 nm
- the third optically anisotropic layer satisfies the following [6] to [8], [6] 100 ⁇ Re3 ⁇ 180 [7] 50 ⁇ Rth3 ⁇ 600 [8] 0.5 ⁇ Rth3 / Re3 ⁇ 3.5
- Re3 means an in-plane retardation value of the third optical anisotropic layer
- Rth3 means a retardation value in the thickness direction of the third optical anisotropic layer.
- ny3 is the main refractive index in the third optical anisotropic layer surface for light with a wavelength of 550 nm
- nz3 is the main refractive index in the thickness direction for light with a wavelength of 550 nm
- Re4 means an in-plane retardation value of the fourth optically anisotropic layer
- Rth4 means a retardation value in the thickness direction of the fourth optically anisotropic layer.
- ny4 is the main refractive index in the fourth optical anisotropic layer surface for light having a wavelength of 550 nm
- nz4 is the main refractive index in the thickness direction for light having a wavelength of 550 nm
- a fifth optical anisotropic layer satisfying the following [13] and [14] is further provided between the vertical alignment type liquid crystal cell and the fourth optical anisotropic layer. 9].
- Nx5 ny5 is the main refractive index in the plane of the fifth optical anisotropic layer for light with a wavelength of 550 nm
- nz5 is the main refractive index in the thickness direction for light with a wavelength of 550 nm
- the second optically anisotropic layer is composed of a homeotropically aligned liquid crystal film in which a liquid crystalline composition exhibiting positive uniaxial property is homeotropically aligned in a liquid crystal state and then fixed in alignment.
- the vertical alignment liquid crystal display device according to [9] or [10].
- liquid crystalline composition exhibiting positive uniaxiality includes a side chain liquid crystalline polymer having an oxetanyl group.
- the fifth optically anisotropic layer is selected from a liquid crystalline compound, triacetylcellulose, cyclic polyolefin, polyolefin, polyamide, polyimide, polyester, polyetherketone, polyaryletherketone, polyamideimide, and polyesterimide.
- the vertical alignment liquid crystal display device according to any one of [9] to [15], wherein the vertical alignment liquid crystal display device is a layer formed of at least one material.
- the angle formed by the absorption axis of the first polarizer and the slow axis of the third optical anisotropic layer is p, the absorption axis of the second polarizer and the fourth optical anisotropy Any one of [9] to [18] above, wherein 40 ° ⁇ p ⁇ 50 ° and 40 ° ⁇ q ⁇ 50 ° are satisfied, where q is an angle formed with the slow axis of the active layer. 4.
- a vertical alignment type liquid crystal display device according to 1.
- one substrate of the vertical alignment type liquid crystal cell is a substrate having a region having a reflection function and a region having a transmission function.
- Vertical alignment type liquid crystal display device is a substrate having a region having a reflection function and a region having a transmission function.
- the vertical alignment type liquid crystal display device of the present invention has a bright display and can display with high contrast in all directions.
- FIG. 6 is a schematic cross-sectional view of a vertical alignment type liquid crystal display device used in Example 2.
- FIG. FIG. 6 is a plan view showing the angular relationship of each component of the vertical alignment type liquid crystal display device used in Example 2. It is a figure which shows contrast ratio when the vertical alignment type liquid crystal display device in Example 2 is seen from all directions.
- 6 is a schematic cross-sectional view of a vertical alignment type liquid crystal display device used in Example 3.
- FIG. FIG. 6 is a plan view showing the angular relationship of each component of the vertical alignment type liquid crystal display device used in Example 3. It is a figure which shows contrast ratio when the vertical alignment type liquid crystal display device in Example 3 is seen from all directions.
- FIG. 6 is a schematic cross-sectional view of a transflective vertical alignment liquid crystal display device used in Example 4.
- FIG. FIG. 6 is a plan view showing the angular relationship of each component of the transflective vertical alignment type liquid crystal display device used in Example 4. It is a figure which shows contrast ratio when the transflective vertical alignment liquid crystal display device in Example 4 is viewed from all directions.
- 6 is a schematic cross-sectional view of a vertical alignment type liquid crystal display device used in Comparative Example 1.
- FIG. 6 is a plan view showing the angular relationship of each component of the vertical alignment type liquid crystal display device used in Comparative Example 1.
- FIG. It is a figure which shows the contrast ratio when the vertical alignment type liquid crystal display device in Comparative Example 1 is viewed from all directions.
- the elliptically polarizing plate of the present invention has at least a first polarizer, a first optical anisotropic layer, a second optical anisotropic layer, and a third optical anisotropic layer in this order as shown in FIG. It is a laminated elliptically polarizing plate.
- the vertical alignment type liquid crystal display device of the present invention is composed of the following two types, and members such as a light diffusion layer, a light control film, a light guide plate, and a prism sheet are further added as necessary. These are not particularly limited except that in the present invention, the second optically anisotropic layer comprising a homeotropic alignment liquid crystal film is used.
- any of the configurations (1) and (2) may be used in terms of obtaining optical characteristics with little viewing angle dependency.
- First polarizer / first optical anisotropic layer / second optical anisotropic layer / third optical anisotropic layer / vertical alignment type liquid crystal cell / fourth optical anisotropic layer / Second polarizer / backlight (2) first polarizer / first optical anisotropic layer / second optical anisotropic layer / third optical anisotropic layer / vertical alignment type liquid crystal cell / Fifth optically anisotropic layer / Fourth optically anisotropic layer / Second polarizer / backlight
- the eight-film configuration proposed in Patent Documents 3 and 4 is replaced with films 4 to 5.
- a negative biaxial optically anisotropic layer is used as the first optically anisotropic layer, so that the absorption axis of the first polarizer and the slow axis of the first optically anisotropic layer are In spite of being orthogonal to each other, it is possible to make an integral production by roll-to-roll rather than pasting by sheet as was done conventionally. As a result, a highly efficient and thin elliptical polarizing plate can be manufactured.
- the driving method of the liquid crystal cell is not particularly limited, and is a passive matrix method used for STN-LCDs, an active matrix method using active electrodes such as TFT (Thin Film Transistor) electrodes, TFD (Thin Film Diode) electrodes, and a plasma addressing method. Any driving method may be used.
- 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 aligning the liquid crystal itself a substrate itself lacking alignment ability, but a transparent substrate provided with an alignment film having the property of aligning liquid crystal, etc.
- 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. When a substrate having an alignment film is used, it can be provided between the substrate and the alignment film.
- the material exhibiting liquid crystallinity for forming the liquid crystal layer is not particularly limited as long as it has a negative dielectric anisotropy, and various ordinary low-molecular liquid crystal substances and polymer liquid crystals capable of constituting various liquid crystal cells. Materials and mixtures thereof.
- a dye, a chiral agent, a non-liquid crystal substance, or the like can be added to these as long as liquid crystallinity is not impaired. If a chiral agent is added to a vertically aligned liquid crystal layer using a liquid crystal material exhibiting negative dielectric anisotropy and the liquid crystal molecules are rotated when voltage is applied, the rotation of the liquid crystal molecules when voltage is applied should be stabilized. Can do.
- the trace of the alignment process is not the same direction, so that the streak is less noticeable.
- the liquid crystal layer is twisted by 90 degrees, retardation occurs in the tilt direction of the liquid crystal molecules when tilted by several degrees with respect to the substrate to prevent disclination when a voltage is applied. Since the directions in which the liquid crystal molecules in the vicinity are inclined at an angle of 90 degrees in the vicinity of the upper and lower substrates, the generated retardation can be canceled and a black display with less leakage light can be obtained.
- a transflective vertical alignment type liquid crystal cell can be obtained by using one substrate of the vertical alignment type liquid crystal cell as a substrate having a region having a reflection function and a region having a transmission function.
- a region having a reflection function (hereinafter sometimes referred to as a reflective layer) included in the transflective electrode used in the transflective vertical alignment type liquid crystal cell is not particularly limited, and may be aluminum, silver, gold Examples thereof include metals such as chromium and platinum, alloys containing them, oxides such as magnesium oxide, dielectric multilayer films, liquid crystals exhibiting selective reflection, and combinations thereof. These reflective layers may be flat or curved.
- the reflective layer is processed to have a surface shape such as an uneven shape to give diffuse reflection, to the electrode on the electrode substrate opposite to the viewer side of the liquid crystal cell, or a combination thereof It may be.
- the vertical alignment type liquid crystal display device of the present invention can be provided with other constituent members in addition to the constituent members described above. For example, by attaching a color filter to the liquid crystal display device of the present invention, a color liquid crystal display device capable of performing multicolor or full color display with high color purity can be manufactured.
- optically anisotropic layer used in the present invention will be described in order.
- first, third, and fourth optical anisotropic layers will be described.
- the optically anisotropic layer for example, a film made of an appropriate polymer such as cyclic polyolefin such as polycarbonate or norbornene resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene or other polyolefin, polyarylate, polyamide is uniaxial.
- a birefringent film manufactured by a method of biaxial stretching treatment or a method of increasing the phase difference in the thickness direction by thermally shrinking the width direction of a long film with a heat-shrinkable film as disclosed in JP-A-5-157911 And an alignment film made of a liquid crystal material such as a liquid crystal polymer, and an alignment layer of the liquid crystal material supported by the film.
- the positive biaxial optically anisotropic layer has a relationship of nx> nz> ny as a refractive index.
- the negative biaxial optically anisotropic layer has a relationship of nx> ny> nz as a refractive index.
- the first optical anisotropic layer has a thickness d1 of the first optical anisotropic layer, nx1 and ny1 in the first optical anisotropic layer plane, and a main refractive index in the thickness direction.
- the following equations [1] to [3] are satisfied.
- the first optically anisotropic layer contributes to the viewing angle compensation of the polarizer, and the retardation value (Re1) in the first optically anisotropic layer plane is 50 nm to 500 nm for light of 550 nm. Preferably, it is in the range of 80 nm to 480 nm, more preferably 100 nm to 450 nm. When the Re1 value is out of the above range, a sufficient viewing angle improvement effect may not be obtained, or unnecessary coloring may occur when viewed from an oblique direction.
- the retardation value (Rth1) in the thickness direction of the first optically anisotropic layer is in the range of 30 nm to 750 nm, preferably 40 nm to 500 nm, more preferably 50 nm to 200 nm. When outside the above range, a sufficient viewing angle improvement effect may not be obtained, or unnecessary coloring may occur when viewed from an oblique direction.
- the ratio between the retardation value (Rth1) in the thickness direction of the first optically anisotropic layer and the in-plane retardation value (Re1) is usually 0.6 to 1.5, preferably 0.6 to 1.5. 1.4, more preferably in the range of 0.6 to 1.3. When the Rth / Re value is out of the above range, a sufficient viewing angle improvement effect may not be obtained, or unnecessary coloring may occur when viewed from an oblique direction.
- r is usually 80 ° to 100 °, preferably 85 to 95 °. More preferably, the angle is in the range of approximately 90 ° (orthogonal).
- the absorption axis of the first polarizer and the long roll of the first optically anisotropic layer are substantially orthogonal (the crossing angle is within 90 ° ⁇ 10 °, preferably within ⁇ 5 °).
- the slow axis of the first optical anisotropic layer is It is necessary to arrange in a direction perpendicular to the roll length direction. For that purpose, it is better to produce the first optically anisotropic layer by lateral uniaxial stretching or biaxial stretching.
- the relationship of the refractive index of the retardation film is known to be negative biaxial with nx> ny> nz.
- the Rth / Re value is preferably in the range of 0.6 to 1.5 described above. In a range other than the above, there is a risk of image quality deterioration due to a decrease in front contrast.
- the third and fourth optically anisotropic layers preferably exhibit a quarter wavelength retardation in the plane, and the thicknesses of the third and fourth optically anisotropic layers are d3, d4, and third.
- the main refractive index in the plane of the fourth optical anisotropic layer is nx3, nx4 and ny3, ny4, the main refractive index in the thickness direction is nz3, nz4, and nx3> ny3 ⁇ nz3, nx4> ny4 ⁇ nz4,
- the third and fourth optically anisotropic layers exhibit retardation values in the planes of the third and fourth optically anisotropic layers with respect to 550 nm light in that they exhibit a phase difference of 1 ⁇ 4 wavelength.
