WO2006067916A1 - 楕円偏光板およびそれを用いた画像表示装置 - Google Patents
楕円偏光板およびそれを用いた画像表示装置 Download PDFInfo
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- WO2006067916A1 WO2006067916A1 PCT/JP2005/020348 JP2005020348W WO2006067916A1 WO 2006067916 A1 WO2006067916 A1 WO 2006067916A1 JP 2005020348 W JP2005020348 W JP 2005020348W WO 2006067916 A1 WO2006067916 A1 WO 2006067916A1
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- liquid crystal
- birefringent layer
- polarizing plate
- polarizer
- layer
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133638—Waveplates, i.e. plates with a retardation value of lambda/n
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/13—Positive birefingence
Definitions
- the present invention relates to an elliptically polarizing plate and an image display device using the elliptically polarizing plate. More specifically
- the present invention relates to an extremely thin, wide-band, wide-viewing-angle elliptical polarizing plate and an image display device using the same.
- Various image films such as a liquid crystal display device and an electro-luminescence (EL) display generally use various optical films in combination with a polarizing film and a phase difference plate for optical compensation. Has been.
- a circularly polarizing plate which is a kind of the optical film, can be usually produced by combining a polarizing film and a ⁇ 4 plate.
- the ⁇ ⁇ 4 plate generally exhibits a characteristic that the phase difference value increases as the wavelength becomes shorter, that is, a so-called “positive wavelength dispersion characteristic”, and generally has a large wavelength dispersion characteristic. is there. Therefore, there is a problem that desired optical characteristics (for example, a function as a ⁇ 4 plate) cannot be exhibited over a wide wavelength range.
- a retardation plate exhibiting a wavelength dispersion characteristic that is, a so-called “reverse dispersion characteristic”, in which a retardation value increases as the wavelength becomes longer in recent years
- a norbornene film and a modified film are used as a retardation plate exhibiting a wavelength dispersion characteristic.
- Polycarbonate films have been proposed. However, these films have problems in terms of cost.
- the absorption axis of the polarizing film is usually parallel to the stretching direction, and the slow axis of the retardation film is also parallel to the stretching direction.
- the angle between the absorption axis and the slow axis is 45 °
- one of the films is oriented with respect to the longitudinal direction (stretching direction). It is necessary to cut in the direction of 45 °.
- the angle of the optical axis may vary in each cut out film, resulting in a variation in quality between products.
- the production of large-sized films is difficult due to increased waste due to clipping.
- Patent Document 1 Japanese Patent No. 3174367
- Patent Document 2 JP 2003-195037
- the present invention has been made to solve the above-described conventional problems, and an object thereof is to provide an extremely thin, wide-band, wide-viewing-angle elliptical polarizing plate and an image display device using the same. There is to do.
- the elliptically polarizing plate of the present invention includes a polarizer, a protective layer formed on one side of the polarizer, a first birefringent layer that functions as a ⁇ / 2 plate, and a first layer that functions as a ⁇ 4 plate.
- the angle formed by the absorption axis of the polarizer and the slow axis of the first birefringent layer is ⁇
- the angle ⁇ is 10 when the angle formed by the slow axis of the layer is
- the thickness of the first birefringent layer is 0.5 to 5 / ⁇ ⁇ .
- the thickness of the second birefringent layer is 0.3-3 / ⁇ ⁇ .
- the first birefringent layer is formed using a liquid crystal material
- the second birefringent layer is formed using a liquid crystal composition including a liquid crystal material and a chiral agent.
- the liquid crystal material forming the second birefringent layer is at least one of compounds represented by the following formulas (4) to (19), and the chiral agent is represented by the following formula (24): It is at least one of the compounds represented by (44).
- the liquid crystal material is a compound represented by the following formula (10), and the chiral agent is a compound represented by the following formula (32):
- a method for producing an elliptically polarizing plate comprises a step of subjecting the surface of the transparent protective film (T) to an orientation treatment; a step of forming a first birefringent layer on the surface of the transparent protective film (T) that has undergone the orientation treatment; Laminating a polarizer on the surface of the film (T), and the polarizer and the first birefringent layer are And a step of laminating a second birefringent layer on the surface of the first birefringent layer, disposed on the opposite side through the transparent protective film (T).
- the transparent protective film (T), the first birefringent layer, the polarizer, and the second birefringent layer are long films, and the long sides are laminated and laminated. .
- the step of forming the first birefringent layer includes a step of applying a coating liquid containing a liquid crystal material, and a step of applying the applied liquid crystal material to the liquid crystal material. Treating the liquid crystal material at a temperature exhibiting a liquid crystal phase and aligning it.
- the liquid crystal material includes a polymerizable monomer and Z or a crosslinkable monomer
- the alignment step of the liquid crystal material further includes performing a polymerization process and a Z or crosslink process.
- the polymerization treatment and Z or crosslinking treatment are performed by heating or light irradiation.
- the step of laminating the second birefringent layer includes a step of applying a coating liquid containing a liquid crystal material and a chiral agent to a substrate, and the step of applying the coating.
- the coating liquid contains 0.03 to 0.11 parts by weight of the chiral agent with respect to 100 parts by weight of the liquid crystal material.
- the substrate is a polyethylene terephthalate film obtained by subjecting to stretching and recrystallization.
- the said base material is used for the coating process of the said coating liquid, without performing the orientation process with respect to this base material surface.
- an image display device includes the elliptically polarizing plate described above.
- the first birefringent layer and the second birefringent layer are formed of a liquid crystal material, and compared with the case where they are formed of a polymer stretched film.
- the difference between ny and ny can be greatly increased.
- the thickness capable of obtaining a desired in-plane retardation for allowing the first birefringent layer to function as a ⁇ 2 plate can be remarkably reduced as compared with the conventional one, and the second birefringent layer can be reduced.
- ⁇ ⁇ Desired in-plane position to function as 4 plates The thickness at which the phase difference can be obtained can be significantly reduced as compared with the conventional thickness.
- the elliptically polarizing plate of the present invention is much thinner than the conventional elliptically polarizing plate, and can greatly contribute to the thinning of the image display device.
- the elliptically polarizing plate of the present invention is fixed in alignment by polymerizing or cross-linking the liquid crystal materials of the first birefringent layer and the second birefringent layer. It has outstanding heat resistance. As a result, it has the extraordinary effect that its optical properties do not deteriorate even in high-temperature environments (for example, in-vehicle applications)!
- the direction of the slow axis can be shifted without doing. That is, the direction can be shifted without annihilating the slow axis.
- the direction of the slow axis of the second birefringent layer can be set to a direction other than parallel or orthogonal to the absorption axis of the polarizer.
- FIG. 1 is a schematic cross-sectional view of an elliptically polarizing plate according to a preferred embodiment of the present invention.
- FIG. 2 is an exploded perspective view of an elliptically polarizing plate according to a preferred embodiment of the present invention.
- FIG. 3 is a perspective view showing an outline of one process in an example of the method for producing an elliptically polarizing plate of the present invention.
- FIG. 4 is a perspective view showing an outline of another process in an example of the method for producing an elliptically polarizing plate of the present invention.
- FIG. 5 is a schematic diagram showing an outline of still another process in an example of the method for producing an elliptically polarizing plate of the present invention.
- FIG. 6 is a schematic diagram showing an outline of still another process in an example of the method for producing an elliptically polarizing plate of the present invention.
- FIG. 7 is a schematic diagram showing an outline of still another process in an example of the method for producing an elliptically polarizing plate of the present invention.
- FIG. 8 is a schematic cross-sectional view of a liquid crystal panel used in a liquid crystal display device according to a preferred embodiment of the present invention.
- FIG. 9 is a schematic cross-sectional view illustrating the alignment state of liquid crystal molecules in the VA mode.
- FIG. 1 is a schematic cross-sectional view of an elliptically polarizing plate according to a preferred embodiment of the present invention.
- Figure 2 is an exploded perspective view for explaining an optical axis of each layer constituting the elliptically polarizing plate of FIG.
- the elliptically polarizing plate 10 includes a polarizer 11, a protective layer (transparent protective film) 12, a first birefringent layer 13, and a second birefringent layer 14.
