WO2012157663A1 - 液晶表示装置、偏光板および偏光子保護フィルム - Google Patents
液晶表示装置、偏光板および偏光子保護フィルム Download PDFInfo
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- WO2012157663A1 WO2012157663A1 PCT/JP2012/062477 JP2012062477W WO2012157663A1 WO 2012157663 A1 WO2012157663 A1 WO 2012157663A1 JP 2012062477 W JP2012062477 W JP 2012062477W WO 2012157663 A1 WO2012157663 A1 WO 2012157663A1
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- liquid crystal
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Classifications
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- 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
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133603—Direct backlight with LEDs
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/031—Polarizer or dye
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
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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
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/40—Materials having a particular birefringence, retardation
Definitions
- the present invention relates to a liquid crystal display device, a polarizing plate and a polarizer protective film. Specifically, the present invention relates to a liquid crystal display device having favorable visibility and suitable for thinning, and a polarizing plate and a polarizer protective film suitable for such a liquid crystal display device.
- a polarizing plate used in a liquid crystal display device usually has a configuration in which a polarizer obtained by dyeing iodine in polyvinyl alcohol (PVA) or the like is sandwiched between two polarizer protective films.
- a polarizer protective film a triacetyl cellulose (TAC) film is generally used.
- TAC triacetyl cellulose
- Patent Documents 1 to 3 it has been proposed to use a polyester film having a relatively high durability even in a thin thickness instead of a TAC film.
- Patent Documents 2 and 3 propose providing a polyester film with an easy-adhesion layer in order to improve the adhesion to the polarizer or the hydrophilic adhesive applied to the polarizer.
- the polyester film is excellent in durability compared with the TAC film, but has a birefringence unlike the TAC film, and therefore, when used as a polarizer protective film, the image quality is deteriorated due to optical distortion. was there. That is, since a polyester film having birefringence has a predetermined optical anisotropy (retardation), when it is used as a polarizer protective film, when observed from an oblique direction, a rainbow-like color spot is produced and the image quality is deteriorated. To do. Therefore, Patent Documents 1 to 3 take measures to reduce retardation by using a copolyester as the polyester. However, even in that case, the iridescent color spots could not be completely eliminated.
- the polyester film has a low affinity for water, and when it has crystal orientation by stretching, the affinity for water is further reduced.
- the polarizer and the adhesive applied on the polarizer are mainly composed of a polyvinyl alcohol-based resin and have high hydrophilicity. Due to the difference in properties, the oriented polyester film, the polarizer, and the adhesive have low affinity, and it is difficult to firmly bond the two. Therefore, even the easy-adhesion layers disclosed in Patent Documents 2 and 3 have not yet obtained sufficient adhesion as compared with the triacetylcellulose film.
- An object of the present invention is to solve the above-described problems, and to provide a liquid crystal display device that is thin and has improved visibility, and a polarizing plate and a polarizer protective film suitable for such a liquid crystal display device. .
- the present inventor has intensively studied the generation mechanism of rainbow-like color spots generated when a polyester film is used as a polarizer protective film. As a result, it was discovered that the iridescent color spots were caused by the retardation of the polyester film and the emission spectrum of the backlight light source.
- a fluorescent tube such as a cold cathode tube or a hot cathode tube is generally used as a backlight source of a liquid crystal display device.
- the spectral distribution of a fluorescent lamp such as a cold cathode tube or a hot cathode tube shows an emission spectrum having a plurality of peaks, and these discontinuous emission spectra are combined to obtain a white light source.
- the present inventors have used the above-mentioned problem by using a specific backlight light source and a polyester film having a specific retardation, and further using an easy-adhesion layer having a specific binder composition. It came to the idea that it can be solved, and by confirming this, the present invention was completed.
- a liquid crystal display device having a backlight light source, two polarizing plates, and a liquid crystal cell disposed between the two polarizing plates,
- the backlight light source is a white light emitting diode light source
- the two polarizing plates have a structure in which a polarizer protective film is laminated on both sides of a polarizer, At least one of the polarizer protective films is a polyester film having an easy adhesion layer, The polyester film has a retardation of 3000 to 30000 nm,
- the easy-adhesion layer is a liquid crystal display device comprising a polyester resin (A) and a polyvinyl alcohol resin (B).
- the polarizer protective film on the output light side of the polarizing plate disposed on the output light side with respect to the liquid crystal cell is a polyester film having the easy-adhesion layer.