- Re3 and Re4 are in the range of 100 nm to 180 nm, preferably 120 nm to 160 nm, more preferably 130 nm to 150 nm. If it is out of the above range, sufficient circular polarization when combined with a polarizer cannot be obtained, and the display characteristics when viewed from the front may be deteriorated.
- the retardation values (Rth3, Rth4) in the thickness direction of the third and fourth optically anisotropic layers are 1 ⁇ 4 wavelength plates when the third and fourth optically anisotropic layers are viewed from the front.
- the ratio between the retardation values (Rth3, Rth4) in the thickness direction of the third and fourth optically anisotropic layers and the in-plane retardation values (Re3, Re4) is usually 0.5 to 3.5.
- the range is preferably 1.0 to 3.0, more preferably 1.5 to 2.5.
- the angle formed by the slow axis of the third optically anisotropic layer and the slow axis of the fourth optically anisotropic layer is usually 80 to 100 degrees, preferably 85 to 95 degrees, more preferably about 90 degrees. (Orthogonal) range. When outside the above range, the contrast when viewed from the front may be lowered.
- the in-plane retardation values of the third and fourth optically anisotropic layers with wavelengths of 450 nm and 590 nm are respectively Re3 (450), Re3 (590), Re4 (450), and Re4 (590).
- the following equations [12] and [15] are satisfied. [12] 0.7 ⁇ Re3 (450) / Re3 (590) ⁇ 1.05 [15] 0.7 ⁇ Re4 (450) / Re4 (590) ⁇ 1.05
- the dependence of the retardation value of the quarter wavelength plate on the wavelength increases as the wavelength increases.
- the phase difference value of the third and fourth optically anisotropic layers with respect to 450 nm light and 590 nm light is usually 0.7 to 1.05, preferably 0. It is in the range of 75 to 1.0. If it is out of the above range, the display characteristics may be deteriorated such that the black display upon reflection becomes a bluish color.
- the circularly polarizing plate has a function of changing linearly polarized light into circularly polarized light or changing circularly polarized light into linearly polarized light with a quarter-wave plate, and has linear polarizers on both sides of the vertical alignment type liquid crystal cell.
- the observation direction of the liquid crystal layer can be adjusted when no voltage is applied. Since the phase difference is 0, dark display is possible by making the upper and lower polarizers orthogonal to each other, and a phase difference in the observation direction occurs when a voltage is applied, thereby enabling bright display.
- the angle between the absorption axis of the first polarizer and the slow axis of the third optically anisotropic layer is defined in that a circularly polarizing plate is formed by combining a linear polarizer with a quarter wave plate.
- p is usually in the range of 40 ° to 50 °, preferably 42 to 48 °, more preferably about 45 °.
- q is usually 40 ° to 50 °, preferably 42.
- the range is ⁇ 48 °, more preferably about 45 °. In a range other than the above, there is a risk of image quality deterioration due to a decrease in front contrast.
- the second optical anisotropic layer of the present invention is composed of a homeotropic alignment liquid crystal film in which a liquid crystal material exhibiting positive uniaxial property is homeotropically aligned in a liquid crystal state and then fixed in alignment.
- selection of a liquid crystal material and an alignment substrate is extremely important for obtaining a liquid crystal film in which the homeotropic alignment of the liquid crystal material is fixed.
- the liquid crystal material used in the present invention contains at least a side chain type liquid crystalline polymer such as poly (meth) acrylate or polysiloxane as a main constituent component.
- the side chain type liquid crystal polymer used in the present invention has a polymerizable oxetanyl group at the terminal. More specifically, the side chain obtained by homopolymerizing the (meth) acrylic moiety of the (meth) acrylic compound having an oxetanyl group represented by the formula (1) or copolymerizing with another (meth) acrylic compound.
- a preferred example is a liquid crystalline polymer material.
- R 1 represents hydrogen or a methyl group
- R 2 represents hydrogen, a methyl group or an ethyl group
- L 1 and L 2 are each independently a single bond, —O—, —O—CO.
- M represents formula (2), formula (3) or formula (4)
- n and m each independently represents an integer of 0 to 10.
- P 1 and P 2 each independently represent a group selected from Formula (5)
- P 3 represents a group selected from Formula (6)
- L 3 and L 4 are Each represents a single bond, —CH ⁇ CH—, —C ⁇ C—, —O—, —O—CO— or —CO—O—.
- the method for synthesizing these (meth) acrylic compounds having an oxetanyl group is not particularly limited, and can be synthesized by applying a method used in a general organic chemical synthesis method. For example, by combining a site having an oxetanyl group and a site having a (meth) acrylic group by means such as Williamson's ether synthesis or ester synthesis using a condensing agent, oxetanyl group and (meth) acrylic group 2 A (meth) acrylic compound having an oxetanyl group having two reactive functional groups can be synthesized.
- radical polymerization a (meth) acryl compound is dissolved in a solvent such as dimethylformamide (DMF), and 2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), or the like is used as an initiator. And reacting at 60 to 120 ° C. for several hours. Moreover, in order to make the liquid crystal phase appear stably, a copper (I) bromide / 2,2′-bipyridyl system, a 2,2,6,6-tetramethylpiperidinooxy free radical (TEMPO) system, etc. are used. A method of controlling the molecular weight distribution by conducting living radical polymerization as an initiator is also effective. These radical polymerizations are preferably performed under deoxygenation conditions.
- a solvent such as dimethylformamide (DMF), and 2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), or the like is used as an initiator. And reacting at 60
- anionic polymerization is a method in which a (meth) acrylic compound is dissolved in a solvent such as tetrahydrofuran (THF) and reacted with a strong base such as an organic lithium compound, an organic sodium compound, or a Grignard reagent as an initiator.
- a strong base such as an organic lithium compound, an organic sodium compound, or a Grignard reagent as an initiator.
- the molecular weight distribution can be controlled by optimizing the initiator and the reaction temperature for living anionic polymerization.
- the (meth) acryl compound to be copolymerized at this time is not particularly limited and may be anything as long as the synthesized polymer substance exhibits liquid crystallinity, but in order to increase the liquid crystallinity of the synthesized polymer substance, A (meth) acrylic compound having a mesogenic group is preferred.
- a (meth) acrylic compound represented by the following formula can be exemplified as a preferred compound.
- R represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a cyano group.
- the side chain type liquid crystalline polymer substance preferably contains 5 to 100 mol% of the unit represented by the formula (7), and particularly preferably contains 10 to 100 mol%.
- the side chain type liquid crystalline polymer substance preferably has a weight average molecular weight of 2,000 to 100,000, particularly preferably 5,000 to 50,000.
- the liquid crystal material used in the present invention may contain various compounds that can be mixed without impairing liquid crystallinity in addition to the side chain liquid crystalline polymer substance.
- examples of compounds that can be contained include compounds having a cationic polymerizable functional group such as an oxetanyl group, an epoxy group, and a vinyl ether group, various polymer substances having film-forming ability, and various low-molecular liquid crystal compounds exhibiting liquid crystallinity. And polymer liquid crystalline compounds.
- the side chain liquid crystalline polymer substance is used as a composition, the proportion of the side chain liquid crystalline polymer substance in the entire composition is 10% by mass or more, preferably 30% by mass or more, and more preferably. Is 50 mass% or more. If the content of the side chain type liquid crystalline polymer substance is less than 10% by mass, the concentration of the polymerizable group in the composition becomes low, and the mechanical strength after polymerization becomes insufficient.
- the liquid crystal material contains a photocation generator and / or a thermal cation generator that generates cations by an external stimulus such as light or heat. If necessary, various sensitizers may be used in combination.
- the photo cation generator means a compound capable of generating a cation by irradiating with light having an appropriate wavelength, and examples thereof include organic sulfonium salt systems, iodonium salt systems, and phosphonium salt systems. Antimonates, phosphates, borates and the like are preferably used as counter ions of these compounds. Specific examples of the compound include Ar 3 S + SbF 6 ⁇ , Ar 3 P + BF 4 ⁇ , Ar 2 I + PF 6 ⁇ (wherein Ar represents a phenyl group or a substituted phenyl group), and the like. In addition, sulfonic acid esters, triazines, diazomethanes, ⁇ -ketosulfone, iminosulfonate, benzoinsulfonate and the like can also be used.
- the thermal cation generator is a compound capable of generating a cation by being heated to an appropriate temperature, for example, benzylsulfonium salts, benzylammonium salts, benzylpyridinium salts, benzylphosphonium salts, hydrazinium salts, carboxylic acid esters, Examples thereof include sulfonic acid esters, amine imides, antimony pentachloride-acetyl chloride complexes, diaryliodonium salts-dibenzyloxycopper, and boron halide-tertiary amine adducts.
- the amount of these cation generators added to the liquid crystal material varies depending on the structure of the mesogenic part and spacer part, the oxetanyl group equivalent, the alignment condition of the liquid crystal, etc. constituting the side chain type liquid crystalline polymer material to be used. However, it is usually 100 mass ppm to 20 mass%, preferably 1000 mass ppm to 10 mass%, more preferably 0.2 mass% to 7 mass%, most preferably based on the side chain type liquid crystalline polymer substance. Is in the range of 0.5% to 5% by weight. If the amount is less than 100 mass ppm, the amount of cations generated may not be sufficient and polymerization may not proceed. If the amount is more than 20 mass%, the remaining cation generator remains in the liquid crystal film. It is not preferable because there is a risk that the light resistance and the like may deteriorate due to an increase in the number of objects.
- a substrate having a smooth plane is preferable, and examples thereof include a film or sheet made of an organic polymer material, a glass plate, and a metal plate. From the viewpoint of cost and continuous productivity, it is preferable to use a material made of an organic polymer.
- organic polymer materials include polyvinyl alcohol, polyimide, polyphenylene oxide, polyether ketone, polyether ether ketone, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, Examples include films made of transparent polymers such as polycarbonate polymers and acrylic polymers such as polymethyl methacrylate.
- styrene polymers such as polystyrene, acrylonitrile / styrene copolymer, olefin polymers such as polyethylene, polypropylene, ethylene / propylene copolymer, cyclopolyolefins having cyclic or norbornene structure, vinyl chloride polymers, nylon and aromatic polyamides.
- styrene polymers such as polystyrene, acrylonitrile / styrene copolymer, olefin polymers such as polyethylene, polypropylene, ethylene / propylene copolymer, cyclopolyolefins having cyclic or norbornene structure, vinyl chloride polymers, nylon and aromatic polyamides.
- olefin polymers such as polyethylene, polypropylene, ethylene / propylene copolymer, cyclopolyolefins having cyclic or norbornene structure, vinyl chloride poly
- imide polymers examples thereof include a film made of a transparent polymer such as a polymer, an epoxy-based polymer, and a blend of the above polymers.
- plastic films such as triacetyl cellulose, polycarbonate, norbornene polyolefin used as an optical film are used.
- organic polymer film examples include norbornene such as ZEONOR (trade name, manufactured by ZEON CORPORATION), ZEONEX (trade name, manufactured by ZEON CORPORATION), Arton (trade name, manufactured by JSR Corporation), etc.
- a plastic film made of a polymer material having a structure is preferable because it has excellent optical properties.
- a metal film the said film formed from aluminum etc. is mentioned, for example.
- the material constituting these substrates has a long chain (usually 4 or more carbon atoms, preferably 8 or more) alkyl group, More preferably, the substrate surface has a compound layer having a long-chain alkyl group. Among them, it is preferable to form a layer made of polyvinyl alcohol having a long-chain alkyl group because the formation method is easy.
- These organic polymer materials may be used alone as a substrate, or may be formed as a thin film on another substrate.
- the homeotropic alignment liquid crystal film of the present invention is an alignment in which in-plane anisotropy basically does not occur. Because of the structure, rubbing is not necessarily required. However, it is more preferable to apply a weak rubbing treatment from the viewpoint of suppressing repelling when a liquid crystal material is applied.
- An important setting value that defines the rubbing condition is a peripheral speed ratio. This represents the ratio between the movement speed of the cloth and the movement speed of the substrate when the rubbing cloth is wound around a roll and rubbed while the substrate is rubbed.
- the weak rubbing treatment usually has a peripheral speed ratio of 50 or less, more preferably 25 or less, and particularly preferably 10 or less.