- the elliptically polarizing plate of the present invention may have a second protective layer (transparent protective film) 15 on the side where the protective layer (transparent protective film) 12 of the polarizer is not laminated.
- the first birefringent layer 13 can function as a so-called ⁇ 2 plate.
- the ⁇ 2 plate refers to converting linearly polarized light having a specific vibration direction into linearly polarized light having a vibration direction orthogonal to the vibration direction of the linearly polarized light, or converting right circularly polarized light to left circularly polarized light. Or the function of converting left circularly polarized light into right circularly polarized light.
- the second birefringent layer 14 can function as a so-called ⁇ 4 plate.
- the ⁇ 4 plate means a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).
- FIG. 2 is an exploded perspective view for explaining the optical axis of each layer constituting the elliptically polarizing plate according to a preferred embodiment of the present invention (in FIG. 2, the second protective layer is shown for the sake of clarity). 15 is omitted).
- the first birefringent layer 13 is laminated so that its slow axis ⁇ defines a predetermined angle oc with respect to the absorption axis ⁇ of the polarizer 11, and the second birefringent layer 13 is laminated.
- the birefringent layer 14 is laminated so that its slow axis C defines a predetermined angle
- the relationship between the angle ⁇ and the angle j8 is preferably 2 a + 40 ° ⁇ 8 ⁇ 2 ⁇ + 50 °, more preferably 2 ⁇ + 42 ° ⁇ ⁇ 2 ⁇ + 48 °, and particularly preferably 2 ⁇ + 43 ° ⁇
- 8 ⁇ 2 ⁇ + 47 °, most preferably j8 2 ⁇ + 45 °.
- a polarizing plate having very excellent circular polarization characteristics can be obtained.
- this relationship is comprehensive, it is not necessary to examine the stacking direction by trial and error for each product.
- the angle ⁇ is 10 ° to 20 ° or ⁇ 10 ° to 20 °, preferably 13 ° to 19 ° or 13 ° to 19 °, and more preferably 14 ° to 20 °. 18 ° or —14 ° to —18 °.
- the angle j8 is 65 ° to 85 ° or 5 ° to 25 ° It is preferably 71 ° to 83 ° or 7 ° to 19 °, and more preferably 73 ° to 81 ° or 9 ° to 17 °.
- 8 other than parallel (0 ° ⁇ 0.5 °) or perpendicular (90 ° ⁇ 0.5 °) is realized. It is.
- the total thickness of the elliptically polarizing plate of the present invention is preferably 80 to 200 / zm, rather more preferably is 90 to 130 111 Deari, most preferably 100 to 120 111 Dearu 0 present invention
- the first birefringent layer and the second birefringent layer are formed of a liquid crystal material (described later), so that the thickness for allowing the first birefringent layer to function as a Z2 plate is larger than the conventional thickness.
- the thickness for making the second birefringent layer function as a ⁇ 4 plate can be made much thinner than before.
- the elliptically polarizing plate of the present invention can be made as thin as a quarter of the total thickness as compared with the conventional elliptically polarizing plate, and can greatly contribute to the thinning of the liquid crystal display device. .
- the elliptically polarizing plate of the present invention can be made as thin as a quarter of the total thickness as compared with the conventional elliptically polarizing plate, and can greatly contribute to the thinning of the liquid crystal display device.
- the first birefringent layer 13 can function as a so-called ⁇ Z2 plate.
- the phase dispersion of the second birefringent layer functioning as a ⁇ ⁇ 4 plate (especially in the wavelength range where the phase difference deviates from ⁇ ⁇ 4) is reduced. It can be adjusted appropriately.
- the in-plane retardation (And) of such a first birefringent layer has a wavelength of 590 nm [this is preferably about 210 to 330 nm, more preferably about 230 to 310 nm, Preferably, it is 245 to 295 nm.
- nx is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction)
- ny is the refractive index in the direction perpendicular to the slow axis in the plane.
- d is the thickness of the first birefringent layer.
- the thickness of the first birefringent layer can be set so as to function most appropriately as the ⁇ 2 plate. In other words, the thickness can be set so as to obtain a desired in-plane retardation. Specifically, the thickness is preferably 0.5 to 5 ⁇ m, more preferably 1 to 4 ⁇ m, and most preferably 1.5 to 3 m.
- any appropriate material can be adopted as long as the above characteristics are obtained.
- a liquid crystal material (nematic liquid crystal) in which the liquid crystal phase preferred by the liquid crystal material is a nematic phase is more preferable.
- a liquid crystal material for example, a liquid crystal polymer or a liquid crystal monomer can be used.
- the mechanism of the liquid crystal property of the liquid crystal material may be either lyotropic or thermotropic pick.
- the alignment state of the liquid crystal is preferably homogenous alignment.
- the liquid crystal material is a liquid crystal monomer
- a polymerizable monomer or a crosslinkable monomer is preferable. This is because the alignment state of the liquid crystal material can be fixed by polymerizing or crosslinking a polymerizable monomer or a crosslinkable monomer, as will be described later. After aligning the liquid crystal monomer, for example, if the liquid crystal monomers (polymerizable monomer or crosslinkable monomer) are polymerized or cross-linked, the alignment state can be fixed accordingly.
- a polymer is formed by polymerization and a three-dimensional network structure is formed by crosslinking, but these are non-liquid crystalline.
- the first birefringent layer for example, a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to the liquid crystalline compound does not occur.
- the first birefringent layer is an extremely stable birefringent layer that is not affected by temperature changes.
- liquid crystal monomer any appropriate liquid crystal monomer can be adopted.
- any appropriate liquid crystal monomer can be adopted.
- liquid crystal monomer any appropriate liquid crystal monomer can be adopted.
- 3 ⁇ 42002-533742 (WO00 / 37585), EP358208 (US5211877), EP6613 7 (US4388453), W093 / 22397, EP0261712, DE19504224, DE4408171, GB2280445, and the like can be used.
- Specific examples of such polymerizable mesogenic compounds include, for example, trade name LC242 from BASF, trade name E7 from Merck, and trade name LC-Sillicon-CC3767 from Wacker-Chem.
- liquid crystal monomer for example, a nematic liquid crystal monomer is preferable. Includes a monomer represented by the following formula (1). These liquid crystal monomers can be used alone or in combination of two or more.
- a 1 and A 2 each represent a polymerizable group, and may be the same or different.
- One of A 1 and A 2 may be hydrogen.
- -C represents an alkyl
- M represents a mesogenic group
- X may be the same or different, but is preferably the same.
- a 2 is preferably located in the ortho position with respect to A 1 .
- Sarako, A 1 and A 2 are each independently represented by the following formula:
- ⁇ 1 and ⁇ 2 are the same group.
- Z represents a crosslinkable group
- X is as defined in the above formula (1)
- Sp is a linear or branched chain having 1 to 30 carbon atoms Represents a spacer that also has a substituted or unsubstituted alkyl group
- n represents 0 or 1.
- the carbon chain in Sp may be interrupted by, for example, oxygen in the ether functional group, sulfur in the thioether functional group, a non-adjacent imino group, or a C to C alkylimino group.
- Z is preferably any one of the atomic groups represented by the following formula.
- examples of R include groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.
- M is preferably represented by the following formula (3).
- X is the same as defined in the above formula (1).
- Q represents, for example, a substituted or unsubstituted linear or branched alkylene or aromatic hydrocarbon group. Q can be, for example, a substituted or unsubstituted linear or branched C to C anolylene etc.
- Q is an aromatic hydrocarbon atomic group
- an atomic group represented by the following formula or a substituted analog thereof is preferable.
- Examples of the substituted analog of the aromatic hydrocarbon group represented by the above formula may have 1 to 4 substituents per aromatic ring, and the aromatic ring or You may have 1 or 2 substituents per group.
- the above substituents may be the same or different.
- Examples of the substituent include C to C alkyl, nitro, F, Cl, Br, and I.
- halogen such as, c-c alkoxy and the like.
- liquid crystal monomer examples include monomers represented by the following formulas (4) to (19).
- the temperature range in which the liquid crystal monomer exhibits liquid crystallinity varies depending on the type. Specifically, the temperature range is preferably 40 120 ° C, more preferably 50 100 ° C, and most preferably 60 90 ° C.
- the second birefringent layer 14 can function as a so-called four-plate.