- Item 2. A liquid crystal display device according to item 1.
- Item 3. Item 3.
- the polyester film has a hard coat layer, an antiglare layer, an antireflection layer, a low reflection layer, a low reflection antiglare layer, and an antireflection antiglare layer on the surface opposite to the side in contact with the polarizer.
- the liquid crystal display device according to any one of Items 1 to 3, comprising one or more selected layers.
- Item 5. Having a structure in which a polarizer protective film is laminated on both sides of the polarizer; At least one of the polarizer protective films is a polyester film having an easy adhesion layer, The polyester film has a retardation of 3000 to 30000 nm,
- the easy adhesion layer includes a polyester resin (A) and a polyvinyl alcohol resin (B).
- the polyester film has a hard coat layer, an antiglare layer, an antireflection layer, a low reflection layer, a low reflection antiglare layer, and an antireflection antiglare layer on a surface opposite to the side in contact with the polarizer. Having one or more layers selected, Item 6.
- a liquid crystal display device using a white light emitting diode as a backlight light source comprising a polyester film having an easy adhesion layer containing a polyester resin (A) and a polyvinyl alcohol resin (B) and having a retardation of 3000 to 30000 nm Polarizer protective film.
- the ratio of the retardation of the polyester film to the retardation in the thickness direction (Re / Rth) is 0.2 or more and 1.2 or less, and the white light-emitting diode according to Item 7 is used as a backlight source for protecting a polarizer for a liquid crystal display device the film.
- the polyester film comprises at least three layers, Contains a UV absorber in a layer other than the outermost layer, The light transmittance at 380 nm is 20% or less, Item 9.
- Item 10 From the group consisting of a hard coat layer, an antiglare layer, an antireflection layer, a low reflection layer, a low reflection antiglare layer, and an antireflection antiglare layer on the surface opposite to the side in contact with the polarizer, the polyester film Item 10.
- a polarizer protective film for a liquid crystal display device using the white light emitting diode according to any one of Items 7 to 9 as a backlight light source which is a polyester film having one or more selected layers.
- the liquid crystal display device, polarizing plate and polarizer protective film of the present invention have excellent adhesion between the polarizer and the protective film, and the spectrum of transmitted light can obtain a spectrum close to that of a light source at any viewing angle. Thus, good visibility without rainbow-like color spots can be secured.
- the liquid crystal panel is composed of a rear module, a liquid crystal cell, and a front module in order from the side facing the backlight light source toward the image display side (emitted light side).
- the rear module and the front module are generally composed of a transparent substrate, a transparent conductive film formed on the liquid crystal cell side surface, and a polarizing plate disposed on the opposite side.
- the polarizing plate is disposed on the side facing the backlight light source in the rear module, and is disposed on the image display side (emitted light side) in the front module.
- the liquid crystal display device of the present invention includes at least a backlight light source, two polarizing plates, and a liquid crystal cell disposed therebetween as constituent members. Moreover, as long as the visibility and the adhesion between the polarizer and the polarizer protective film are not impaired, other constitutions such as a color filter, a lens film, a diffusion sheet, and an antireflection film may be appropriately included. Absent.
- the configuration of the backlight may be an edge light method using a light guide plate, a reflection plate, or the like, or a direct type, but in the present invention, white is used as the backlight light source of the liquid crystal display device. It is necessary to use a light emitting diode (white LED).
- a white LED is a phosphor type, that is, an element that emits white light by combining a light emitting diode that emits blue light or ultraviolet light using a compound semiconductor and a phosphor, or an organic light emitting diode (OLED). That is.
- white light-emitting diodes which are composed of light-emitting elements that combine blue light-emitting diodes using compound semiconductors with yttrium, aluminum, and garnet-based yellow phosphors, have a continuous and broad emission spectrum and are also efficient in light emission. Since it is excellent, it is suitable as the backlight light source of the present invention.
- Organic light emitting diodes are also preferred because they have a continuous and broad emission spectrum.
- the continuous broad emission spectrum is a continuous broad emission spectrum in which the emission spectrum is continuous in the visible light region and the emission spectrum intensity does not become zero in the wavelength region of at least 450 to 650 nm. It is.
- liquid crystal display device of the present invention uses a white LED with low power consumption, it is possible to achieve an energy saving effect.