- the peripheral speed ratio is greater than 50, the effect of rubbing is too strong, and the liquid crystal material cannot be completely aligned vertically, and there is a possibility that the alignment is tilted in the in-plane direction from the vertical direction.
- the manufacturing method of a homeotropic alignment liquid crystal film is demonstrated.
- the method for producing the liquid crystal film is not limited to these, the above-mentioned liquid crystal material is spread on the above-mentioned alignment substrate, and after aligning the liquid crystal material, light irradiation and / or heat treatment is performed. It can manufacture by fixing the said orientation state.
- the liquid crystal material is spread on the alignment substrate to form the liquid crystal material layer.
- the liquid crystal material is applied directly on the alignment substrate in a molten state, or the liquid crystal material solution is applied on the alignment substrate, and then the coating film is applied. And drying the solvent to distill off the solvent.
- the solvent used for preparing the solution is not particularly limited as long as it can dissolve the liquid crystal material of the present invention and can be distilled off under suitable conditions.
- ketones such as acetone, methyl ethyl ketone, isophorone, and cyclohexanone
- butoxyethyl Ethers such as alcohol, hexyloxyethyl alcohol, methoxy-2-propanol
- glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether
- esters such as ethyl acetate and ethyl lactate
- phenols such as phenol and chlorophenol
- N Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, halogens such as chloroform, tetrachloroethane, dichlorobenzene, etc.
- Mixed system is preferably used. Further, in order to form a uniform coating film
- the application method is not particularly limited as long as the uniformity of the coating film is ensured, and a known method may be adopted. It can. Examples thereof include spin coating, die coating, curtain coating, dip coating, and roll coating.
- a drying step for removing the solvent after the application As long as the uniformity of a coating film is maintained, this drying process can employ
- the film thickness of the liquid crystal film cannot be generally described because it depends on the type of the liquid crystal display device and various optical parameters, but is usually 0.2 ⁇ m to 10 ⁇ m, preferably 0.3 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m. ⁇ 2 ⁇ m.
- the film thickness is thinner than 0.2 ⁇ m, there is a possibility that a sufficient viewing angle improvement or brightness enhancement effect cannot be obtained. If it exceeds 10 ⁇ m, the liquid crystal display device may be unnecessarily colored.
- the liquid crystal material layer formed on the alignment substrate is liquid crystal aligned by a method such as heat treatment, and is cured and fixed by light irradiation and / or heat treatment.
- the liquid crystal is aligned by the self-alignment ability inherent in the liquid crystal material by heating to the liquid crystal phase expression temperature range of the used liquid crystal material.
- the conditions for the heat treatment cannot be generally stated because the optimum conditions and limit values differ depending on the liquid crystal phase behavior temperature (transition temperature) of the liquid crystal material to be used, but are usually 10 to 250 ° C., preferably 30 to 160 ° C.
- the heat treatment time is usually in the range of 3 seconds to 30 minutes, preferably 10 seconds to 10 minutes. If the heat treatment time is shorter than 3 seconds, the liquid crystal alignment may not be completed sufficiently, and if the heat treatment time exceeds 30 minutes, the productivity is deteriorated.
- the liquid crystal material layer is formed into a liquid crystal alignment by a method such as heat treatment
- the liquid crystal material is cured by a polymerization reaction of oxetanyl groups in the composition while maintaining the liquid crystal alignment state.
- the curing step is aimed at fixing the liquid crystal alignment state of the completed liquid crystal alignment by a curing (crosslinking) reaction and modifying it into a stronger film.
- the liquid crystal material of the present invention has a polymerizable oxetanyl group, as described above, it is preferable to use a cationic polymerization initiator (cation generator) for the polymerization (crosslinking) of the reactive group.
- a cationic polymerization initiator cation generator
- the polymerization initiator it is preferable to use a photo cation generator rather than a thermal cation generator.
- the liquid crystal material can be obtained by adding the photo cation generator to the heat treatment for aligning the liquid crystal under dark conditions (light blocking conditions that do not cause the photo cation generator to dissociate). The liquid crystal can be aligned with sufficient fluidity without curing until the alignment stage. Thereafter, the liquid crystal material layer is cured by generating cations by irradiating light from a light source that emits light of an appropriate wavelength.
- a photocation is generated by irradiating light from a light source such as a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, or a laser having a spectrum in the absorption wavelength region of the photocation generator used. Cleave the generator.
- the dose per square centimeter is usually in the range of 1 to 2000 mJ, preferably 10 to 1000 mJ, as the cumulative dose. However, this is not the case when the absorption region of the photocation generator and the spectrum of the light source are remarkably different, or when the liquid crystal material itself has the ability to absorb the light source wavelength.
- the temperature at the time of light irradiation needs to be within a temperature range in which the liquid crystal material takes liquid crystal alignment. In order to sufficiently enhance the curing effect, it is preferable to perform light irradiation at a temperature equal to or higher than Tg of the liquid crystal material.
- the liquid crystal material layer produced by the above process is a sufficiently strong film.
- the mesogens are three-dimensionally bonded by the curing reaction, and not only the heat resistance (the upper limit temperature for maintaining the liquid crystal alignment) is improved as compared to before curing, but also scratch resistance, abrasion resistance, crack resistance.
- the mechanical strength such as property is also greatly improved.
- As the alignment substrate it is not optically isotropic, or the liquid crystal film to be obtained is finally opaque in the intended use wavelength region, or the alignment substrate is too thick, resulting in problems in actual use.
- a form transferred from a form formed on an alignment substrate to a stretched film having a retardation function may be used.
- As a transfer method a known method can be adopted.
- a liquid crystal film layer is laminated with a substrate different from the alignment substrate via an adhesive or an adhesive, and if necessary, Examples thereof include a method of transferring only a liquid crystal film by performing a surface curing treatment using an adhesive or an adhesive and peeling the alignment substrate from the laminate.
- the pressure-sensitive adhesive or adhesive used for transfer is not particularly limited as long as it is of optical grade, and generally used ones such as acrylic, epoxy, and urethane can be used.
- the homeotropic alignment liquid crystal layer obtained as described above can be quantified by measuring the optical phase difference of the liquid crystal layer at an angle inclined from the normal incidence. In the case of homeotropic alignment liquid crystal layers, this retardation value is symmetric with respect to normal incidence.
- Several methods can be used for measuring the optical phase difference. For example, an automatic birefringence measuring apparatus (manufactured by Oji Scientific Instruments) and a polarizing microscope can be used. This homeotropic alignment liquid crystal layer appears black between the crossed Nicol polarizers. Thus, homeotropic orientation was evaluated.
- the homeotropic alignment liquid crystal film used in the present invention has a liquid crystal film thickness of d2, a liquid crystal film in-plane main refractive index of nx2 and ny2, a thickness direction main refractive index of nz2, and nz2> nx2 ⁇
- the Re2 value and Rth2 value which are optical parameters of the homeotropic alignment liquid crystal film, cannot be generally described because they depend on the type of the liquid crystal display device and various optical parameters, but the homeotropic alignment for monochromatic light of 550 nm
- the retardation value (Re2) in the plane of the liquid crystal film is in the range of 0 nm to 20 nm, preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm, and the retardation value (Rth2) in the thickness direction is ⁇ 500. It is controlled to ⁇ 30 nm, preferably ⁇ 400 to ⁇ 50 nm, more preferably ⁇ 400 to ⁇ 100 nm.
- the viewing angle improving film of the liquid crystal display device can widen the viewing angle while correcting the color tone of the liquid crystal display.
- the Re value is larger than 20 nm, the front characteristics of the liquid crystal display element may be deteriorated due to the large front retardation value.
- the Rth value is larger than ⁇ 30 nm or smaller than ⁇ 500 nm, a sufficient viewing angle improvement effect cannot be obtained, or unnecessary coloring may occur when viewed from an oblique direction.
- the fifth optical anisotropic layer is not particularly limited, but the non-liquid crystal material is excellent in heat resistance, chemical resistance, transparency, and rich in rigidity.
- the non-liquid crystal material is excellent in heat resistance, chemical resistance, transparency, and rich in rigidity.
- any one kind of these polymers may be used alone, or a mixture of two or more kinds having different functional groups, such as a mixture of polyaryletherketone and polyamide.
- polyimide is particularly preferable because of its high transparency and high orientation.
- the material made of a liquid crystal compound include a cholesteric alignment film made of a liquid crystal material such as a cholesteric liquid crystal polymer, and a film in which a cholesteric alignment layer of a liquid crystal material is supported by a film.
- the fifth optically anisotropic layer compensates for the viewing angle of the vertical alignment liquid crystal layer of the vertical alignment type liquid crystal cell, so that the thickness of the fifth optical anisotropic layer is d5 and the fifth optical anisotropy.
- the retardation value (Re5) in the plane of the optically anisotropic layer is usually in the range of 0 nm to 20 nm, preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm.
- Re5 value is out of the above range, there is a risk that the contrast is lowered when viewed from the front.
- the retardation value (Rth5) in the fifth thickness direction is such that the retardation value in the thickness direction of the vertical alignment type liquid crystal cell is usually 100 nm to 400 nm, preferably 180 nm to 360 nm, more preferably 200 nm to 300 nm. It is a range. When outside the above range, a sufficient viewing angle improvement effect may not be obtained, or unnecessary coloring may occur when viewed from an oblique direction.
- the polarizer used in the present invention one having a protective film on one side or both sides of the polarizer is usually used.
- the first optically anisotropic layer also functions as a protective film.
- the elliptically polarizing plate of the present invention is laminated so that the slow axis of the first optically anisotropic layer and the absorption axis of the first polarizer are perpendicular to each other, and is a negative biaxially stretched in the width direction.
- the polarizer is not particularly limited, and various types can be used.
- a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, an ethylene / vinyl acetate copolymer partially saponified film.
- polyene-based oriented films such as those obtained by adsorbing dichroic substances such as iodine and dichroic dyes and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- dichroic substances such as iodine and dichroic dyes
- the thickness of the polarizer is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
- the protective film provided on one side or both sides of the polarizer preferably has excellent transparency, mechanical strength, thermal stability, moisture shielding properties, isotropic properties, and the like.
- the material for the protective film include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene, acrylonitrile / styrene copolymer, and the like.
- polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic polymers such as polymethyl methacrylate, polystyrene, acrylonitrile / styrene copolymer, and the like.
- styrene polymers such as coalesced (AS resin), polycarbonate polymers, and the like.
- polyolefin polymers such as polyethylene, polypropylene, ethylene / propylene copolymers, polyolefins having cycloolefin or norbornene structures, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfones Polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the protective film include blends of the aforementioned polymers.
- the thickness of the protective film is generally 500 ⁇ m or less, and preferably 1 to 300 ⁇ m. In particular, the thickness is preferably 5 to 200 ⁇ m.
- the protective film is preferably an optically isotropic substrate.
- a triacetyl cellulose (TAC) film such as Fujitac (product of Fujifilm) or Konicatak (product of Konica Minolta Opto), Arton film (product of JSR) And ZEONOR film, ZEONEX film (product of ZEON Corporation), cycloolefin polymer, TPX film (product of Mitsui Chemicals), acrylene film (product of Mitsubishi Rayon Co., Ltd.)
- TAC triacetyl cellulose
- TPX film product of Mitsui Chemicals
- acrylene film product of Mitsubishi Rayon Co., Ltd.
- the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used.
- the polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like.
- aqueous adhesives include polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, aqueous polyurethanes, aqueous polyesters, and the like.
- a hard coat layer As the protective film, a hard coat layer, an antireflection treatment, an anti-sticking treatment, or a treatment subjected to diffusion or anti-glare treatment can be used.
- the hard coat treatment is performed for the purpose of preventing the surface of the polarizer from being scratched.
- a hard coating with an appropriate UV curable resin such as an acrylic or silicone resin is applied to the protective film. It can be formed by a method of adding to the surface.
- the antireflection treatment is performed for the purpose of preventing the reflection of external light on the surface of the polarizer, and can be achieved by forming an antireflection film or the like according to the prior art. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer.
- Anti-glare treatment is applied for the purpose of preventing external light from being reflected on the surface of the polarizer and obstructing the visibility of the light transmitted through the polarizer.
- roughening by sandblasting or embossing It can be formed by imparting a fine concavo-convex structure to the surface of the protective film by an appropriate method such as a method or a compounding method of transparent fine particles.