- the wavelength dispersion characteristic of the second birefringent layer functioning as the ⁇ 4 plate is the same as that of the ⁇ 2 plate.
- the in-plane retardation (And) of such a second birefringent layer is preferably 80 to 200 nm, more preferably 100 to 180 nm, and most preferably 120 to 160 nm at a wavelength of 590 nm. .
- the second birefringent layer 14 preferably has a refractive index distribution of nx>ny> nz.
- the thickness of the second birefringent layer can be set so as to function most appropriately as a ⁇ 4 plate.
- the thickness can be set so as to obtain a desired in-plane retardation.
- the thickness is preferably 0.3 to 3 m, more preferably 0.5 to 2.5 ⁇ m, and most preferably 0.8 to 2 / ⁇ ⁇ . .
- the realization of such a very thin second birefringent layer ( ⁇ 4 plate) is one of the features of the present invention.
- the thickness of a ⁇ ⁇ ⁇ ⁇ ⁇ 4 plate by a conventional stretched film is about 60 m, whereas according to the elliptically polarizing plate of the present invention, the ⁇ 4 plate having a thickness of about 1Z20 to: LZ200 (second A birefringent layer) is feasible.
- the second birefringent layer is formed from a liquid crystal composition containing a liquid crystal material and a chiral agent.
- a liquid crystal material By using a liquid crystal material, the difference between ⁇ and ny can be significantly increased compared to conventional polymer stretched films (for example, norbornene-based resin and polycarbonate resin). The thickness for obtaining the phase difference can be significantly reduced.
- the slow axis of the obtained second birefringent layer can be changed in a desired direction. Both the liquid crystal material and the chiral agent can be used alone or in combination of two or more.
- liquid crystal material a material similar to the material used for the first birefringent layer may be used.
- the details of the liquid crystal material are as described in the above section 2-2.
- the torsional force of such a chiral agent is preferably 1 X 10 " 6 nm _ 1- (wt%) _1 or more, More preferably, 1 X 10 nm ⁇ (wt%) ⁇ : LX 10 nm ⁇ (wt%), most preferably l X 10 _4 nm _1 '(wt%) _1 ⁇ : LX 10 _3 nm _ 1 '(wt%) _1 .
- the slow axis of the second birefringent layer can be expressed in a desired direction.
- twisting force means the ability of a chiral agent to twist the liquid crystal material and shift the slow axis of the second birefringent layer.
- the chiral agent is preferably a polymerizable chiral agent.
- Specific examples of the polymerizable chiral agent include chiral ichthy compounds represented by the following general formulas (20) to (23).
- Z and Sp are as defined in the above formula (2), and X 2, X 3 and X 4 are each independently a chemical single bond, O—, — S—, — O— CO—, One CO— O, One O— CO— O, One CO— NR—, One NR— CO, One O— CO— NR One, NR— CO— O, 1 represents NR—CO—NR—, R represents H, C to C
- R represents H, C 1 -C alkyl as described above.
- M is
- P 1 is substituted by hydrogen, 1 to 3 C 1 -C alkyl.
- N is an integer of 1-6.
- Ch represents an n-valent chiral group.
- at least one of X 3 and X 4 is one O—CO—O, one O—CO—NR—, —NR—CO—O or one NR—CO—NR—. It is preferable.
- P 1 is an alkyl group, an acyl group or a cycloalkyl group, for example, the carbon chain is oxygen in the ether functional group, sulfur in the thioether functional group, non-adjacent imino group Or it may be interrupted by a C 1 -C alkylimino group.
- L is C-C alkyl, C-C alkoxy, halogen, COO
- R represents C to C alkyl.
- R represents C to C alkyl.
- the terminal in the atomic group represented by the above formula represents a bond with an adjacent group.
- an atomic group represented by the following formula is particularly preferable.
- chiral compound examples include compounds represented by the following formulas (24) to (44). Note that these chiral compounds have a torsional force of 1 ⁇ 10 ” 6 nm _1 ⁇ (wt%) _ 1 or more.
- chiral compounds described in RE-A4342280 and German Patent Applications 19520660.6 and 19520704.1 can be preferably used.
- the combination of the liquid crystal material and the chiral agent may be arbitrarily selected depending on the purpose. Appropriate combinations can be employed. Particularly preferable combinations include the liquid crystal monomer Z of the above formula (10) Z, the combination of the chiral agent of the above formula (32), the liquid crystal monomer Z of the above formula (10), the combination of the chiral agent of the above formula (38), 11) Liquid crystal monomer agent Z The combination of the chiral agent of the above formula (39), etc. are mentioned.
- the chiral agent is preferably 0.03 to 0.11 parts by weight, more preferably 0.045 to 0.105 parts by weight, and most preferably 0.05 to 0.1 parts by weight with respect to 100 parts by weight of the liquid crystal material. It can be used in a proportion of 0.09 parts by weight.
- the amount of the chiral agent used is less than 0.03 parts by weight, the liquid crystal material may not be sufficiently twisted and the slow axis of the second birefringent layer may not be sufficiently shifted.
- the slow axis may not be formed in the second birefringent layer.
- One of the features of the present invention is that the slow axis can be shifted without forming a negative C plate by adjusting the use amount of the strength agent within such a range.
- the liquid crystal composition further contains at least one of a polymerization initiator and a crosslinking agent (curing agent) as necessary.
- a polymerization initiator and Z or a cross-linking agent (curing agent) it is possible to fix misalignment formed by the liquid crystal material in the liquid crystal state. As a result, a slow axis shifted in a desired direction can be stably formed in the second birefringent layer.
- a polymerization initiator or crosslinking agent any appropriate substance can be adopted as long as the effects of the present invention can be obtained.
- the polymerization initiator include benzoyl peroxide (BPO) and azobisisobutyrate-tolyl (AIBN).
- crosslinking agent examples include an ultraviolet curing agent, a photocuring agent, and a thermosetting agent. More specifically, an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal chelate crosslinking agent, and the like can be given. These may be used alone or in combination of two or more.
- the content of the polymerization initiator or crosslinking agent in the liquid crystal composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, and most preferably 1 to 5% by weight. When the content is less than 0.1% by weight, there is a case where the fixation of the deviation of the liquid crystal material is insufficient.
- the liquid crystal composition may further contain any appropriate additive as required.
- the additive include an antioxidant, a modifier, a surfactant, a dye, a pigment, a discoloration inhibitor, and an ultraviolet absorber. These additives can be used alone or in combination of two or more. More specifically, examples of the anti-aging agent include phenol compounds, amine compounds, organic sulfur compounds, and phosphine compounds. Examples of the modifier include glycols, silicones, and alcohols.
- the surfactant is added, for example, to smooth the surface of the birefringent layer. For example, silicone-based, acrylic-based, and fluorine-based surfactants can be used, and silicone-based surfactants are particularly preferable.
- any appropriate polarizer may be adopted as the polarizer 11 depending on the purpose.
- a hydrophilic polymer film such as a polybulal alcohol film, a partially formalized polybulal alcohol film, or an ethylene / acetic acid copolymer copolymer ken-yi film is used for two colors such as iodine or a dichroic dye.
- examples include polyaxially oriented films such as those obtained by adsorbing volatile substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a uniaxially stretched polarizer obtained by adsorbing a dichroic substance such as iodine on a polybulualcohol-based film is particularly preferred because of its high polarization dichroic ratio.
- the thickness of these polarizers is not particularly limited, but is generally about 1 to 80 / ⁇ ⁇ .
- a polarizer uniaxially stretched by adsorbing iodine to a polybulualcohol-based film is dyed by immersing polyvinyl alcohol in an aqueous solution of iodine and stretched to 3 to 7 times the original length.
- it may contain boric acid, zinc sulfate, zinc chloride or the like, or may be immersed in an aqueous solution of potassium iodide or the like.
- the polybulal alcohol film may be immersed in water and washed before dyeing.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be stretched. It can be stretched and dyed with iodine. It can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
- the protective layer 12 and the second protective layer 15 also have any suitable film force that can be used as a protective film for a polarizing plate.
- a transparent protective film is preferred.
- the material that is the main component of such a film include a cell mouth type resin such as triacetyl cellulose (TAC), polyester, polyvinyl alcohol, polycarbonate, polyamide, and polyimide.