- fluorescent tubes such as cold cathode tubes and hot cathode tubes, which have been widely used as backlight light sources, have a discontinuous emission spectrum having a peak at a specific wavelength. It is difficult to obtain the desired effect of the invention.
- the polarizing plate has a configuration in which a polarizer in which iodine is dyed on PVA or the like is bonded with two polarizer protective films.
- at least one of the polarizer protective films constituting the polarizing plate is A polyester film having a specific range of retardation.
- the linearly polarized light emitted from the polarizer is disturbed when passing through the polyester film.
- the transmitted light shows an interference color peculiar to retardation which is the product of birefringence and thickness of the polyester film. Therefore, if a discontinuous emission spectrum such as a cold cathode tube or a hot cathode tube is used as the light source, the transmitted light intensity varies depending on the wavelength, resulting in a rainbow-like color spot (see: Proceedings of the 15th Micro Optical Conference Proceedings, No. 1) 30-31).
- white light emitting diodes have a continuous and broad emission spectrum in the visible light region. Therefore, when attention is paid to the envelope shape of the interference color spectrum by the transmitted light transmitted through the birefringent body, it is possible to obtain a spectrum similar to the emission spectrum of the light source by controlling the retardation of the polyester film.
- the emission spectrum of the light source and the envelope shape of the interference color spectrum by the transmitted light that has passed through the birefringent body are similar to each other, so that rainbow-like color spots do not occur and the visibility is remarkable. It is thought to improve.
- the polyester film used for the polarizer protective film is preferably an oriented polyester film having a retardation of 3000 to 30000 nm.
- the retardation is less than 3000 nm, when used as a polarizer protective film, it exhibits a strong interference color when observed from an oblique direction, so the envelope shape is different from the emission spectrum of the light source, and good visibility cannot be ensured.
- a preferable lower limit of retardation is 4500 nm, a more preferable lower limit is 6000 nm, a still more preferable lower limit is 8000 nm, and a still more preferable lower limit is 10000 nm.
- the upper limit of retardation is 30000 nm. Even if a polyester film having a retardation of more than that is used, it is not only possible to substantially improve the visibility, but also because the film thickness becomes considerably thick and the handling property as an industrial material is reduced, it is preferable. Absent.
- the retardation of the polyester film can be obtained by measuring the refractive index and thickness in the biaxial direction, and can also be obtained by using a commercially available automatic birefringence measuring apparatus such as KOBRA-21ADH (Oji Scientific Instruments).
- At least one of the polarizer protective films is a polarizer protective film having the specific retardation.
- the arrangement of the polarizer protective film having the specific retardation in the liquid crystal display device is not particularly limited as long as good visibility is obtained, but the polarizer protective film on the light source side of the polarizing plate arranged closer to the light source than the liquid crystal.
- the polarizer protective film on the outgoing light side of the polarizing plate disposed on the outgoing light side with respect to the liquid crystal is a polarizer protective film made of a polyester film having the specific retardation.
- the polarizer protective film on the outgoing light side of the polarizing plate arranged on the outgoing light side with respect to the liquid crystal is a polyester film having the specific retardation.
- the polyester film is disposed at a position other than the above, the polarization characteristics of the liquid crystal cell may be changed. Since the polymer film of the present invention cannot be used in places where polarization characteristics are required, it is preferably used only in such limited places.
- the polarizing plate of the present invention has a configuration in which a polarizer in which iodine is dyed on polyvinyl alcohol (PVA) or the like is sandwiched between two polarizer protective films, and at least one of the polarizer protective films is the above specific one. It is a polarizing plate protective film which has retardation.
- the other polarizer protective film it is preferable to use a film having no birefringence such as a TAC film, an acrylic film, and a norbornene-based film.
- the polarizing plate used in the present invention can be provided with various functional layers for the purpose of preventing reflection, suppressing glare, and suppressing scratches.
- Such functional layers are not particularly limited, but include a hard coat layer, an antiglare layer (AG), an antireflection layer (AR), a low reflection layer (LR), a low reflection antiglare layer (AG / LR), and reflection.
- An antiglare layer (AG / AR) can be mentioned.
- the functional layer is preferably provided on the surface of the polyester film (the surface on the side opposite to the side in contact with the polarizer of the polyester film). As for these layers, only 1 type may be provided on the polyester film, and may be laminated
- the refractive index of the easy-adhesion layer can be adjusted by a known method, for example, by adding titanium, zirconium, or other metal species to a binder resin such as polyester or polyurethane.