- the fine particles to be included in the formation of the fine surface uneven structure include conductive particles made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, and the like having an average particle size of 0.5 to 50 ⁇ m.
- transparent fine particles such as inorganic fine particles, organic fine particles composed of a crosslinked or uncrosslinked polymer, and the like are used.
- the amount of fine particles used is generally about 2 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the transparent resin forming the surface fine uneven structure.
- the antiglare layer may also serve as a diffusion layer (viewing angle expanding function or the like) for diffusing the light transmitted through the polarizer to expand the viewing angle.
- the antireflection layer, antisticking layer, diffusion layer, antiglare layer, and the like can be provided on the protective film itself, or can be provided separately from the transparent protective layer as an optical layer.
- the first, second, third, fourth, and fifth optically anisotropic layers and the polarizer can be produced by sticking each other through an adhesive layer.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
- an acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer is appropriately used as a base polymer.
- those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.
- the pressure-sensitive adhesive layer can be formed by an appropriate method.
- a pressure-sensitive adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of an appropriate solvent alone or a mixture such as toluene and ethyl acetate is prepared.
- a method in which it is directly attached on the liquid crystal layer by an appropriate development method such as a casting method or a coating method, or an adhesive layer is formed on the separator according to the above and transferred onto the liquid crystal layer Examples include methods.
- the pressure-sensitive adhesive layer includes, for example, natural and synthetic resins, in particular, tackifier resins, glass fibers, glass beads, metal powder, fillers made of other inorganic powders, pigments, colorants, You may contain the additive added to adhesion layers, such as antioxidant. Moreover, the adhesive layer etc. which contain microparticles
- the surface treatment means is not particularly limited, and a surface treatment method such as corona discharge treatment, sputtering treatment, low-pressure UV irradiation, or plasma treatment that can maintain the transparency of each optically anisotropic layer can be suitably employed.
- a surface treatment method such as corona discharge treatment, sputtering treatment, low-pressure UV irradiation, or plasma treatment that can maintain the transparency of each optically anisotropic layer can be suitably employed.
- corona discharge treatment is good.
- a liquid crystal material solution was prepared by filtration through a 0.45 ⁇ m polytetrafluoroethylene filter.
- the alignment substrate was prepared as follows.
- a 38 ⁇ m-thick polyethylene naphthalate film (manufactured by Teijin Limited) was cut into a 15 cm square, and a 5% by mass solution of alkyl-modified polyvinyl alcohol (PVA: Kuraray Co., Ltd., MP-203) (the solvent was water and isopropyl).
- a mixed solvent having an alcohol mass ratio of 1: 1) was applied by spin coating, dried on a hot plate at 50 ° C. for 30 minutes, and then heated in an oven at 120 ° C. for 10 minutes. Subsequently, it was rubbed with a rayon rubbing cloth.
- the film thickness of the obtained PVA layer was 1.2 ⁇ m.
- the peripheral speed ratio during rubbing was 4.
- the liquid crystal material solution described above was applied to the alignment substrate thus obtained by spin coating. Next, it was dried on a hot plate at 60 ° C. for 10 minutes and heat-treated in an oven at 150 ° C. for 2 minutes to align the liquid crystal material. Next, the sample is placed in close contact with an aluminum plate heated to 60 ° C., and then a 600 mJ / cm 2 ultraviolet light (however, measured at 365 nm) is irradiated with a high-pressure mercury lamp lamp to cure the liquid crystal material. It was.
- the obtained liquid crystalline film on the alignment substrate is converted to a triacetyl cellulose (TAC) film via an ultraviolet curable adhesive.
- TAC triacetyl cellulose
- an adhesive is applied to a thickness of 5 ⁇ m, laminated with a TAC film, and irradiated with ultraviolet rays from the TAC film side to cure the adhesive. After that, the polyethylene naphthalate film and the PVA layer were peeled off.
- the obtained optical film (liquid crystal layer / adhesive layer / TAC film) is observed under a polarizing microscope, it has a uniform uniaxial refractive index structure from conoscopic observation with uniform orientation of monodomains without disclination. It was found to be homeotropic alignment.
- the retardation in the in-plane direction of the TAC film and the liquid crystal layer measured using KOBRA21ADH was 0.5 nm, and the retardation in the thickness direction was -195 nm.
- the retardation of the liquid crystal layer alone was Re 0 nm and Rth Estimated at -230 nm.
- the TAC film of the substrate was removed and only the homeotropic alignment liquid crystal layer was taken out and used when bonded to another substrate.
- the thickness of the homeotropic alignment liquid crystal layer was 1.3 ⁇ m.
- the homeotropic alignment liquid crystal layer corresponds to the second optically anisotropic layer.
- Example 1 The structure of the elliptically polarizing plate will be described with reference to FIG.
- a triacetylcellulose (TAC) film 2 having a thickness of 40 ⁇ m, a front phase difference of 6 nm, and a thickness direction retardation of 60 nm is adhered to one side of the polarizer obtained in Reference Example 1 via a polyvinyl alcohol-based adhesive and is transparent.
- a protective layer was formed.
- the first optical element having a slow axis in the roll width direction produced by transverse uniaxial stretching with an absorption axis of a polarizer having an absorption axis in the roll length direction via a polyvinyl alcohol-based adhesive on the other surface of the polarizer.
- the second optically anisotropic layer 4 produced in Reference Example 2 was bonded via an acrylic pressure-sensitive adhesive, and further the third optically anisotropic layer 5 (manufactured by Nippon Zeon Co., Ltd.). ZEONOR) was bonded via an acrylic adhesive to obtain an elliptically polarizing plate. The thickness of the obtained elliptically polarizing plate was 231 ⁇ m.
- Re1 of the first optical anisotropic layer 3 is 100 nm and Rth1 indicates a phase difference of 90 nm
- Re3 of the third optical anisotropic layer 5 is 137.5 nm
- Rth3 indicates a phase difference of 210 nm. .
- Example 2 A vertical alignment type liquid crystal display device used in Example 2 will be described with reference to FIGS.
- a transparent electrode 8 made of a material having a high transmittance made of an ITO layer is formed on the substrate 7
- a counter electrode 10 is formed on the substrate 9, and a liquid crystal exhibiting negative dielectric anisotropy between the transparent electrode 8 and the counter electrode 10.
- a liquid crystal layer 11 made of a material is sandwiched.
- a vertical alignment film (not shown) is formed on the surface of the transparent electrode 8 and the counter electrode 10 in contact with the liquid crystal layer 11. After the alignment film is applied, alignment such as rubbing is performed on at least one alignment film. Processing is in progress.
- the liquid crystal molecules of the liquid crystal layer 11 have a tilt angle of 1 ° with respect to the vertical direction of the substrate surface by an alignment treatment such as rubbing on the vertical alignment film. Since a liquid crystal material exhibiting negative dielectric anisotropy is used for the liquid crystal layer 11, when a voltage is applied between the transparent electrode 8 and the counter electrode 10, the liquid crystal molecules are inclined in a direction parallel to the substrate surface. .
- Ne (refractive index for extraordinary light) 1.561
- No (refractive index for normal light) 1.478
- ⁇ N (Ne ⁇ No) 0.083
- a cell gap was set to 4.7 ⁇ m.
- the elliptically polarizing plate produced in Example 1 was disposed on the display surface side (upper side in the figure) of the vertical alignment type liquid crystal cell 12.
- a linearly polarizing plate 13 (thickness: about 105 ⁇ m; SQW-062 manufactured by Sumitomo Chemical Co., Ltd.) is disposed on the back side of the vertical alignment type liquid crystal cell 12 (the lower side in the figure).
- a fourth optically anisotropic layer 14 (Zeonor manufactured by Nippon Zeon Co., Ltd.) was disposed between them.
- the Rth of triacetyl cellulose used for the support substrate of the linear polarizing plate (SQW-062 manufactured by Sumitomo Chemical Co., Ltd.) was 35 nm.
- the directions of the absorption axes of the polarizer 1 and the linearly polarizing plate 13 indicated by arrows in FIG. 3 were in-plane 90 degrees and 0 degrees, respectively.
- the first optical anisotropic layer 3 is formed of an optical element having an in-plane optical axis and negative biaxial optical anisotropy.
- the slow axis orientation of the first optically anisotropic layer 3 indicated by an arrow in FIG. 3 is 0 degree, and the in-plane Re1 has a phase difference of 100 nm and the Rth1 has a phase difference of 90 nm.
- the third and fourth optically anisotropic layers 5 and 14 are formed of optical elements having an in-plane optical axis and negative biaxial optical anisotropy.
- the slow axis orientations of the third and fourth optically anisotropic layers 5 and 14 indicated by arrows in FIG. 3 are 45 degrees and 135 degrees, respectively, and Re3 and Re4 have a phase difference of 137.5 nm as Rth3 and Rth4 indicates a phase difference of 210 nm.
- the second optically anisotropic layer 4 made of a homeotropic alignment liquid crystal film exhibits a phase difference in which Re2 is 0 nm and Rth2 is ⁇ 230 nm.
- FIG. 4 shows the contrast ratio from all directions, where the transmittance ratio (white display) / (black display) of black display 0V and white display 5V is used as the contrast ratio. Contrast contour lines were set to 500, 200, 100, and 50 in order from the inside. Further, the concentric circles indicate an angle of 10 degrees from the center. Therefore, the outermost circle shows 80 degrees from the center (the same applies to the following figures).
- Example 3 The vertical alignment type liquid crystal display device used in Example 3 will be described with reference to FIGS.
- a fifth optically anisotropic layer 15 (ARTON manufactured by JSR Corporation) is disposed between the vertical alignment type liquid crystal cell 12 of Example 2 and the fourth optically anisotropic layer 14 to obtain a third optical anisotropic.
- a vertical alignment type liquid crystal display device was produced in the same manner as in Example 2 except that the phase difference between the conductive layer 5 and the fourth optically anisotropic layer 14 was 137.5 nm for Re3 and Re4 and 145 nm for Rth3 and Rth4. did.
- the fifth optically anisotropic layer 15 has a Re5 value of 0 and an Rth5 value of 120 nm.
- FIG. 7 shows the contrast ratio from all directions, with the transmittance ratio (white display) / (black display) of black display 0V and white display 5V as the contrast ratio.
- Example 4 A transflective vertical alignment liquid crystal display device was manufactured in the same manner as in Example 2 except that the transflective vertical alignment liquid crystal display device shown below was manufactured.
- a transflective vertical alignment liquid crystal display device will be described with reference to FIGS.
- the substrate 7 is provided with a reflective electrode 16 made of an Al layer made of a highly reflective material and a transparent electrode 8 made of an ITO layer made of a highly transparent material
- the substrate 9 is provided with a counter electrode 10
- the reflective electrode 16 a liquid crystal layer 11 made of a liquid crystal material exhibiting negative dielectric anisotropy is sandwiched between the transparent electrode 8 and the counter electrode 10.
- a vertical alignment film (not shown) is formed on the surface of the reflective electrode 16, the transparent electrode 8, and the counter electrode 10 in contact with the liquid crystal layer 11. After the alignment film is applied, at least one alignment film is formed. Alignment treatment such as rubbing is performed. The liquid crystal molecules of the liquid crystal layer 11 have a tilt angle of 1 ° with respect to the vertical direction of the substrate surface by an alignment treatment such as rubbing on the vertical alignment film. Since a liquid crystal material exhibiting negative dielectric anisotropy is used for the liquid crystal layer 11, when a voltage is applied between the reflective electrode 16, the transparent electrode 8, and the counter electrode 10, the liquid crystal molecules are parallel to the substrate surface. Tilt toward.
- FIG. 10 shows the contrast ratio from all directions, where the transmittance ratio (white display) / (black display) of black display 0V and white display 5V is used as the contrast ratio.
- Comparative Example 1 The vertical alignment type liquid crystal display device used in Comparative Example 1 will be described with reference to FIGS.
- a linearly polarizing plate 20 (thickness: about 105 ⁇ m; SQW-062 manufactured by Sumitomo Chemical Co., Ltd.) is disposed on the display surface side (upper side of the figure) of the vertical alignment type liquid crystal cell 12 used in Example 2, and the upper linear polarizing plate 20 And a liquid crystal cell 12, a positive uniaxial optically anisotropic layer 18 (Zeonor manufactured by Nippon Zeon Co., Ltd.) produced by longitudinal uniaxial stretching, and a second optical film composed of a homeotropically oriented liquid crystal film produced in Reference Example 2.