- TAC triacetyl cellulose
- examples thereof include transparent resins such as polyetherolesone, polysnolephone, polystyrene, polybornene, polyolefin, acrylic, and acetate.
- thermosetting type resin such as acrylic type, urethane type, acrylic urethane type, epoxy type, and silicone type or ultraviolet curable type resin.
- glassy polymers such as siloxane polymers are also included.
- a polymer film described in JP-A-2001-343529 (WO01Z37007) can also be used.
- the material for this film include a thermoplastic resin having a substituted or unsubstituted imide group in the side chain, and a thermoplastic resin having a substituted or unsubstituted phenyl group and -tolyl group in the side chain.
- a resin composition having an alternating copolymer of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer can be used.
- the polymer film can be, for example, an extruded product of the resin composition.
- TAC, polyimide resin, polyalcohol resin, and glassy polymer are preferable. TAC is more preferable.
- the protective layer is preferably transparent and has no color.
- the thickness direction retardation value Rth force is preferably 1 to 90 nm, more preferably 1 to 80 nm, and most preferably ⁇ 70 to +70 nm.
- the thickness of the protective layer any appropriate thickness can be adopted as long as the above preferred thickness direction retardation is obtained.
- the thickness of the protective layer is preferably 5 mm or less, more preferably 1 mm or less, and particularly preferably 1 to 500 / zm. And most preferably 5 to 150 ⁇ m.
- the surface of the second protective layer 15 opposite to the polarizer (that is, the outermost part of the elliptically polarizing plate) may be subjected to a hard coat treatment, an antireflection treatment, an anti-sticking treatment, an anti-glare treatment, if necessary. Processing or the like can be performed.
- the method for producing an elliptically polarizing plate in a preferred embodiment of the present invention includes a step of subjecting the surface of the transparent protective film (T) (which finally becomes the protective layer 12) to orientation treatment; and the orientation of the transparent protective film (T). Forming a first birefringent layer on the treated surface; and laminating a polarizer on the surface of the transparent protective film (T), the polarizer and the first birefringent layer comprising: And a step of laminating a second birefringent layer on the surface of the first birefringent layer, disposed on opposite sides of each other through the transparent protective film (T).
- a manufacturing method for example, an elliptically polarizing plate as shown in FIGS.
- the polarizer laminating step may be performed after any birefringent layer forming step or laminating step.
- the orientation treatment may be applied to any appropriate base material that may be applied to the transparent protective film (T).
- T transparent protective film
- the film (specifically, the first birefringent layer) formed on the substrate is in an appropriate order depending on the desired laminated structure of the elliptically polarizing plate. Can be transferred (laminated). Details of each step will be described below.
- a first birefringent layer 13 having a slow axis B that forms an angle ⁇ with respect to the absorption axis of the polarizer 11 can be formed (the process of forming the first birefringent layer will be described later).
- any appropriate alignment treatment may be employed as the alignment treatment for the transparent protective film ( ⁇ ⁇ ). Specific examples include rubbing treatment, oblique vapor deposition method, stretching treatment, photo-alignment treatment, magnetic field orientation treatment, and electric field orientation treatment. A rubbing process is preferred. Note that any appropriate conditions may be adopted as the processing conditions for the various alignment treatments depending on the purpose.
- the orientation direction of the orientation treatment is not uniform when the transparent protective film ( ⁇ ⁇ ⁇ ⁇ ) and the polarizer are laminated.
- the direction forms a predetermined angle with the absorption axis of the photon.
- the orientation direction is substantially the same as the direction of the slow axis B of the first birefringent layer 13 to be formed. Therefore, the predetermined angle is 10 ° to 20 ° or 10 ° to 20 °, preferably 13 ° to 19 ° or 13 ° to 19 °, and more preferably 14 ° to 18 °. ° or -1 4 ° to 1 18 °.
- a treatment is performed in the longitudinal direction of the long transparent protective film (T).
- the long transparent protective film (T) should be processed in the longitudinal direction or in an oblique direction (specifically, a direction defining a predetermined angle as described above) with respect to the vertical direction (width direction).
- the polarizer is produced by stretching a polymer film dyed with a dichroic substance as described above, and has an absorption axis in the stretching direction. When mass-producing a polarizer, a long polymer film is prepared and continuously stretched in the longitudinal direction.
- the longitudinal direction of both is the absorption axis direction of the polarizer.
- the orientation treatment may be any suitable orientation layer that may be directly applied to the surface of the transparent protective film (T).
- a polyimide layer or polyvinyl alcohol layer is formed and applied to the alignment layer.
- B-2 Liquid crystal material coating process for forming the first birefringent layer
- a coating liquid containing the liquid crystal material as described in the above section A-2 is applied to the surface of the transparent protective film (T) subjected to the alignment treatment, and the liquid crystal material is then aligned in the following manner.
- the birefringent layer is formed. Specifically, a coating solution in which a liquid crystal material is dissolved or dispersed in an appropriate solvent is prepared, and this coating solution is applied to the surface of the transparent protective film (T) that has been subjected to the alignment treatment.
- the alignment process of the liquid crystal material will be described in Section B-3 below.
- any suitable solvent that can dissolve or disperse the liquid crystal material may be employed.
- the type of solvent used can be appropriately selected according to the type of liquid crystal material.
- Specific examples of the solvent include halogenated hydrocarbons such as chloroform, formaldehyde, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, methylene chloride, trichloroethylene, tetrachloroethylene, chloroform, benzene, orthodichlorobenzene, phenol, p Phenolics such as chlorophenol, o black mouth phenol, m-cresol, o cresol, p cresol monole, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methoxybenzene, 1,2-dimethoxybenzene, acetone , Ketone solvents such as methyl ethyl ketone (MEK), methinoi
- Ester solvents t— Alcohol-based solvents such as butyl alcohol, glycerin, ethylene glycol, triethylene glycolone, ethylene glycol monomethinoate ethere, diethylene glyconoresin methylol ether, propylene glycol, dipropylene glycol, 2-methanole 2, 4-pentanediol, Amide solvents such as dimethylformamide and dimethylacetamide, acetonitrile solvents, -tolyl solvents such as butyl-tolyl, ether solvents such as jetyl ether, dibutyl ether, tetrahydrofuran and dioxane, or carbon disulfide , Cetyl solvate, butyl cetyl sorb, and ethyl cetyl solvate.
- Alcohol-based solvents such as butyl alcohol, glycerin, ethylene glycol, triethylene glycolone, ethylene glycol monomethinoate ethere, diethylene glyconoresin
- solvents can be used alone or in combination of two or more.
- the content of the liquid crystal material in the coating liquid can be appropriately set according to the type of the liquid crystal material, the thickness of the target layer, and the like. Specifically, the content of the liquid crystal material is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and most preferably 15 to 30% by weight.
- the coating solution may further contain any appropriate additive as required. Specific examples of the additive include a polymerization initiator and a crosslinking agent. These are particularly preferably used when a liquid crystal monomer (polymerizable monomer or crosslinkable monomer) is used as the liquid crystal material. Details of the polymerization initiator and the crosslinking agent are as described in the above section A-3.
- the coating amount of the coating liquid can be appropriately set according to the concentration of the coating liquid, the thickness of the target layer, and the like.
- the coating amount is preferably 0.03-0.17 ml per area (100 cm 2 ) of the transparent protective film (T).
- T transparent protective film
- ⁇ or 0.05 ⁇ 0.15ml Preferably ⁇ or 0.08 ⁇ 0.12ml.
- any appropriate method can be adopted as the coating method.
- Specific examples include a roll coat method, a spin coat method, a wire bar coat method, a dip coat method, an etching method, a curtain coat method, and a spray coat method.
- the liquid crystal material forming the first birefringent layer is aligned according to the alignment direction of the surface of the transparent protective film (T).
- the alignment of the liquid crystal material is performed by processing at a temperature showing a liquid crystal phase according to the type of the liquid crystal material used. By performing such temperature treatment, the liquid crystal material takes a liquid crystal state, and the liquid crystal material is aligned according to the alignment direction of the surface of the transparent protective film (T). As a result, birefringence occurs in the layer formed by coating, and the first birefringent layer is formed.