- the polyester used in the present invention may be polyethylene terephthalate or polyethylene naphthalate, but may contain other copolymerization components. These resins are excellent in transparency and excellent in thermal and mechanical properties, and the retardation can be easily controlled by stretching.
- polyethylene terephthalate is preferable because it has a large intrinsic birefringence and relatively large retardation can be obtained even if the film is thin.
- the film of the present invention preferably has a light transmittance of 20% or less at a wavelength of 380 nm.
- the light transmittance at 380 nm is more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less. If the light transmittance is 20% or less, the optical functional dye can be prevented from being deteriorated by ultraviolet rays.
- the transmittance in the present invention is a value measured by a method perpendicular to the plane of the film, and can be measured using a spectrophotometer (for example, Hitachi U-3500 type).
- the ultraviolet absorber used in the present invention is a known substance.
- the ultraviolet absorber include an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
- the organic ultraviolet absorber include benzotoazole, benzophenone, and cyclic imino ester. These may be used singly or in combination of two or more as long as the above-described absorbance range is obtained.
- ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.
- benzotoazole-based and cyclic imino ester-based organic ultraviolet absorbers are particularly preferable.
- benzophenone ultraviolet absorber examples include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2,2 ′ -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2′-hydroxy-3′-tert-butyl-5 ′ Methylphenyl) -5-chlorobenzotriazole, 2- (5-chlor
- Examples of the cyclic iminoester-based ultraviolet absorber include 2,2 ′-( 1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazine-4 -One, 2-phenyl-3,1-benzoxazin-4-one, etc., but are not particularly limited thereto.
- additives other than the catalyst can be contained within a range not impeding the effects of the present invention.
- additives include inorganic particles, heat resistant polymer particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, light proofing agents, flame retardants, thermal stabilizers, antioxidants, and antigelling agents. And surfactants.
- a polyester film does not contain a particle
- “Substantially free of particles” means, for example, in the case of inorganic particles, a content that is 50 ppm or less, preferably 10 ppm or less, particularly preferably the detection limit or less when the inorganic element is quantified by fluorescent X-ray analysis. Means.
- the polyester film has a polyester resin (A) and a polyvinyl alcohol type on at least one side in order to improve the adhesiveness with a polarizer or a polyvinyl alcohol type resin layer such as a water-based adhesive provided on one side or both sides thereof.
- the easy adhesion layer which consists of a resin composition containing resin (B) is laminated
- the easy adhesion layer may be provided on both sides of the polyester film, may be provided only on one side of the polyester film, and a different type of resin coating layer may be provided on the other side.
- Adhesion with the base film is achieved with the polyester-based resin (A), and adhesion with the polarizer or the water-based adhesive is achieved with the polyvinyl alcohol-based resin (B). Can be compatible.
- the polyester resin (A) used in the easy-adhesion layer of the present invention is a copolymer obtained by polycondensation of a dicarboxylic acid component and a diol component, and the materials described below can be used as the dicarboxylic acid component and the diol component. it can. From the viewpoint of improving the adhesion to the polyester film substrate, it is preferable to use a dicarboxylic acid component having the same or similar structure and properties as the dicarboxylic acid component in the polyester film as the dicarboxylic acid component of the polyester resin (A). .
- an aromatic dicarboxylic acid when employed as the dicarboxylic acid component of the polyester film, it is preferable to use the aromatic dicarboxylic acid as the dicarboxylic acid component of the polyester resin (A).
- aromatic dicarboxylic acid component terephthalic acid and isophthalic acid are most preferred.
- Other aromatic dicarboxylic acids may be added and copolymerized within a range of 10 mol% or less with respect to the total dicarboxylic acid component.
- the material of the polyester-based resin (A) is not particularly limited, but a copolymer formed by polycondensation of a dicarboxylic acid component and a diol component or a blend resin thereof can be used.
- the dicarboxylic acid component include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyl Carboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfonecarboxylic acid, anthracenedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydro
- diol component constituting the polyester resin (A) examples include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexadiol, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. Is mentioned. These may be used alone or in combination of two or more.
- glycol component of the polyester resin (A) it is preferable to use a combination of ethylene glycol and branched glycol.
- branched glycol component include 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-butyl-1,3.
- the molar ratio of the branched glycol component is preferably 10 mol%, particularly preferably 20 mol%, based on the total glycol component.