- An anisotropic layer 4 and a third optically anisotropic layer 5 were disposed.
- a linearly polarizing plate 13 (thickness: about 105 ⁇ m; SQW-062 manufactured by Sumitomo Chemical Co., Ltd.) is disposed on the back side of the vertical alignment type liquid crystal cell 12 (the lower side in the figure).
- a fourth optically anisotropic layer 14 (Zeonor manufactured by Nippon Zeon Co., Ltd.) was disposed between them.
- Rth of the triacetyl cellulose used for the support substrate of the linear polarizing plate (SQW-062 manufactured by Sumitomo Chemical Co., Ltd.) was 35 nm.
- the thickness of the elliptically polarizing plate disposed on the display surface side of the vertical alignment type liquid crystal cell 12 was 286 ⁇ m.
- the orientations of the absorption axes of the polarizer 1 and the linearly polarizing plate 13 indicated by arrows in FIG. 12 were in-plane 90 degrees and 0 degrees, respectively.
- the positive uniaxial optically anisotropic layer 18 has an optical axis in the plane and is formed of an optical element having positive uniaxiality.
- the azimuth of the slow axis of the positive uniaxial optically anisotropic layer 18 indicated by an arrow in FIG. 12 is 0 degree, and shows a phase difference of 120 nm for in-plane Re and 60 nm for Rth.
- the third and fourth optically anisotropic layers 5 and 14 are formed of optical elements having an in-plane optical axis and negative biaxial optical anisotropy.
- the slow axis directions of the third and fourth optically anisotropic layers 5 and 14 indicated by arrows in FIG. 12 are 45 degrees and 135 degrees, respectively, and the phase difference of Re3 and Re4 of 137.5 nm is represented by Rth3 and Rth4 indicates a phase difference of 210 nm.
- the second optically anisotropic layer 4 made of a homeotropic alignment liquid crystal film exhibits a phase difference in which Re2 is 0 nm and Rth2 is ⁇ 230 nm.
- FIG. 13 shows the contrast ratio from all directions, where the transmittance ratio (white display) / (black display) of black display 0V and white display 5V is used as the contrast ratio. Comparing the omnidirectional isocontrast curves in FIG. 4, FIG. 7 and FIG. 13, it can be seen that the viewing angle characteristics are substantially the same. However, with respect to the elliptically polarizing plate (thickness: 231 ⁇ m) produced in Example 1, the total thickness of the stacked body disposed on the upper side of the vertical alignment type liquid crystal cell 12 in FIG. 11 was as thick as 286 ⁇ m.
- the positive uniaxial optically anisotropic layer 18 produced by longitudinal uniaxial stretching is roll-to-roll so that the absorption axis of the polarizing plate and the slow axis of the positive uniaxial optically anisotropic layer 18 are orthogonal to each other.
- the thickness of the transparent protective layer 19 that protects the polarizer between the polarizer and the positive uniaxial optically anisotropic layer is increased.
- an elliptically polarizing plate having a low price and excellent viewing angle characteristics and a vertical alignment type liquid crystal display device using the same are provided.
- 1 polarizer
- 2 transparent protective layer
- 3 first optical anisotropic layer
- 4 second optical anisotropic layer
- 5 third optical anisotropic layer
- 6 elliptically polarizing plate
- 7 substrate
- 8 transparent electrode
- 9 substrate
- 10 counter electrode
- 11 liquid crystal layer (vertical alignment)
- 12 vertical alignment type liquid crystal cell
- 13 linearly polarizing plate
- 14 fourth optical anisotropy Layer
- 16 reflective electrode
- 17 transflective vertically aligned liquid crystal cell
- 18 positive uniaxial optically anisotropic layer
- 19 transparent protective layer
- 20 linear Polarizer
Abstract
Description
液晶セル内の光学特性は面内方向で等方的であり、理想的な視野角補償が容易に可能である。液晶セルの厚さ方向に正の一軸光学異方性を補償するため、厚さ方向に負の一軸光学異方性を有する光学素子を液晶セルの片面又は両面と直線偏光子との間に挿入すると、非常に良好な黒表示視角特性が得られる。
電圧印加時においては、液晶分子が基板表面に垂直な方向から基板表面に平行な方向に向って配向を変化させる。この際、液晶配列の均一化が困難である。通常の配向処理である基板表面のラビング処理を用いると、表示品位が著しく低下する。
電圧印加時における液晶配列を均一化するため、基板上の電極形状を工夫し、液晶層内に斜め電界が発生するようにし、均一配向を得る等の提案がある。この方法によれば、均一な液晶配列は得られるが、ミクロ的には不均一な配向領域が生じ、電圧印加時にこの領域が暗領域となる。従って、液晶表示装置の透過率が低下する。
すなわち、本発明は以下のとおりである。
前記第1の光学異方性層が、以下の[1]~[3]を満たし、
[1]50≦Re1≦500
[2]30≦Rth1≦750
[3]0.6≦Rth1/Re1≦1.5
(ここで、Re1は第1の光学異方性層の面内のリターデーション値を意味し、Rth1は第1の光学異方性層の厚さ方向のリターデーション値を意味する。Re1及びRth1は、それぞれRe1=(nx1-ny1)×d1[nm]、Rth1={(nx1+ny1)/2-nz1}×d1[nm]である。また、d1は第1の光学異方性層の厚さ、nx1,ny1は波長550nmの光に対する第1の光学異方性層面内の主屈折率、nz1は波長550nmの光に対する厚さ方向の主屈折率であり、nx1>ny1>nz1である。)
前記第2の光学異方性層が、以下の[4]、[5]を満たし、
[4]0≦Re2≦20
[5]-500≦Rth2≦-30
(ここで、Re2は第2の光学異方性層の面内のリターデーション値を意味し、Rth2は第2の光学異方性層の厚さ方向のリターデーション値を意味する。Re2及びRth2は、それぞれRe2=(nx2-ny2)×d2[nm]、Rth2={(nx2+ny2)/2-nz2}×d2[nm]である。また、d2は第2の光学異方性層の厚さ、nx2,ny2は波長550nmの光に対する第2の光学異方性層面内の主屈折率、nz2は波長550nmの光に対する厚さ方向の主屈折率であり、nz2>nx2≧ny2である。)
前記第3の光学異方性層が、以下の[6]~[8]を満たすことを特徴とする楕円偏光板。
[6]100≦Re3≦180
[7]50≦Rth3≦600
[8]0.5≦Rth3/Re3≦3.5
(ここで、Re3は第3の光学異方性層の面内のリターデーション値を意味し、Rth3は第3の光学異方性層の厚さ方向のリターデーション値を意味する。Re3及びRth3は、それぞれRe3=(nx3-ny3)×d3[nm]、Rth3={(nx3+ny3)/2-nz3}×d3[nm]である。また、d3は第3の光学異方性層の厚さ、nx3,ny3は波長550nmの光に対する第3の光学異方性層面内の主屈折率、nz3は波長550nmの光に対する厚さ方向の主屈折率であり、nx3>ny3≧nz3である。)
[12]0.7≦Re3(450)/Re3(590)≦1.05
(ここで、Re3(450)、Re3(590)は、波長450nm、590nmの光における第3の光学異方性層の面内のリターデーション値を意味する。)
前記第1の光学異方性層が、以下の[1]~[3]を満たし、
[1]50≦Re1≦500
[2]30≦Rth1≦750
[3]0.6≦Rth1/Re1≦1.5
(ここで、Re1は第1の光学異方性層の面内のリターデーション値を意味し、Rth1は第1の光学異方性層の厚さ方向のリターデーション値を意味する。Re1及びRth1は、それぞれRe1=(nx1-ny1)×d1[nm]、Rth1={(nx1+ny1)/2-nz1}×d1[nm]である。また、d1は第1の光学異方性層の厚さ、nx1,ny1は波長550nmの光に対する第1の光学異方性層面内の主屈折率、nz1は波長550nmの光に対する厚さ方向の主屈折率であり、nx1>ny1>nz1である。)
前記第2の光学異方性層が、以下の[4]、[5]を満たし、
[4]0≦Re2≦20
[5]-500≦Rth2≦-30
(ここで、Re2は第2の光学異方性層の面内のリターデーション値を意味し、Rth2は第2の光学異方性層の厚さ方向のリターデーション値を意味する。Re2及びRth2は、それぞれRe2=(nx2-ny2)×d2[nm]、Rth2={(nx2+ny2)/2-nz2}×d2[nm]である。また、d2は第2の光学異方性層の厚さ、nx2,ny2は波長550nmの光に対する第2の光学異方性層面内の主屈折率、nz2は波長550nmの光に対する厚さ方向の主屈折率であり、nz2>nx2≧ny2である。)
前記第3の光学異方性層が、以下の[6]~[8]を満たし、
[6]100≦Re3≦180
[7]50≦Rth3≦600