- the treatment temperature can be appropriately determined according to the type of the liquid crystal material.
- the treatment temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C, and most preferably 60 to 90 ° C.
- the treatment time is preferably 30 seconds or longer, more preferably 1 minute or longer, particularly preferably 2 minutes or longer, and most preferably 4 minutes or longer. If the treatment time is less than 30 seconds, the liquid crystal material may not take a sufficient liquid crystal state.
- the treatment time is preferably 10 minutes or less, more preferably 8 minutes or less, and most preferably 7 minutes or less. If the treatment time exceeds 10 minutes, the additive may sublime.
- the layer formed by the coating is further layered. It is preferable to perform a combined treatment or a crosslinking treatment.
- the polymerization treatment By performing the polymerization treatment, the liquid crystal monomer is polymerized, and the liquid crystal monomer is fixed as a repeating unit of the polymer molecule.
- the crosslinking treatment by performing the crosslinking treatment, the liquid crystal monomer forms a three-dimensional network structure, and the liquid crystal monomer is fixed as a part of the crosslinked structure. As a result, the alignment state of the liquid crystal material is fixed.
- the polymer or three-dimensional network structure formed by polymerizing or crosslinking the liquid crystal monomer is “non-liquid crystalline”. Therefore, in the formed first birefringent layer, for example, a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to liquid crystal molecules does not occur. As a result, it is possible to obtain a first birefringent layer having very excellent stability that is not affected by temperature.
- the specific procedure for the polymerization treatment or the crosslinking treatment can be appropriately selected depending on the kind of the polymerization initiator and the crosslinking agent to be used.
- a photopolymerization initiator or a photocrosslinking agent an ultraviolet polymerization initiator that is irradiated with light or when an ultraviolet crosslinking agent is used, a polymerization initiator by heat that is irradiated with ultraviolet light or When a cross-linking agent is used, heating may be performed.
- the type of liquid crystal material depend on the type of liquid crystal material, the type of transparent protective film (T), the type of alignment treatment, the characteristics desired for the first birefringent layer, etc. Can be set as appropriate. Similarly, the heating temperature, heating time, and the like can be set as appropriate.
- the liquid crystal material is aligned in accordance with the alignment direction of the transparent protective film (T), so that the slow axis B of the formed first birefringent layer is
- the orientation direction of the transparent protective film (T) is substantially the same. Therefore, the direction of the slow axis B of the first birefringent layer is 10 ° to 20 ° or 10 ° to 20 ° with respect to the longitudinal direction of the transparent protective film (T), preferably 13 ° to 19 °. Or 13 ° to 19 °, more preferably 14 ° to 18 ° or 14 ° to 18 °.
- a polarizer is laminated on the surface of the transparent protective film (T).
- the lamination of the polarizer can be performed at any appropriate time in the production method of the present invention.
- the polarizer may be laminated on the transparent protective film (T) in advance, and then the first birefringent layer may be formed and then the second birefringent layer may be laminated. May be.
- any suitable laminating method for example, adhesion
- Adhesion can be performed using any suitable adhesive or adhesive.
- the type of adhesive or pressure-sensitive adhesive can be appropriately selected according to the type of adherend (that is, the transparent protective film (T) and the polarizer).
- the adhesive include polymer adhesives such as acrylic, vinyl alcohol, silicone, polyester, polyurethane, and polyether, isocyanate adhesives, rubber adhesives, and the like.
- Specific examples of the pressure-sensitive adhesive include acrylic-based, butyl alcohol-based, silicone-based, polyester-based, polyurethane-based, polyether-based, isocyanate-based and rubber-based pressure-sensitive adhesives.
- the thickness of the adhesive or pressure-sensitive adhesive is not particularly limited, but is preferably 10 to 200 nm, more preferably 30 to 180 nm, and most preferably 50 to 150 nm.
- the slow axis of the first birefringent layer can be set in the alignment treatment of the transparent protective film (T), so that the film was stretched in the longitudinal direction (ie, in the longitudinal direction).
- T transparent protective film
- polarizer long polarizing film having an absorption axis.
- a long transparent protective film (T) that has been aligned to form a predetermined angle with respect to the longitudinal direction and a long polarizing film (polarizer) are aligned in the longitudinal direction.
- the absorption axis direction of the polarizer is substantially parallel to the longitudinal direction of the long film.
- substantially parallel means that the angle between the longitudinal direction and the absorption axis direction includes 0 °, 10 °, preferably 0 ° ⁇ 5 °, more preferably 0 °. ⁇ 3 °.
- a second birefringent layer is laminated on the surface of the first birefringent layer.
- the detailed procedure of the lamination process of the second birefringent layer is as follows. First, a coating liquid containing a liquid crystal composition (including a liquid crystal material and a chiral agent) that forms the second birefringent layer is applied to a base material, and the liquid crystal material in the liquid crystal composition is used as the base material. Orient above. The alignment of the liquid crystal material is performed by processing at a temperature showing a liquid crystal phase according to the type of the liquid crystal material used.
- the liquid crystal material takes a liquid crystal state, and the liquid crystal material is aligned according to the alignment direction of the substrate surface.
- birefringence occurs in the layer formed by coating, and a second birefringent layer is formed.
- the obtained second birefringent layer has a slow axis shifted in a desired direction.
- the coating amount is also about half.
- the coating amount is preferably 0.02-0.08 ml per area (100 cm 2 ) of the base material, more preferably 0.03 to 0.07 ml, and most preferably 0. It is 0.04 ⁇ 0.06ml.
- the substrate is a polyethylene terephthalate (PET) film obtained by performing a stretching treatment and a recrystallization treatment. More specifically, the substrate is obtained by forming an extruded PET resin film into an extruded film, stretching, and then recrystallizing.
- PET polyethylene terephthalate
- the stretching method is preferably lateral uniaxial stretching or longitudinal / lateral biaxial stretching. In longitudinal and transverse biaxial stretching, it is preferable to make the stretching ratio in the transverse direction larger than the stretching ratio in the longitudinal direction. By such a method, a substrate having an alignment axis in the width direction can be obtained.
- the base material may be stretched after the polyimide layer or the polyvinyl alcohol layer is formed.
- the stretching temperature is preferably 120 to 160 ° C.
- the draw ratio is preferably 2 to 7 times.
- the stretching direction can be set according to the direction of the slow axis desired for the second birefringent layer.
- the slow axis of the second birefringent layer is preferably shifted in a direction other than parallel or perpendicular to the absorption axis of the polarizer (longitudinal direction of the long film).
- the direction of the slow axis of the second birefringent layer can be controlled by changing the amount of the chiral agent used within a predetermined range.
- Direction direction perpendicular to the longitudinal direction: In the direction orthogonal to the absorption axis of the polarizer.
- the recrystallization temperature is preferably 150 to 250 ° C. By performing recrystallization in such a temperature range, it becomes possible to obtain a substrate in which the direction of PET molecules becomes more uniform and the variation in the orientation axis is extremely small.
- the thickness of the substrate is preferably 20 to: L00 ⁇ m, more preferably 30 to 90 ⁇ m, and most preferably 30 to 80 / ⁇ ⁇ . By having a thickness in this range, the strength to support the very thin second birefringent layer in the laminating process is given, and the operability such as slipperiness and roll running performance is properly maintained. Is done.
- the variation in the orientation axis of the obtained substrate is preferably within ⁇ 1 °, more preferably within ⁇ 0.5 ° with respect to the average direction of the orientation axis.
- an alignment treatment for example, rubbing treatment, oblique vapor deposition method, stretching treatment, photo-alignment treatment, magnetic alignment treatment, electric field alignment
- the second birefringent layer is formed using a base material that can omit the alignment treatment.
- Such base materials are available from Toray Industries, Inc. and Mitsubishi Polyester Corporation.
- the second birefringent layer formed on the substrate is transferred to the surface of the first birefringent layer.
- the transfer method is not particularly limited.
- the transfer is performed by laminating the second birefringent layer supported on the substrate with the first birefringent layer via an adhesive.
- a typical example of the adhesive is a curable adhesive.
- the curable adhesive include an ultraviolet curable photocurable adhesive, a moisture curable adhesive, and a thermosetting adhesive.
- Specific examples of the thermosetting adhesive include thermosetting resin adhesives such as epoxy resin, isocyanate resin, and polyimide resin.