- the upper limit is preferably 80 mol%, more preferably 70 mol%, and particularly preferably 60 mol%. If necessary, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol or the like may be used in combination.
- the polyester resin (A) used in the present invention is preferably a water-soluble or water-dispersible resin from the viewpoint of compatibility with the polyvinyl alcohol resin (B).
- a compound containing a hydrophilic group such as a sulfonate group or a carboxylate group.
- a dicarboxylic acid component having a sulfonate group is preferable from the viewpoint of imparting hydrophilicity while maintaining the acid value of the polyester-based resin (A) low and controlling the reactivity with the crosslinking agent.
- dicarboxylic acid component having a sulfonate group examples include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthaleneisophthalic acid-2,7-dicarboxylic acid and 5- (4-sulfophenoxy) isophthalic acid and alkalis thereof.
- metal salt examples include 5-sulfoisophthalic acid.
- the dicarboxylic acid component having a sulfonate group is preferably 1 to 15 mol%, more preferably 1.5 to 12 mol%, and still more preferably 2 to 10 mol% in the dicarboxylic acid component of the polyester resin (A).
- the dicarboxylic acid component having a sulfonate group is at least the above lower limit, it is suitable for water-solubilization or water-dispersion of the polyester resin. Moreover, when the dicarboxylic acid component which has a sulfonate group is below the said upper limit, it is suitable for adhesiveness with a polyester film base material.
- the polyester resin (A) preferably has fewer carboxylic acid groups that are reactive groups with the crosslinking agent (C).
- the cross-linking polyvinyl alcohol-based resin does not completely mix with the polyvinyl alcohol-based resin. It is considered possible to maintain the domain structure that is formed.
- the acid value of the polyester resin (A) is desirably 20 KOH mg / g or less, preferably 15 KOH mg / g or less, more preferably 10 KOH mg / g or less, still more preferably 8 KOH mg / g or less, and even more. Preferably it is 5 KOHmg / g or less.
- the acid value of the polyester resin (A) can be theoretically determined from the result of component analysis by titration method described later or NMR.
- the introduction amount of the carboxylic acid base for water solubilization or water dispersion is reduced, or hydrophilic groups other than the carboxylic acid base are employed.
- lowering the carboxylic acid terminal concentration of the polyester resin As a method of lowering the carboxylic acid terminal concentration of the polyester resin, a polyester resin in which the carboxylic acid end group is modified may be adopted, or a polyester resin having a large number average molecular weight of the polyester resin may be adopted. preferable.
- the number average molecular weight of the polyester resin (A) is preferably 5000 or more, more preferably 6000 or more, and further preferably 10,000 or more.
- the glass transition temperature of the polyester resin (A) is not particularly limited, but is preferably 20 to 90 ° C, and more preferably 30 to 80 ° C. When the glass transition temperature is not less than the above lower limit, it is suitable for blocking resistance, and when the glass transition temperature is not more than the above upper limit, it is suitable for adhesiveness to a polyester film substrate.
- 40 mass% or more and 90 mass% or less are preferable, as for content of the polyester-type resin (A) in an easily bonding layer, 45 mass% or more and 85 mass% or less are more preferable, and 50 mass% or more and 80 mass% or less are more preferable.
- content of the polyester resin (A) is at least the above lower limit, it is suitable for adhesion to the polyester film substrate, and when it is at most the above upper limit, it is suitable for adhesion to the polarizer / aqueous resin.
- the polyvinyl alcohol resin (B) in the easy-adhesion layer is not particularly limited.
- polyvinyl alcohol obtained by saponifying polyvinyl acetate; a derivative thereof; and a monomer copolymerizable with vinyl acetate; And saponified products of the above-mentioned copolymers; modified polyvinyl alcohol obtained by acetalizing, urethanizing, etherifying, grafting, phosphoric esterifying, etc.
- polyvinyl alcohol examples include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ⁇ -olefins such as ethylene and propylene; (meth) Examples include allyl sulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, and N-vinylpyrrolidone derivatives. . These polyvinyl alcohol resins may be used alone or in combination of two or more.
- Examples of the polyvinyl alcohol resin (B) used in the present invention include vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-vinyl butyral copolymer, and ethylene-vinyl alcohol copolymer. Among these, vinyl alcohol-vinyl acetate A copolymer and an ethylene-vinyl alcohol copolymer are preferred.