[8]0.5≦Rth3/Re3≦3.5
(ここで、Re3は第3の光学異方性層の面内のリターデーション値を意味し、Rth3は第3の光学異方性層の厚さ方向のリターデーション値を意味する。Re3及びRth3は、それぞれRe3=(nx3-ny3)×d3[nm]、Rth3={(nx3+ny3)/2-nz3}×d3[nm]である。また、d3は第3の光学異方性層の厚さ、nx3,ny3は波長550nmの光に対する第3の光学異方性層面内の主屈折率、nz3は波長550nmの光に対する厚さ方向の主屈折率であり、nx3>ny3≧nz3である。)
前記第4の光学異方性層が、以下の[9]~[11]を満たすことを特徴とする垂直配向型液晶表示装置。
[9]100≦Re4≦180
[10]50≦Rth4≦600
[11]0.5≦Rth4/Re4≦3.5
(ここで、Re4は第4の光学異方性層の面内のリターデーション値を意味し、Rth4は第4の光学異方性層の厚さ方向のリターデーション値を意味する。Re4及びRth4は、それぞれRe4=(nx4-ny4)×d4[nm]、Rth4={(nx4+ny4)/2-nz4}×d4[nm]である。また、d4は第4の光学異方性層の厚さ、nx4,ny4は波長550nmの光に対する第4の光学異方性層面内の主屈折率、nz4は波長550nmの光に対する厚さ方向の主屈折率であり、nx4>ny4≧nz4である。)
[13]0≦Re5≦20
[14]100≦Rth5≦400
(ここで、Re5は第5の光学異方性層の面内のリターデーション値を意味し、Rth5は第5の光学異方性層の厚さ方向のリターデーション値を意味する。Re5及びRth5は、それぞれRe5=(nx5-ny5)×d5[nm]、Rth5={(nx5+ny5)/2-nz5}×d5[nm]である。また、d5は第5の光学異方性層の厚さ、nx5,ny5は波長550nmの光に対する第5の光学異方性層面内の主屈折率、nz5は波長550nmの光に対する厚さ方向の主屈折率であり、nx5≧ny5>nz5である。)
[12]0.7≦Re3(450)/Re3(590)≦1.05
(ここで、Re3(450)、Re3(590)は、波長450nm、590nmの光における第3の光学異方性層の面内のリターデーション値を意味する。)
[15]0.7≦Re4(450)/Re4(590)≦1.05
(ここで、Re4(450)、Re4(590)は、波長450nm、590nmの光における第4の光学異方性層の面内のリターデーション値を意味する。)
本発明の楕円偏光板は、図1に示すような少なくとも第1の偏光子、第1の光学異方性層、第2の光学異方性層、第3の光学異方性層がこの順に積層された楕円偏光板である。
また、本発明の垂直配向型液晶表示装置は、以下のような2通りから構成され、必要に応じて光拡散層、光制御フィルム、導光板、プリズムシート等の部材が更に追加されるが、これらに本発明においてホメオトロピック配向液晶フィルムからなる第2の光学異方性層を使用する点を除いては特に制限は無い。視野角依存性の少ない光学特性を得ると言う点では、(1)~(2)いずれの構成を用いても構わない。
(1)第1の偏光子/第1の光学異方性層/第2の光学異方性層/第3の光学異方性層/垂直配向型液晶セル/第4の光学異方性層/第2の偏光子/バックライト
(2)第1の偏光子/第1の光学異方性層/第2の光学異方性層/第3の光学異方性層/垂直配向型液晶セル/第5の光学異方性層/第4の光学異方性層/第2の偏光子/バックライト
上記構成により、特許文献3及び4で提案されていたフィルム8枚構成をフィルム4ないし5枚まで削減することで広視野角特性を維持しつつコストダウンを図ることができる。
また、本発明では第1の光学異方性層として負の二軸性光学異方性層を用いることにより第1の偏光子の吸収軸と第1の光学異方性層の遅相軸が直交しているにも関わらず、従来行われていたようなシートでの貼り合わせでは無く、ロールトゥロールでの一体製造を可能にすることができる。その結果、高効率かつ薄型の楕円偏光板の製造が可能となる。
まず、本発明に使用する垂直配向型液晶セルについて説明する。
液晶セルとしては、特に制限はないが、透過型、反射型、半透過型の各種液晶セルを挙げることができる。液晶セルの駆動方式も特に制限はなく、STN-LCD等に用いられるパッシブマトリクス方式、TFT(Thin Film Transistor)電極、TFD(Thin Film Diode)電極等の能動電極を用いるアクティブマトリクス方式、プラズマアドレス方式等のいずれの駆動方式であっても良い。
半透過反射型の垂直配向型液晶セルに使用する半透過反射性電極に含まれる反射機能を有する領域(以下、反射層ということがある。)としては、特に制限されず、アルミニウム、銀、金、クロム、白金等の金属やそれらを含む合金、酸化マグネシウム等の酸化物、誘電体の多層膜、選択反射を示す液晶又はこれらの組み合わせ等を例示することができる。これら反射層は平面であっても良く、また曲面であっても良い。さらに反射層は、凹凸形状など表面形状に加工を施して拡散反射性を持たせたもの、液晶セルの観察者側と反対側の該電極基板上の電極を兼備させたもの、またそれらを組み合わせたものであっても良い。
まず、第1、第3、第4の光学異方性層について説明する。
前記光学異方性層としては、例えば、ポリカーボネート、ノルボルネン系樹脂等の環状ポリオレフィン、ポリビニルアルコール、ポリスチレン、ポリメチルメタクリレート、ポリプロピレンやその他のポリオレフィン、ポリアリレート、ポリアミドの如き適宜なポリマーからなるフィルムを一軸あるいは二軸延伸処理する手法や特開平5-157911号公報に示されるような熱収縮フィルムにより長尺フィルムの幅方向を熱収縮させて厚み方向に位相差を大きくする手法により製造した複屈折フィルム、液晶ポリマーなどの液晶材料からなる配向フィルム、液晶材料の配向層をフィルムにて支持したものなどが挙げられる。
[1]50≦Re1≦500
[2]30≦Rth1≦750
[3]0.6≦Rth1/Re1≦1.5
第1の光学異方性層の厚さ方向のリターデーション値(Rth1)は、30nm~750nm、好ましくは40nm~500nm、さらに好ましくは50nm~200nmの範囲である。上記範囲を外れた場合には、十分な視野角改良効果が得られないかあるいは、斜めから見たときに不必要な色付きが生じる恐れがある。
また、第1の光学異方性層の厚さ方向のリターデーション値(Rth1)と面内のリターデーション値(Re1)の比は、通常0.6~1.5、好ましくは0.6~1.4、さらに好ましくは0.6~1.3の範囲である。Rth/Re値が上記範囲を外れた場合には、十分な視野角改良効果が得られないかあるいは、斜めから見たときに不必要な色付きが生じる恐れがある。
[6]100≦Re3≦180
[7]50≦Rth3≦600
[8]0.5≦Rth3/Re3≦3.5
[9]100≦Re4≦180
[10]50≦Rth4≦600
[11]0.5≦Rth4/Re4≦3.5
第3及び第4の光学異方性層の厚さ方向のリターデーション値(Rth3、Rth4)は、第3及び第4の光学異方性層が、正面から見た場合は1/4波長板であり、同時に垂直配向型液晶セルの厚さ方向の位相差を補償することによる視野角補償の効果を発揮するよう条件設定する必要がある。従って、垂直配向型液晶セルの厚さ方向の位相差値にもよるが、50nm~600nm、好ましくは100nm~400nm、さらに好ましくは140nm~300nmの範囲である。上記範囲を外れた場合には、十分な視野角改良効果が得られないかあるいは、斜めから見たときに不必要な色付きが生じる恐れがある。
また、第3及び第4の光学異方性層の厚さ方向のリターデーション値(Rth3、Rth4)と面内のリターデーション値(Re3、Re4)の比は、通常0.5~3.5、好ましくは1.0~3.0、さらに好ましくは1.5~2.5の範囲である。Rth/Re値が上記範囲を外れた場合には、十分な視野角改良効果が得られないかあるいは、斜めから見たときに不必要な色付きが生じる恐れがある。
また、第3及び第4の光学異方性層の波長450nm、波長590nmの光における面内のリターデーション値をそれぞれ、Re3(450)、Re3(590)、Re4(450)、Re4(590)とした場合、以下の[12]、[15]式を満たす。
[12]0.7≦Re3(450)/Re3(590)≦1.05
[15]0.7≦Re4(450)/Re4(590)≦1.05
また同様に、前記第2の偏光子の吸収軸と前記第4の光学異方性層の遅相軸とのなす角度をqとしたときに、qは通常40°~50°、好ましくは42~48°、更に好ましくは略45°の範囲である。上記以外の範囲においては、正面コントラストの低下による画質の低下の恐れがある。
本発明の第2の光学異方性層は、正の一軸性を示す液晶材料を液晶状態においてホメオトロピック配向させた後、配向固定化したホメオトロピック配向液晶フィルムからなる。
本発明において、液晶材料のホメオトロピック配向を固定化した液晶フィルムを得るに当たっては、液晶材料と配向基板の選択が極めて重要である。
本発明に用いられる液晶材料は、少なくともポリ(メタ)アクリレートやポリシロキサンなどの側鎖型の液晶性ポリマーを主たる構成成分として含むものである。
また本発明において用いられる側鎖型液晶ポリマーは末端に重合可能なオキセタニル基を有するものである。より具体的には、式(1)で表されるオキセタニル基を有する(メタ)アクリル化合物の(メタ)アクリル部位を単独重合、もしくは他の(メタ)アクリル化合物と共重合させて得られる側鎖型液晶性高分子物質を好ましい例として挙げることができる。
-P1-L3-P2-L4-P3- (2)
-P1-L3-P3- (3)
-P3- (4)
配向基板としては、まず平滑な平面を有するものが好ましく、有機高分子材料からなるフィルムやシート、ガラス板、金属板などを挙げることができる。コストや連続生産性の観点からは有機高分子からなる材料を用いることが好ましい。有機高分子材料の例としては、ポリビニルアルコール、ポリイミド、ポリフェニレンオキシド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロース、トリアセチルセルロース等のセルロース系ポリマー、ポリカーボネート系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー等の透明ポリマーからなるフィルムが挙げられる。またポリスチレン、アクリロニトリル・スチレン共重合体等のスチレン系ポリマー、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体等のオレフィン系ポリマー、環状ないしノルボルネン構造を有するシクロポリオレフィン、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー等の透明ポリマーからなるフィルムも挙げられる。さらにイミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマーや前記ポリマーのブレンド物等の透明ポリマーからなるフィルムなども挙げられる。これらのなかでも、光学フィルムとして用いられるトリアセチルセルロース、ポリカーボネート、ノルボルネンポリオレフィン等のプラスチックフィルムが使用される。有機高分子材料のフィルムとしては、特にゼオノア(商品名,日本ゼオン(株)製)、ゼオネックス(商品名,日本ゼオン(株)製)、アートン(商品名,JSR(株)製)などのノルボルネン構造を有するポリマー物質からなるプラスチックフィルムが光学的にも優れた特性を有するので好ましい。また金属フィルムとしては、例えばアルミニウムなどから形成される当該フィルムが挙げられる。
液晶フィルム製造の方法としてはこれらに限定されるものではないが、前述の液晶材料を前述の配向基板上に展開し、当該液晶材料を配向させた後、光照射および/または加熱処理することにより当該配向状態を固定化することにより製造することができる。
液晶材料を配向基板上に展開して液晶材料層を形成する方法としては、液晶材料を溶融状態で直接配向基板上に塗布する方法や、液晶材料の溶液を配向基板上に塗布後、塗膜を乾燥して溶媒を留去させる方法が挙げられる。
液晶材料の溶液を塗布する方法では、塗布後に溶媒を除去するための乾燥工程を入れることが好ましい。この乾燥工程は、塗膜の均一性が維持される方法であれば、特に限定されることなく公知の方法を採用することができる。例えば、ヒーター(炉)、温風吹きつけなどの方法が挙げられる。
該液晶材料層を熱処理などの方法で液晶配向を形成したのち、液晶配向状態を保ったまま液晶材料を組成物中のオキセタニル基の重合反応により硬化させる。硬化工程は、完成した液晶配向を硬化(架橋)反応により液晶配向状態を固定化し、より強固な膜に変性することを目的にしている。
光カチオン発生剤を用いた場合、光カチオン発生剤の添加後、液晶配向のための熱処理までの工程を暗条件(光カチオン発生剤が解離しない程度の光遮断条件)で行えば、液晶材料は配向段階までは硬化することなく、充分な流動性をもって液晶配向することができる。この後、適当な波長の光を発する光源からの光を照射することによりカチオンを発生させ、液晶材料層を硬化させる。
光照射時の温度は、該液晶材料が液晶配向をとる温度範囲である必要がある。また、硬化の効果を充分にあげるためには、該液晶材料のTg以上の温度で光照射を行うのが好ましい。