- a specific example of the moisture curable adhesive is an isocyanate-based moisture curable adhesive.
- Moisture curable adhesives are preferred.
- Moisture curing Mold adhesives cure by reacting with moisture in the air, adsorbed water on the surface of the adherend, active hydrogen groups such as hydroxyl groups and carboxyl groups, and so on. It can be cured and has excellent operability. Furthermore, since it is not necessary to heat for curing, the first and second birefringent layers are not heated during bonding (adhesion). As a result, since there is no concern about heat shrinkage, even when the first and second birefringent layers are extremely thin as in the present invention, cracks during lamination can be remarkably prevented.
- the isocyanate isocyanate-based adhesive is a general term for polyisocyanate-based adhesives and polyurethane resin-based adhesives.
- the curable adhesive is, for example, a curable resin adhesive solution (or dispersion) obtained by dissolving or dispersing the above-mentioned various curable resins in a solvent using a commercially available adhesive. It may be prepared as When preparing a solution (or dispersion), the content of the curable resin in the solution is preferably from 10 to 80% by weight, more preferably from 20 to 65% by weight of solid content, Preferably it is 25 to 65% by weight, most preferably 30 to 50% by weight.
- a solvent to be used any appropriate solvent can be adopted depending on the type of curable resin. Specific examples include ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like. These may be used alone or in combination of two or more.
- the coating amount of the adhesive may be appropriately set according to the purpose.
- the coating amount is preferably 0.3 to 3 ml, more preferably 0.5 to 2 ml, most preferably 1 to 2 ml per area (cm 2 ) of the first or second birefringent layer.
- the solvent contained in the adhesive is volatilized by natural drying or heat drying, if necessary.
- the thickness of the adhesive layer thus obtained is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 m, and most preferably 1 ⁇ m to 10 m.
- the indentation hardness (microhardness) of the adhesive layer is preferably 0.1 to 0.5 GPa, more preferably 0.2 to 0.5 GPa, and most preferably 0.3 to 0.4 GPa. is there.
- the indentation hardness can be converted to Vickers hardness because its correlation with Vickers hardness is known.
- the indentation hardness can be calculated from the indentation depth and the indentation load using, for example, a thin film hardness tester manufactured by NEC Corporation (NEC) (for example, trade name MH4000, trade name MHA-400). it can.
- FIGS. 3 to 7 are the rolls for winding the film forming the respective layers and the ridges or laminates, with reference numerals 111, 111 ′, 112, 112 ′ 115.
- a long polymer film as a raw material of a polarizer is prepared, and dyeing, stretching, and the like are performed as described in Section IV-4 above. Stretching is performed continuously in the longitudinal direction of a long polymer film. As a result, as shown in the perspective view of FIG. 3, a long polarizer 11 having an absorption axis in the longitudinal direction (stretching direction: arrow ⁇ direction) is obtained.
- a long transparent protective film 12 (which eventually becomes the first protective layer) is prepared, and one surface thereof is coated with a labinda roll 120. Rubbing is performed. At this time, the rubbing direction is a direction different from the longitudinal direction of the transparent protective film 12, for example, ⁇ 17.5 °.
- the first birefringence is formed on the transparent protective film 12 subjected to the rubbing treatment as described in the paragraphs B-2 and B-3. Layer 13 is formed. In the first birefringent layer 13, since the liquid crystal material is aligned along the rubbing direction, the slow axis direction thereof is substantially the same direction (arrow B direction) as the rubbing direction of the transparent protective film 12.
- the laminated body 121 of the refracting layer 13 is sent out in the direction of the arrow, and bonded with an adhesive or the like (not shown) in a state where the longitudinal directions thereof are aligned.
- reference numeral 122 denotes a guide roll for bonding the films together (the same applies to FIGS. 6 and 7).
- a long laminate 125 (with the second birefringent layer 14 supported on the base material 26) was prepared, and this and the laminate 123 (second protective layer (transparent protective film) 15, polarizer 11, protective layer (transparent protective film) 12 and first birefringent layer 13), It is fed out in the direction of the arrow, and pasted together with an adhesive or the like (not shown) with the respective longitudinal directions aligned.
- an adhesive or the like (not shown) with the respective longitudinal directions aligned.
- the substrate 26 is peeled off to obtain the elliptically polarizing plate 10 of the present invention.
- a long polarizer 11 is manufactured.
- a long transparent protective film 12 (which eventually becomes the first protective layer) is prepared, and one surface thereof is coated with a labinda roll 120. Rubbing is performed. At this time, the rubbing direction is a direction different from the longitudinal direction of the transparent protective film 12, for example, ⁇ 17.5 °.
- the second transparent protective film 15 (which becomes the second protective layer), the polarizer 11 and the transparent protective film 12 (which becomes the protective layer) Send out in the direction of the arrow, and paste them together with an adhesive or the like (not shown) with their longitudinal directions aligned.
- the transparent protective film 12 that has been subjected to the rubbing process is sent out with the side opposite to the surface that has been subjected to the rubbing process facing the polarizer 11.
- a laminate 126 of the second protective layer (transparent protective film) 15Z polarizer 11Z protective layer (transparent protective film) 12 is obtained.
- the first birefringent layer 13 is formed as described in items 2 and B-3 (not shown).
- the slow axis direction is substantially the same as the rubbing direction of the protective layer (transparent protective film) 12.
- a laminate 123 of the second protective layer (transparent protective film) 15Z polarizer 11Z protective layer (transparent protective film) 12Z first birefringent layer 13 is obtained.
- a long laminate 125 (with the second birefringent layer 14 supported on the base material 26) was prepared, and this and the laminate 123 (second protective layer (transparent protective film) 15, polarizer 11, protective layer (transparent protective film) 12 and first birefringent layer 13), It is fed out in the direction of the arrow, and pasted together with an adhesive or the like (not shown) with the respective longitudinal directions aligned.
- the base material 26 is peeled off to obtain the elliptically polarizing plate 10 of the present invention.
- the long polarizer 11 is manufactured.
- the second transparent protective film 15 (which becomes the second protective layer), the polarizer 11 and the transparent protective film 12 (which becomes the protective layer) Send out in the direction of the arrow, and paste them together with an adhesive or the like (not shown) with their longitudinal directions aligned.
- a laminate 126 of the second protective layer (transparent protective film) 15Z polarizer 11Z protective layer (transparent protective film) 12 is obtained.
- the surface of one of the transparent protective films 12 (on the side opposite to the polarizer 11) is subjected to a rubbing treatment with a lavender roll (not shown).
- the rubbing direction is a direction different from the longitudinal direction of the transparent protective film 12, for example, + 23 ° to + 24 ° or 23. ⁇ One 24.
- the first birefringent layer 13 is formed as described in items 2 and B-3 (not shown).
- the slow axis direction is substantially the same as the rubbing direction of the protective layer (transparent protective film) 12.
- a laminate 123 of the second protective layer (transparent protective film) 15Z polarizer 11Z protective layer (transparent protective film) 12Z first birefringent layer 13 is obtained.
- a long laminate 125 (with the second birefringent layer 14 supported by the base material 26) was prepared, and this and the laminate 123 (second protective layer (transparent protective film) 15, polarizer 11, protective layer (transparent protective film) 12 and first birefringent layer 13) are sent out in the direction of the arrow, and their longitudinal directions are aligned. Bonded with an adhesive or the like (not shown).
- the direction (angle) of the slow axis of the first birefringent layer 13 is + 23 ° to + 24 ° or ⁇ 23 ° to the longitudinal direction of the film (absorption axis of the polarizer 11). If the angle is set to 24 °, the slow axis of the second birefringent layer 14 It should be substantially perpendicular to the absorption axis of the child 11!
- the base material 26 is peeled off to obtain the elliptically polarizing plate 10 of the present invention.
- the elliptically polarizing plate of the present invention may further include another optical layer.
- another optical layer any appropriate optical layer can be adopted depending on the purpose and the type of the image display device. Specific examples include another birefringent layer (retardation film), a liquid crystal film, a light scattering film, a diffraction film, and the like.
- the elliptically polarizing plate of the present invention may further have an adhesive layer as an outermost layer on at least one side.