なお、配向基板として、光学的に等方でない、あるいは得られる液晶フィルムが最終的に目的とする使用波長領域において不透明である、もしくは配向基板の膜厚が厚すぎて実際の使用に支障を生じるなどの問題がある場合、配向基板上で形成された形態から、位相差機能を有する延伸フィルムに転写した形態も使用しうる。転写方法としては公知の方法を採用することができる。例えば、特開平4-57017号公報や特開平5-333313号公報に記載されているように液晶フィルム層を粘着剤もしくは接着剤を介して、配向基板とは異なる基板を積層した後に、必要により粘着剤もしくは接着剤を使って表面の硬化処理を施し、該積層体から配向基板を剥離することで液晶フィルムのみを転写する方法等を挙げることができる。
転写に使用する粘着剤もしくは接着剤は、光学グレードのものであれば特に制限はなく、アクリル系、エポキシ系、ウレタン系など一般に用いられているものを用いることができる。
[4]0≦Re2≦20
[5]-500≦Rth2≦-30
前記第5の光学異方性層としては、特に限定されないが、非液晶材料としては、耐熱性、耐薬品性、透明性に優れ、剛性にも富むことから、例えば、トリアセチルセルロース、ゼオネックス、ゼオノア(共に日本ゼオン(株)製)、ARTON(JSR(株)製)のような環状ポリオレフィン類、ポリプロピレンやその他のポリオレフィン類、ポリアミド、ポリイミド、ポリエステル、ポリエーテルケトン、ポリアリールエーテルケトン、ポリアミドイミド、ポリエステルイミド等のポリマーが好ましい。これらのポリマーは、いずれか一種類を単独で使用してもよいし、ポリアリールエーテルケトンとポリアミドとの混合物のように、異なる官能基を持つ2種以上の混合物として使用してもよい。このようなポリマーの中でも、高透明性、高配向性であることから、ポリイミドが特に好ましい。また液晶性化合物からなる材料としては、コレステリック液晶ポリマーなどの液晶材料からなるコレステリック配向フィルム、液晶材料のコレステリック配向層をフィルムにて支持したものなどが挙げられる。
[13]0≦Re5≦20
[14]100≦Rth5≦400
なお、偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いてもよく、異なるポリマー材料等からなる保護フィルムを用いてもよい。前記偏光子と保護フィルムとは通常、水系粘着剤等を介して密着している。水系接着剤としては、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリウレタン、水系ポリエステル等を例示できる。
ハードコート処理は偏光子表面の傷付き防止などを目的に施されるものであり、例えばアクリル系、シリコーン系などの適宜な紫外線硬化型樹脂による硬度や滑り特性等に優れる硬化皮膜を保護フィルムの表面に付加する方式などにて形成することができる。反射防止処理は偏光子表面での外光の反射防止を目的に施されるものであり、従来に準じた反射防止膜などの形成により達成することができる。また、スティッキング防止処理は隣接層との密着防止を目的に施される。
なお、前記反射防止層、スティッキング防止層、拡散層やアンチグレア層等は、保護フィルムそのものに設けることができるほか、別途光学層として透明保護層とは別体のものとして設けることもできる。
なお、各光学異方性層を粘着剤層を介して、相互に貼り合わせる際には、フィルム表面を表面処理して粘着剤層との密着性を向上することができる。表面処理の手段は、特に制限されないが、前記の各光学異方性層の透明性を維持できるコロナ放電処理、スパッタ処理、低圧UV照射、プラズマ処理などの表面処理法を好適に採用できる。これら表面処理法のなかでもコロナ放電処理が良好である。
なお、実施例で用いた各分析方法は以下の通りである。
(1)1H-NMRの測定
化合物を重水素化クロロホルムに溶解し、400MHzの1H-NMR(Variant社製INOVA-400)で測定した。
(2)GPCの測定
化合物をテトラヒドロフランに溶解し、東ソー社製8020GPCシステムで、TSK-GEL SuperH1000、SuperH2000、SuperH3000、SuperH4000を直列につなぎ、溶出液としてテトラヒドロフランを用いて測定した。分子量の較正にはポリスチレンスタンダードを用いた。
(3)顕微鏡観察
オリンパス光学社製BH2偏光顕微鏡で液晶の配向状態を観察した。
(4)膜厚測定法
SLOAN製SURFACE TEXTURE ANALYSIS SYSTEM Dektak 3030STを用いた。また、干渉波測定(日本分光(株)製 紫外・可視・近赤外分光光度計V-570)と屈折率のデータから膜厚を求める方法も併用した。
(5)液晶フィルムのパラメータ測定
王子計測機器(株)製自動複屈折計KOBRA21ADHを用いた。
(偏光子の作製)
ポリビニルアルコールフィルムを温水中に浸漬して膨張させたあと、ヨウ素/ヨウ化カリウム水溶液中にて染色し、次いでホウ酸水溶液中で一軸延伸処理して偏光子を得た。これの偏光子は、分光光度計にて単体透過率、平行透過率および直交透過率を調べたところ透過率43.5%、偏光度99.9%であった。
下記式(8)で示される液晶性ポリマーを合成した。分子量はポリスチレン換算で、Mn=8000、Mw=15000であった。なお、式(8)はブロック重合体の構造で表記しているがモノマーの構成比を表すものである。
配向基板は以下のようにして調製した。厚さ38μmのポリエチレンナフタレートフィルム(帝人(株)製)を15cm角に切り出し、アルキル変性ポリビニルアルコール(PVA:(株)クラレ製、MP-203)の5質量%溶液(溶媒は、水とイソプロピルアルコールの質量比1:1の混合溶媒)をスピンコート法により塗布し、50℃のホットプレートで30分乾燥した後、120℃のオーブンで10分間加熱した。次いで、レーヨンのラビング布でラビングした。得られたPVA層の膜厚は1.2μmであった。ラビング時の周速比(ラビング布の移動速度/基板フィルムの移動速度)は4とした。
このようにして得られた配向基板に、前述の液晶材料溶液をスピンコート法により塗布した。次いで60℃のホットプレートで10分乾燥し、150℃のオーブンで2分間熱処理し、液晶材料を配向させた。次いで、60℃に加熱したアルミ板に試料を密着させて置き、その上から、高圧水銀灯ランプにより600mJ/cm2の紫外光(ただし365nmで測定した光量)を照射して、液晶材料を硬化させた。
なお、上記のホメオトロピック配向液晶層が第2の光学異方性層に該当する。
楕円偏光板の構造について図1を用いて説明する。
参考例1で得た偏光子の片面にポリビニルアルコール系接着剤を介して、厚み40μm、正面位相差:6nm、厚み方向の位相差:60nmのトリアセチルセルロース(TAC)フィルム2を接着して透明保護層を形成した。その偏光子の他面にポリビニルアルコール系接着剤を介して、ロール長尺方向に吸収軸を有する偏光子の吸収軸と横一軸延伸により作製したロール幅方向に遅相軸を有する第1の光学異方性層3(日本ゼオン(株)製ゼオノア)をロールトゥロール貼合することにより、偏光子の吸収軸と第1の光学異方性層3の遅相軸が直交になるように接着し、その上に参考例2で作製した第2の光学異方性層4をアクリル系粘着剤を介して貼り合せを行い、さらに第3の光学異方性層5(日本ゼオン(株)製ゼオノア)をアクリル系粘着剤を介して貼り合わせを行い、楕円偏光板を得た。得られた楕円偏光板の厚さは231μmであった。ここで、第1の光学異方性層3のRe1は100nm、Rth1は90nmの位相差を示し、第3の光学異方性層5のRe3は137.5nm、Rth3は210nmの位相差を示す。
本実施例2に用いた垂直配向型液晶表示装置について図2、図3を用いて説明する。
基板7にITO層からなる透過率の高い材料で透明電極8が形成され、基板9に対向電極10が形成され、透明電極8と対向電極10の間に負の誘電率異方性を示す液晶材料からなる液晶層11が挟持されている。
透明電極8及び対向電極10の液晶層11と接する表面にはそれぞれ垂直配向性の配向膜(図示せず)が形成されており、配向膜の塗布後、少なくとも一方の配向膜にラビング等の配向処理を行っている。
液晶層11の液晶分子は垂直配向性の配向膜に対するラビング等の配向処理により、基板面の垂直方向に対して1゜のチルト角を持つ。
液晶層11には負の誘電率異方性を示す液晶材料が用いられているため、透明電極8と対向電極10の間に電圧を印加すると、液晶分子が基板面と平行方向に向かって傾く。
液晶層11の液晶材料として、Ne(異常光に対する屈折率)=1.561、No(正常光に対する屈折率)=1.478、ΔN(Ne-No)=0.083の屈折率異方性を有する液晶材料を用い、セルギャップは4.7μmとした。
図3に矢印で示す、偏光子1および直線偏光板13の吸収軸の方位はそれぞれ面内90度、0度とした。第1の光学異方性層3は、面内に光軸を有し、負の二軸光学異方性を有する光学素子で形成されている。図3に矢印で示す、第1の光学異方性層3の遅相軸の方位は0度とし、面内Re1で100nm、Rth1で90nmの位相差を示す。
第3、第4の光学異方性層5,14は、面内に光軸を有し、負の二軸光学異方性を有する光学素子で形成されている。図3で矢印に示す、第3及び第4の光学異方性層5,14の遅相軸の方位はそれぞれ45度、135度とし、Re3およびRe4が137.5nmの位相差を、Rth3およびRth4は210nmの位相差を示す。
ホメオトロピック配向液晶フィルムからなる第2の光学異方性層4はRe2が0nm、Rth2が-230nmの位相差を示す。
図4は、黒表示0V、白表示5Vの透過率の比(白表示)/(黒表示)をコントラスト比として、全方位からのコントラスト比を示している。コントラストの等高線は内側から順に500、200、100、50とした。また、同心円は中心から10度間隔の角度を示す。したがって最外円は中心から80度を示す(以下の図も同様)。
本実施例3に用いた垂直配向型液晶表示装置について図5、図6を用いて説明する。
実施例2の垂直配向型液晶セル12と第4の光学異方性層14の間に第5の光学異方性層15(JSR(株)製ARTON)を配置し、第3の光学異方性層5と第4の光学異方性層14の位相差をRe3およびRe4を137.5nm、Rth3およびRth4を145nmとした以外は、実施例2と同様にして垂直配向型液晶表示装置を作製した。第5の光学異方性層15のRe5値は0、Rth5値は120nmである。
図7は、黒表示0V、白表示5Vの透過率の比(白表示)/(黒表示)をコントラスト比として、全方位からのコントラスト比を示している。
以下に示す半透過反射型の垂直配向型液晶表示装置を作製した以外は、実施例2と同様にして半透過反射型垂直配向型液晶表示装置を作製した。
半透過反射型垂直配向型液晶表示装置について図8、図9を用いて説明する。
基板7にAl層からなる反射率の高い材料で形成された反射電極16とITO層からなる透過率の高い材料で透明電極8とが設けられ、基板9に対向電極10が設けられ、反射電極16及び透明電極8と対向電極10の間に負の誘電率異方性を示す液晶材料からなる液晶層11が挟持されている。
反射電極16、透明電極8及び対向電極10の液晶層11と接する表面にはそれぞれ垂直配向性の配向膜(図示せず)が形成されており、配向膜の塗布後、少なくとも一方の配向膜にラビング等の配向処理を行っている。
液晶層11の液晶分子は垂直配向性の配向膜に対するラビング等の配向処理により、基板面の垂直方向に対して1゜のチルト角を持つ。
液晶層11には負の誘電率異方性を示す液晶材料が用いられているため、反射電極16、透明電極8と対向電極10の間に電圧を印加すると、液晶分子が基板面と平行方向に向かって傾く。
液晶層11の液晶材料は、実施例2と同様の材料を用い、セルギャップは、反射部分を2.4μm、透過部分を4.7μmとした。
第3及び第4の光学異方性層5,14の遅相軸方位をそれぞれ45度、135度とし、Re3およびRe4が137.5nmであり、Rth3およびRth4が210nmであることは実施例2と同様である。
図10は、黒表示0V、白表示5Vの透過率の比(白表示)/(黒表示)をコントラスト比として、全方位からのコントラスト比を示している。
本比較例1に用いた垂直配向型液晶表示装置について図11、図12を用いて説明する。実施例2で用いた垂直配向型液晶セル12の表示面側(図の上側)に直線偏光板20(厚み約105μm;住友化学(株)製SQW-062)を配置し、上側直線偏光板20と液晶セル12の間に縦一軸延伸により作製した正の一軸性光学異方性層18(日本ゼオン(株)製ゼオノア)、参考例2で作製したホメオトロピック配向液晶フィルムからなる第2の光学異方性層4、第3の光学異方性層5(日本ゼオン(株)製ゼオノア)を配置した。垂直配向型液晶セル12の背面側(図の下側)に直線偏光板13(厚み約105μm;住友化学(株)製SQW-062)を配置し、下側直線偏光板13と液晶セル12の間に第4の光学異方性層14(日本ゼオン(株)製ゼオノア)を配置した。直線偏光板(住友化学(株)製SQW-062)の支持基板に使用されるトリアセチルセルロースのRth=35nmであった。垂直配向型液晶セル12の表示面側に配置された楕円偏光板の厚さは286μmであった。
図12に矢印で示す、偏光子1および直線偏光板13の吸収軸の方位はそれぞれ面内90度、0度とした。正の一軸性光学異方性層18は、面内に光軸を有し、正の一軸性を有する光学素子で形成されている。図12に矢印で示す、正の一軸性光学異方性層18の遅相軸の方位は0度とし、面内Reで120nm、Rthで60nmの位相差を示す。
第3、第4の光学異方性層5,14は、面内に光軸を有し、負の二軸光学異方性を有する光学素子で形成されている。図12で矢印に示す、第3及び第4の光学異方性層5,14の遅相軸の方位はそれぞれ45度、135度とし、Re3およびRe4が137.5nmの位相差を、Rth3およびRth4は210nmの位相差を示す。
ホメオトロピック配向液晶フィルムからなる第2の光学異方性層4はRe2が0nm、Rth2が-230nmの位相差を示す。
図13は、黒表示0V、白表示5Vの透過率の比(白表示)/(黒表示)をコントラスト比として、全方位からのコントラスト比を示している。
全方位の等コントラスト曲線を図4、図7と図13で比較してみると、ほぼ同程度の視野角特性を持つことが分かる。
但し、実施例1で作製した楕円偏光板(厚さ231μm)に対し、図11の垂直配向型液晶セル12の上側に配置された積層体全体の厚さは286μmと厚くなってしまった。これは、縦一軸延伸により作製した正の一軸光学異方性層18では、偏光板の吸収軸と正の一軸光学異方性層18の遅相軸を直交関係になるようにロールトゥロールで貼り合わせることが出来ないため、偏光子と正の一軸光学異方性層の間に偏光子を保護する透明保護層19を設けた分厚くなってしまったためである。
Claims (21)
- 少なくとも第1の偏光子、第1の光学異方性層、第2の光学異方性層および第3の光学異方性層がこの順に積層された楕円偏光板であって、
前記第1の光学異方性層が、以下の[1]~[3]を満たし、
[1]50≦Re1≦500
[2]30≦Rth1≦750
[3]0.6≦Rth1/Re1≦1.5
(ここで、Re1は第1の光学異方性層の面内のリターデーション値を意味し、Rth1は第1の光学異方性層の厚さ方向のリターデーション値を意味する。Re1及びRth1は、それぞれRe1=(nx1-ny1)×d1[nm]、Rth1={(nx1+ny1)/2-nz1}×d1[nm]である。また、d1は第1の光学異方性層の厚さ、nx1,ny1は波長550nmの光に対する第1の光学異方性層面内の主屈折率、nz1は波長550nmの光に対する厚さ方向の主屈折率であり、nx1>ny1>nz1である。)
前記第2の光学異方性層が、以下の[4]、[5]を満たし、
[4]0≦Re2≦20
[5]-500≦Rth2≦-30
(ここで、Re2は第2の光学異方性層の面内のリターデーション値を意味し、Rth2は第2の光学異方性層の厚さ方向のリターデーション値を意味する。Re2及びRth2は、それぞれRe2=(nx2-ny2)×d2[nm]、Rth2={(nx2+ny2)/2-nz2}×d2[nm]である。また、d2は第2の光学異方性層の厚さ、nx2,ny2は波長550nmの光に対する第2の光学異方性層面内の主屈折率、nz2は波長550nmの光に対する厚さ方向の主屈折率であり、nz2>nx2≧ny2である。)
前記第3の光学異方性層が、以下の[6]~[8]を満たすことを特徴とする楕円偏光板。
[6]100≦Re3≦180
[7]50≦Rth3≦600
[8]0.5≦Rth3/Re3≦3.5
(ここで、Re3は第3の光学異方性層の面内のリターデーション値を意味し、Rth3は第3の光学異方性層の厚さ方向のリターデーション値を意味する。Re3及びRth3は、それぞれRe3=(nx3-ny3)×d3[nm]、Rth3={(nx3+ny3)/2-nz3}×d3[nm]である。また、d3は第3の光学異方性層の厚さ、nx3,ny3は波長550nmの光に対する第3の光学異方性層面内の主屈折率、nz3は波長550nmの光に対する厚さ方向の主屈折率であり、nx3>ny3≧nz3である。) - 前記第2の光学異方性層が、正の一軸性を示す液晶性組成物を液晶状態においてホメオトロピック配向させた後、配向固定化したホメオトロピック配向液晶フィルムからなることを特徴とする請求項1に記載の楕円偏光板。
- 前記の正の一軸性を示す液晶性組成物が、オキセタニル基を有する側鎖型液晶性高分子を含むことを特徴とする請求項2に記載の楕円偏光板。
- 前記第1及び第3の光学異方性層が、ポリカーボネートあるいは環状ポリオレフィンを含むことを特徴とする請求項1に記載の楕円偏光板。
- 前記第3の光学異方性層が、更に以下の[12]を満たすことを特徴とする請求項1~4のいずれかに記載の楕円偏光板。
[12]0.7≦Re3(450)/Re3(590)≦1.05
(ここで、Re3(450)、Re3(590)は、波長450nm、590nmの光における第3の光学異方性層の面内のリターデーション値を意味する。) - 前記第1の偏光子の吸収軸と前記第1の光学異方性層の遅相軸とのなす角度をrとしたときに、80°≦r≦100°を満たすように積層されていることを特徴とする請求項1~5のいずれかに記載の楕円偏光板。
- 前記第1の偏光子の吸収軸と前記第3の光学異方性層の遅相軸とのなす角度をpとしたときに、40°≦p≦50°を満たすことを特徴とする請求項1~6のいずれかに記載の楕円偏光板。
- 前記第1の光学異方性層が前記第1の偏光子の保護層を兼ねることを特徴とする請求項1~7のいずれかに記載の楕円偏光板。
- 少なくとも第1の偏光子、第1の光学異方性層、第2の光学異方性層、第3の光学異方性層、電極を備えた1対の基板間に電圧無印加時に基板表面に対して垂直配向する液晶分子を含む垂直配向型液晶セル、第4の光学異方性層、第2の偏光子がこの順に配置された垂直配向型液晶表示装置であって、
前記第1の光学異方性層が、以下の[1]~[3]を満たし、
[1]50≦Re1≦500
[2]30≦Rth1≦750
[3]0.6≦Rth1/Re1≦1.5
(ここで、Re1は第1の光学異方性層の面内のリターデーション値を意味し、Rth1は第1の光学異方性層の厚さ方向のリターデーション値を意味する。Re1及びRth1は、それぞれRe1=(nx1-ny1)×d1[nm]、Rth1={(nx1+ny1)/2-nz1}×d1[nm]である。また、d1は第1の光学異方性層の厚さ、nx1,ny1は波長550nmの光に対する第1の光学異方性層面内の主屈折率、nz1は波長550nmの光に対する厚さ方向の主屈折率であり、nx1>ny1>nz1である。)
前記第2の光学異方性層が、以下の[4]、[5]を満たし、
[4]0≦Re2≦20
[5]-500≦Rth2≦-30
(ここで、Re2は第2の光学異方性層の面内のリターデーション値を意味し、Rth2は第2の光学異方性層の厚さ方向のリターデーション値を意味する。Re2及びRth2は、それぞれRe2=(nx2-ny2)×d2[nm]、Rth2={(nx2+ny2)/2-nz2}×d2[nm]である。また、d2は第2の光学異方性層の厚さ、nx2,ny2は波長550nmの光に対する第2の光学異方性層面内の主屈折率、nz2は波長550nmの光に対する厚さ方向の主屈折率であり、nz2>nx2≧ny2である。)
前記第3の光学異方性層が、以下の[6]~[8]を満たし、
[6]100≦Re3≦180
[7]50≦Rth3≦600
[8]0.5≦Rth3/Re3≦3.5
(ここで、Re3は第3の光学異方性層の面内のリターデーション値を意味し、Rth3は第3の光学異方性層の厚さ方向のリターデーション値を意味する。Re3及びRth3は、それぞれRe3=(nx3-ny3)×d3[nm]、Rth3={(nx3+ny3)/2-nz3}×d3[nm]である。また、d3は第3の光学異方性層の厚さ、nx3,ny3は波長550nmの光に対する第3の光学異方性層面内の主屈折率、nz3は波長550nmの光に対する厚さ方向の主屈折率であり、nx3>ny3≧nz3である。)
前記第4の光学異方性層が、以下の[9]~[11]を満たすことを特徴とする垂直配向型液晶表示装置。
[9]100≦Re4≦180
[10]50≦Rth4≦600
[11]0.5≦Rth4/Re4≦3.5
(ここで、Re4は第4の光学異方性層の面内のリターデーション値を意味し、Rth4は第4の光学異方性層の厚さ方向のリターデーション値を意味する。Re4及びRth4は、それぞれRe4=(nx4-ny4)×d4[nm]、Rth4={(nx4+ny4)/2-nz4}×d4[nm]である。また、d4は第4の光学異方性層の厚さ、nx4,ny4は波長550nmの光に対する第4の光学異方性層面内の主屈折率、nz4は波長550nmの光に対する厚さ方向の主屈折率であり、nx4>ny4≧nz4である。) - 垂直配向型液晶セルと第4の光学異方性層の間に、更に以下の[13]、[14]を満たす第5の光学異方性層を有することを特徴とする請求項9に記載の垂直配向型液晶表示装置。
[13]0≦Re5≦20
[14]100≦Rth5≦400
(ここで、Re5は第5の光学異方性層の面内のリターデーション値を意味し、Rth5は第5の光学異方性層の厚さ方向のリターデーション値を意味する。Re5及びRth5は、それぞれRe5=(nx5-ny5)×d5[nm]、Rth5={(nx5+ny5)/2-nz5}×d5[nm]である。また、d5は第5の光学異方性層の厚さ、nx5,ny5は波長550nmの光に対する第5の光学異方性層面内の主屈折率、nz5は波長550nmの光に対する厚さ方向の主屈折率であり、nx5≧ny5>nz5である。) - 前記第2の光学異方性層が、正の一軸性を示す液晶性組成物を液晶状態においてホメオトロピック配向させた後、配向固定化したホメオトロピック配向液晶フィルムからなることを特徴とする請求項9または10に記載の垂直配向型液晶表示装置。
- 前記の正の一軸性を示す液晶性組成物が、オキセタニル基を有する側鎖型液晶性高分子を含むことを特徴とする請求項11に記載の垂直配向型液晶表示装置。
- 前記第1、第3及び第4の光学異方性層が、ポリカーボネートあるいは環状ポリオレフィンを含むことを特徴とする請求項9~12のいずれかに記載の垂直配向型液晶表示装置。
- 前記第3の光学異方性層が、更に以下の[12]を満たすことを特徴とする請求項9~13のいずれかに記載の垂直配向型液晶表示装置。
[12]0.7≦Re3(450)/Re3(590)≦1.05
(ここで、Re3(450)、Re3(590)は、波長450nm、590nmの光における第3の光学異方性層の面内のリターデーション値を意味する。) - 前記第4の光学異方性層が、更に以下の[15]を満たすことを特徴とする請求項9~14のいずれかに記載の垂直配向型液晶表示装置。
[15]0.7≦Re4(450)/Re4(590)≦1.05
(ここで、Re4(450)、Re4(590)は、波長450nm、590nmの光における第4の光学異方性層の面内のリターデーション値を意味する。) - 前記第5の光学異方性層が、液晶性化合物、トリアセチルセルロース、環状ポリオレフィン、ポリオレフィン、ポリアミド、ポリイミド、ポリエステル、ポリエーテルケトン、ポリアリールエーテルケトン、ポリアミドイミド、ポリエステルイミドから選ばれる少なくとも1種の素材から形成された層であることを特徴とする請求項9~15のいずれかに記載の垂直配向型液晶表示装置。
- 前記第1の偏光子の吸収軸と前記第1の光学異方性層の遅相軸とのなす角度をrとしたときに、80°≦r≦100°を満たすように積層されていることを特徴とする請求項9~16のいずれかに記載の垂直配向型液晶表示装置。
- 前記第3の光学異方性層の遅相軸と前記第4の光学異方性層の遅相軸とのなす角度が80°~100°となるように積層されていることを特徴とする請求項9~17のいずれかに記載の垂直配向型液晶表示装置。
- 前記第1の偏光子の吸収軸と前記第3の光学異方性層の遅相軸とのなす角度をp、前記第2の偏光子の吸収軸と前記第4の光学異方性層の遅相軸とのなす角度をqとしたときに、40°≦p≦50°、40°≦q≦50°を満たすことを特徴とする請求項9~18のいずれかに記載の垂直配向型液晶表示装置。
- 前記第1の光学異方性層が前記第1の偏光子の保護層を兼ねることを特徴とする請求項9~19のいずれかに記載の垂直配向型液晶表示装置。
- 前記垂直配向型液晶セルの一方の基板が反射機能を有する領域と透過機能を有する領域とを有する基板であることを特徴とする請求項9~20のいずれかに記載の垂直配向型液晶表示装置。
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- 2009-04-20 KR KR1020117000337A patent/KR20110033183A/ko not_active Application Discontinuation
- 2009-04-20 EP EP09762211.2A patent/EP2290414A4/en not_active Withdrawn
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WO2018225542A1 (ja) * | 2017-06-09 | 2018-12-13 | 日東電工株式会社 | 位相差層付偏光板および画像表示装置 |
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Also Published As
Publication number | Publication date |
---|---|
US20110063547A1 (en) | 2011-03-17 |
EP2290414A4 (en) | 2014-07-02 |
JP2009300760A (ja) | 2009-12-24 |
EP2290414A1 (en) | 2011-03-02 |
CN102171591B (zh) | 2014-05-28 |
US8134659B2 (en) | 2012-03-13 |
KR20110033183A (ko) | 2011-03-30 |
CN102171591A (zh) | 2011-08-31 |
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