- an adhesive layer as an outermost layer in this manner, for example, lamination with other members (for example, liquid crystal cells) is facilitated, and peeling from the other members of the elliptically polarizing plate can be prevented.
- Any appropriate material can be adopted as the material of the adhesive layer.
- Specific examples of the adhesive include those described in the above section B-4.
- a material excellent in hygroscopicity and heat resistance is used. This is because foaming and peeling due to moisture absorption, deterioration of optical characteristics due to thermal expansion differences, and warpage of the liquid crystal cell can be prevented.
- the surface of the pressure-sensitive adhesive layer is covered with any appropriate separator until the elliptically polarizing plate is actually used, and contamination can be prevented.
- the separator can be formed by, for example, a method of providing a release coat with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based, molybdenum sulfide, or the like on any appropriate film as necessary. .
- Each layer in the elliptically polarizing plate of the present invention is treated with an ultraviolet absorber such as a salicylic acid ester compound, a benzophenone compound, a benzotriazole compound, a cyanoacrylate compound, or a nickel complex compound. Even those with UV absorption capability.
- an ultraviolet absorber such as a salicylic acid ester compound, a benzophenone compound, a benzotriazole compound, a cyanoacrylate compound, or a nickel complex compound. Even those with UV absorption capability.
- the elliptically polarizing plate of the present invention can be suitably used for various image display devices (for example, liquid crystal display devices, self-luminous display devices). Specific examples of applicable image display devices include liquid crystal display devices, EL displays, plasma displays (PD), and field emission displays (F ED: Field Emission Display).
- image display devices for example, liquid crystal display devices, EL displays, plasma displays (PD), and field emission displays (F ED: Field Emission Display).
- PD plasma displays
- F ED Field Emission Display
- the elliptically polarizing plate of the present invention is used in, for example, a circular polarization mode liquid crystal display device, and includes a homogeneous alignment type TN liquid crystal display device, a horizontal electrode type (IPS) type liquid crystal display device, and a vertical alignment (VA) type liquid crystal display. Especially useful for devices.
- IPS horizontal electrode type
- VA vertical alignment
- FIG. 8 is a schematic sectional view of a liquid crystal panel according to a preferred embodiment of the present invention.
- the liquid crystal panel 100 includes a liquid crystal cell 20, phase difference plates 30 and 30 ′ disposed on both sides of the liquid crystal cell 20, and polarizing plates 10 and 10 ′ disposed on the outer sides of the respective phase difference plates.
- the retardation plates 30 and 30 ′ any appropriate retardation plate can be adopted depending on the purpose and the alignment mode of the liquid crystal cell.
- the polarizing plate 10 is the elliptically polarizing plate of the present invention described in the above sections A and B. This polarizing plate (elliptical polarizing plate) 10 is arranged so that the birefringent layers 13 and 14 are between the polarizer 11 and the liquid crystal cell 20.
- the polarizing plate 10 ′ is any appropriate polarizing plate (preferably, the elliptically polarizing plate of the present invention described in the above sections A and B).
- the polarizing plates 10 and 10 ′ are typically arranged so that their absorption axes are orthogonal to each other. As shown in FIG.
- the elliptically polarizing plate 10 of the present invention is preferably disposed on the viewing side (upper side).
- the liquid crystal cell 20 has a pair of glass substrates 21 and 21 ′ and a liquid crystal layer 22 as a display medium disposed between the substrates.
- One substrate (active matrix substrate) 21 ′ has a switching element (typically TFT) that controls the electro-optic characteristics of the liquid crystal, and a signal that gives a scanning signal and a source signal to give a gate signal to this active element. Lines (not shown).
- the other glass substrate (color filter substrate) 21 is provided with a color filter (not shown). The color filter may be provided on the active matrix substrate 21 ′. Yes.
- the distance (cell gap) between the substrates 21 and 21 is controlled by a spacer (not shown).
- An alignment film (not shown) made of polyimide, for example, is provided on the side of the substrates 21 and 21 ′ in contact with the liquid crystal layer 22.
- FIG. 9 is a schematic cross-sectional view illustrating the alignment state of liquid crystal molecules in the VA mode.
- the liquid crystal molecules are aligned perpendicular to the substrates 21 and 21 ′.
- Such vertical alignment can be realized by arranging a nematic liquid crystal having negative dielectric anisotropy between substrates on which a vertical alignment film (not shown) is formed.
- the incident light is a long axis of the vertically aligned liquid crystal molecules.
- the light passing through the liquid crystal layer 22 when a predetermined maximum voltage is applied becomes, for example, linearly polarized light whose polarization direction is rotated by 90 °, so that a bright display can be obtained through the polarizing plate 10.
- the display can be returned to the dark state by the orientation regulating force.
- gradation display is possible by changing the intensity of transmitted light from the polarizing plate 10 by changing the applied voltage to control the tilt of the liquid crystal molecules.
- the refractive indices nx , ny and nz of the sample film are measured by an automatic birefringence measuring device (manufactured by Oji Scientific Instruments Co., Ltd., automatic birefringence meter KOBRA31PR), and the in-plane retardation And and thickness direction retardation Rth are obtained. Calculated.
- the measurement temperature was 23 ° C and the measurement wavelength was 590 nm.
- the thickness of the first and second birefringent layers was measured by the interference film thickness measurement method using MCPD2000 manufactured by Otsuka Electronics. Use a dial gauge to measure the thickness of various other films.
- Example 2 The same elliptically polarizing plates obtained in Example 1 were bonded together.
- the transmittance of the bonded sample was measured by the trade name DOT-3 (Murakami Color Co., Ltd.).
- the same elliptical polarizers are overlapped and illuminated with a backlight to display a white image (with the polarizer's absorption axis parallel) and a black image (with the polarizer's absorption axis orthogonal), and the ELDIM product name "EZ Contrastl60D"
- scanning was performed in the direction of 45 ° to 135 ° with respect to the absorption axis of the polarizer on the viewing side and from 60 ° to 60 ° with respect to the normal.
- the contrast ratio “YWZ YB” in the oblique direction was calculated from the Y value (YW) in the white image and the Y value (YB) in the black image.
- the transparent protective film (T) was subjected to an alignment treatment to produce an alignment substrate (which eventually becomes the protective layer 12).
- Substrates (1) to (8) After forming a PVA film (thickness 0.1 m) on the surface of a TAC film (thickness 40 m), using a rubbing cloth, the PVA film at the rubbing angle shown in the table below The surface was rubbed to create an alignment substrate.
- Substrates (9) to (10) A TAC film (thickness 40 ⁇ m) was rubbed at a rubbing angle shown in the following table using a rubbing cloth to prepare an oriented substrate.
- a polymerizable liquid crystal (liquid crystal monomer) exhibiting a nematic liquid crystal phase (manufactured by BASF: trade name Paliocolor LC242) and a photopolymerization initiator for the polymerizable liquid crystal compound (manufactured by Ciba Specialty Chemicals: trade name Irgacure) 907) 3 g was dissolved in 40 g of toluene to prepare a liquid crystal coating solution. Then, the liquid crystal coating liquid was applied onto the alignment substrate prepared as described above by a bar coater, and then the liquid crystal was aligned by heating and drying at 90 ° C. for 2 minutes.
- the liquid crystal layer is irradiated with light of lmj / cm 2 using a metal nitride lamp, and the liquid crystal layer is polymerized to fix the orientation of the liquid crystal layer, thereby fixing the first birefringent layer (1 ) To (3) were formed.
- the thickness and retardation of the first birefringent layer were adjusted by changing the coating amount of the liquid crystal coating liquid.
- the following table shows the thickness and in-plane retardation value (nm) of the formed first birefringent layer.
- polymerizable liquid crystal showing a nematic liquid crystal phase (manufactured by BASF: trade name: Paliocolor LC242: represented by the above formula (10)) 9. 9964 g and a chiral agent (BASF: trade name: Paliocolor LC756: (Represented by the above formula (32)) 0.003 g and 3 g of a photopolymerization initiator for the polymerizable liquid crystal compound (manufactured by Ciba Specialty Chemicals: trade name Irgacure 9 07) were dissolved in 40 g of toluene. A liquid crystal coating solution was prepared.
- the following procedure was carried out in the same manner as II above to form the second birefringent layer (21).
- the following table shows the thickness of the formed second birefringent layer, the in-plane retardation value (nm), and the direction of the slow axis relative to the absorption axis of the polarizer.
- a polymerizable liquid crystal (liquid crystal monomer) exhibiting a nematic liquid crystal phase (BASF: trade name: Paliocolor LC242) 9. 9930 g, a chiral agent (BASF: trade name: Paliocolor LC756) 0.0 070 g, and the polymerizable liquid crystal 3 g of a photopolymerization initiator for the compound (manufactured by Ciba Specialty Chemicals, Inc., trade name: Irgacure 907) was dissolved in 40 g of toluene to prepare a liquid crystal coating solution.
- the following procedure was performed in the same manner as II above to form the second birefringent layer (22).
- the table below shows the thickness of the formed second birefringent layer, the in-plane retardation value (nm), and the direction of the slow axis relative to the absorption axis of the polarizer.
- polymerizable liquid crystal liquid crystal monomer
- a nematic liquid crystal phase manufactured by BASF: trade name Paliocolor LC242
- BASF company trade name Paliocolor LC756
- a photopolymerization initiator for the compound manufactured by Ciba Specialty Chemicals, Inc., trade name: Irgacure 907
- the following procedure was performed in the same manner as II above to form the second birefringent layer (23).
- the table below shows the thickness of the formed second birefringent layer, the in-plane retardation value (nm), and the direction of the slow axis relative to the absorption axis of the polarizer.
- a polarizer was obtained by uniaxially stretching 6 times between rolls having different speed ratios in an aqueous solution containing boric acid.
- a protective layer, a first birefringent layer, and a second birefringent layer were used in combinations as shown in the following table.
- These polarizers, protective layer, first birefringent layer, and second birefringent layer are laminated by the manufacturing procedure shown in FIGS. 3 to 7 to obtain elliptically polarizing plates A01 to A18 as shown in FIG. It was.
- the contrast ratio was measured by superimposing the elliptical polarizing plates A09. According to this elliptically polarizing plate, the angle of contrast 10 was 40 degrees minimum, 50 degrees maximum in all directions, and the maximum minimum difference was 10 degrees. It was a practically desirable level that the angle of contrast 10 was a minimum of 40 degrees in all directions. In addition, the difference between the maximum and minimum is as small as 10 degrees. This is also a very favorable level for practical use.
- the contrast ratio was measured by superposing the elliptically polarizing plates A01. According to this elliptically polarizing plate, the angle of contrast 10 was 40 degrees minimum and 60 degrees maximum in all directions, and the difference between the maximum and minimum was 20 degrees. The angle of contrast 10 is a minimum of 40 degrees in all directions.
- the elliptically polarizing plate of the present invention can be suitably used for various image display devices (for example, liquid crystal display devices, self-luminous display devices).
Abstract
Description
Claims
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US10/582,774 US20080291389A1 (en) | 2004-12-22 | 2005-11-07 | Elliptically Polarizing Plate and Image Display Apparatus Using the Same |
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JP2004370503 | 2004-12-22 | ||
JP2004-370503 | 2004-12-22 |
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US (1) | US20080291389A1 (ja) |
CN (2) | CN100489575C (ja) |
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WO2006064621A1 (ja) * | 2004-12-14 | 2006-06-22 | Nitto Denko Corporation | 楕円偏光板およびその製造方法、ならびに楕円偏光板を用いた画像表示装置 |
CN102062723B (zh) * | 2009-11-16 | 2013-01-16 | 中芯国际集成电路制造(上海)有限公司 | 检测铝连接线过热缺陷的方法 |
KR20150093591A (ko) * | 2014-02-07 | 2015-08-18 | 스미또모 가가꾸 가부시키가이샤 | 장척 편광 필름의 제조 방법 |
KR102571446B1 (ko) * | 2014-09-17 | 2023-08-25 | 니폰 제온 가부시키가이샤 | 원편광판, 광대역 λ/4 판, 및, 유기 일렉트로루미네선스 표시 장치 |
WO2016047517A1 (ja) * | 2014-09-26 | 2016-03-31 | 日本ゼオン株式会社 | 円偏光板及びその製造方法、広帯域λ/4板、有機エレクトロルミネッセンス表示装置、並びに液晶表示装置 |
KR102440078B1 (ko) * | 2015-03-10 | 2022-09-06 | 삼성디스플레이 주식회사 | 편광판 및 이를 포함하는 표시장치 |
JP6766318B2 (ja) * | 2015-04-15 | 2020-10-14 | 大日本印刷株式会社 | 光学フィルム、転写フィルム、画像表示装置、光学フィルムの製造方法及び転写フィルムの製造方法 |
CN107193072B (zh) * | 2016-03-15 | 2018-08-28 | 住友化学株式会社 | 椭圆偏振板 |
TWI596389B (zh) * | 2016-07-13 | 2017-08-21 | 鼎茂光電股份有限公司 | 超薄型廣波域相位延遲膜 |
JPWO2020085309A1 (ja) * | 2018-10-26 | 2021-09-24 | 東洋紡株式会社 | 液晶化合物配向層転写用フィルム |
CN111308603A (zh) * | 2020-04-09 | 2020-06-19 | 四川龙华光电薄膜股份有限公司 | 一种斜向光轴相位差膜 |
JP2021002059A (ja) * | 2020-09-10 | 2021-01-07 | 大日本印刷株式会社 | 光学フィルム、転写フィルム、画像表示装置、光学フィルムの製造方法及び転写フィルムの製造方法 |
JP2020204783A (ja) * | 2020-09-10 | 2020-12-24 | 大日本印刷株式会社 | 光学フィルム、画像表示装置 |
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JP2002189124A (ja) * | 2000-12-20 | 2002-07-05 | Dainippon Printing Co Ltd | 円偏光抽出光学素子及びその製造方法、偏光光源装置、液晶表示装置 |
JP2003195041A (ja) * | 2001-12-25 | 2003-07-09 | Fuji Photo Film Co Ltd | 光学積層体、及びその製造方法、並びに円偏光板 |
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JP2004309772A (ja) * | 2003-04-07 | 2004-11-04 | Nippon Oil Corp | 光学積層体の製造方法、当該積層体からなる楕円偏光板、円偏光板および液晶表示装置 |
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JPH0453929A (ja) * | 1990-06-22 | 1992-02-21 | Fujitsu Ltd | 反射型液晶装置 |
DE60143552D1 (de) * | 2000-12-20 | 2011-01-05 | Dainippon Printing Co Ltd | Optisches extraktionselement für zirkularpolarisiertes licht und verfahren zur herstellung des optischen elements |
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2005
- 2005-11-07 CN CNB2005800060105A patent/CN100489575C/zh not_active Expired - Fee Related
- 2005-11-07 CN CNA2008101742319A patent/CN101419305A/zh active Pending
- 2005-11-07 WO PCT/JP2005/020348 patent/WO2006067916A1/ja active Application Filing
- 2005-11-07 US US10/582,774 patent/US20080291389A1/en not_active Abandoned
- 2005-11-17 TW TW094140404A patent/TWI288836B/zh not_active IP Right Cessation
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JP2002189124A (ja) * | 2000-12-20 | 2002-07-05 | Dainippon Printing Co Ltd | 円偏光抽出光学素子及びその製造方法、偏光光源装置、液晶表示装置 |
JP2003195041A (ja) * | 2001-12-25 | 2003-07-09 | Fuji Photo Film Co Ltd | 光学積層体、及びその製造方法、並びに円偏光板 |
JP2004272202A (ja) * | 2003-02-21 | 2004-09-30 | Fuji Photo Film Co Ltd | 偏光板、円偏光板、楕円偏光板 |
JP2004309772A (ja) * | 2003-04-07 | 2004-11-04 | Nippon Oil Corp | 光学積層体の製造方法、当該積層体からなる楕円偏光板、円偏光板および液晶表示装置 |
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US20080291389A1 (en) | 2008-11-27 |
CN101419305A (zh) | 2009-04-29 |
CN100489575C (zh) | 2009-05-20 |
TW200624887A (en) | 2006-07-16 |
TWI288836B (en) | 2007-10-21 |
CN1922514A (zh) | 2007-02-28 |
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