- the polymerization degree of the polyvinyl alcohol-based resin (B) is not particularly limited, but the polymerization degree is preferably 3000 or less from the viewpoint of the coating solution viscosity.
- the copolymerization ratio of vinyl alcohol is represented by the degree of saponification.
- the saponification degree of the polyvinyl alcohol resin (B) of the present invention is preferably 60 mol% or more and 85 mol% or less, more preferably 65 mol% or more and 83 mol% or less, further preferably 68 mol% or more and 80 mol% or less, and 70 More preferably, it is more than mol% and less than 80 mol%, still more preferably 71 mol% or more and 78 mol% or less, and particularly preferably 73 mol% or more and 75 mol% or less.
- a crosslinked structure can be more suitably formed with the crosslinking agent (C) when the saponification degree of the polyvinyl alcohol-based resin (B) is not less than the above lower limit. Further, when the degree of saponification of the polyvinyl alcohol-based resin (B) is not more than the above upper limit (or less), compatibility with the polyester-based resin (A) can be more suitably achieved.
- the degree of saponification of the vinyl alcohol-based resin can be determined by the amount of alkali consumption required for hydrolysis of copolymer units such as vinyl acetate or the composition analysis by NMR.
- the content of the polyvinyl alcohol resin (B) is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, and more preferably 20% by mass or more and 50% by mass or less in the easy-adhesion layer. Further preferred.
- the content of the polyvinyl alcohol resin (B) is not less than the above lower limit, it is suitable for adhesiveness with a polarizer and an aqueous resin, and when it is not more than the above upper limit, it is suitable for adhesiveness with a polyester film substrate.
- the crosslinking agent (C) is not particularly limited as long as it has crosslinkability with a hydroxyl group, and examples thereof include melamine-based, isocyanate-based, carbodiimide-based, oxazoline-based, and epoxy-based compounds. Melamine-based, isocyanate-based, carbodiimide-based, and oxazoline-based compounds are preferable from the viewpoint of the temporal stability of the coating solution. Furthermore, the crosslinking agent is preferably a melamine compound or an isocyanate compound that suitably cross-links with the hydroxyl group of the polyvinyl alcohol resin (B).
- a carbodiimide-based cross-linking agent reacts with a carboxyl group
- a melamine-based compound or an isocyanate-based compound reacts with a hydroxyl group
- a polyvinyl alcohol resin (B) having a hydroxyl group as a functional group is more preferably a crosslinked structure.
- an isocyanate type compound from a viewpoint that it forms a crosslinking reaction suitably with the hydroxyl group of polyvinyl alcohol-type resin, and is excellent in transparency.
- you may use a catalyst etc. suitably as needed.
- the polyester resin (A) having an acid value of 20 KOHmg / g or less and the polyvinyl alcohol resin (B) having a saponification degree of 60 to 85 mol% are crosslinked. It is preferable to combine with the agent (C).
- the polyester resin and the polyvinyl alcohol resin more preferably form separate domain units in the easy-adhesion layer, and the phase separation generally referred to as a sea-island structure. It is thought to form a structure.
- the adhesiveness to the polyester film by the domain constituted by the polyester resin and the adhesiveness to the polyvinyl alcohol resin layer by the domain constituted by the polyvinyl alcohol resin are two. It is considered that the two functions are more preferably compatible with each other without being impaired.
- the crosslinking agent (C) is considered to promote and maintain the formation of the domain structure by crosslinking and aggregating the polyvinyl alcohol resin (B).
- isocyanate compound a low molecular or high molecular diisocyanate or a trivalent or higher polyisocyanate can be used.
- Specific isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1, 5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, phenylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane -4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-
- aliphatic diisocyanates such as alicyclic diisocyanates, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, and trimers of these isocyanate compounds.
- an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly Mention may be made of a polymer containing a terminal isocyanate group of a polymer obtained by reacting a polymer active hydrogen compound such as ether polyols and polyamides. These may be used alone or in combination of two or more.
- Block isocyanate compounds are also preferred crosslinking agents (C). By adding the blocked isocyanate compound, it is possible to more suitably improve the temporal stability of the coating solution.
- the blocked isocyanate compound can be prepared by subjecting the isocyanate compound and the blocking agent to an addition reaction by a known method.
- the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methyl etiketooxime, and cyclohexanone oxime.
- Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol ; Lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propyllactam; aromatic amines; imides; acetylacetone, acetoacetate Active methylene compounds such as malonic acid ethyl ester; mercaptans; imines; ureas; diaryl compounds; and sodium bisulfite and the like.
- R is preferably methyl.
- Specific examples of melamine compounds include Sumitomo Chemical's Sumtex resin series M-3, MK, M-6, M-100, MC, etc. and Miwa Chemical Co., Ltd. methylated melamine resin MW-22, MX. -706, MX-042 and the like.
- a crosslinking agent (C) As content of a crosslinking agent (C), 2 to 50 mass% is preferable in an easily bonding layer, 5 to 40 mass% is more preferable, 8 to 30 mass% is further more preferable. .
- the content of the crosslinking agent (C) is not less than the above lower limit, it is suitable for forming a crosslinked polyvinyl alcohol resin, and when it is not more than the above upper limit, it is suitable for expression of an adhesive effect by the binder resin.
- the blending ratio (A) / (B) of the polyester resin (A) and the polyvinyl alcohol resin (B) is preferably 0.8 to 5, more preferably 1 to 4, more preferably 2 Is more preferably 4 and particularly preferably 2.5 to 3.5.
- (A) / (B) is not less than the above lower limit, it is suitable for adhesion to a polyester film substrate, and when it is not more than the above upper limit, it is suitable for adhesion to a polarizer / water-based resin.
- the blending ratio ((A) + (B)) / (C) of the polyester resin (A) and polyvinyl alcohol resin (B) to the crosslinking agent (C) is preferably 2 to 50 in terms of mass ratio. More preferably, it is ⁇ 40, and more preferably 8-30.
- ((A) + (B)) / (C) is not less than the above lower limit, it is suitable for expression of the adhesive effect by the binder resin component, and when it is not more than the above upper limit, it is suitable for the adhesive effect by phase separation. .
- the easy-adhesion layer of the present invention adopts the above composition, and exhibits high adhesiveness equivalent to that of triacetyl cellulose to polarizers and aqueous adhesives, particularly polyvinyl alcohol-based polarizers and aqueous adhesives.
- the remaining area after being peeled once with respect to the aqueous adhesive according to the adhesive test described later is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more, and most preferably 100%.
- the remaining area after 5 continuous peelings and the remaining area after 10 peelings are as follows.
- the remaining area after 5 continuous peelings is preferably 75% or more, more preferably 85% or more, and even more preferably 95% or more, and the remaining area after 10 continuous peelings is preferably 50% or more, more preferably 80%. % Or more, more preferably 90% or more, still more preferably 93% or more, and particularly preferably 95% or more.
- additives such as surfactants, antioxidants, catalysts, heat stabilizers, weathering stabilizers, UV absorbers, organic absorbers, and the like within a range that does not inhibit the effects of the present invention.
- Lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, and the like may be added.
- the particles contained in the easy-adhesion layer in the present invention include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, calcium phosphate, mica, hectorite, zirconia, tungsten oxide, Examples thereof include inorganic particles such as lithium fluoride and calcium fluoride, and organic polymer particles such as styrene, acrylic, melamine, benzoguanamine, and silicone. These may be used alone or in combination of two or more.
- the average particle diameter of the particles in the easy-adhesion layer is preferably 0.04 to 2.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m.
- the average particle size of the inert particles is less than 0.04 ⁇ m, the formation of irregularities on the film surface becomes insufficient, so that the handling properties such as the slipping property and the winding property of the film are lowered, and the pasting is performed. There are cases where the workability of the steel deteriorates. If the average particle diameter of the inert particles exceeds 2.0 ⁇ m, the particles are likely to fall off, which is not preferable.
- the particle concentration in the easy-adhesion layer is preferably 1 to 20% by mass, more preferably 5 to 15% by mass in the solid component.
- the thickness of the easy-adhesion layer can be appropriately set in the range of 0.001 to 2 ⁇ m.
- the range of 0.01 to 1 ⁇ m is preferable, and more preferable.
- Adhesiveness becomes inadequate that the thickness of an easily bonding layer is less than 0.01 micrometer.
- the thickness of the easy-adhesion layer exceeds 2 ⁇ m, blocking may occur.
- a polyester resin is melted, and a non-oriented polyester extruded and formed into a sheet is stretched in the machine direction at a temperature equal to or higher than the glass transition temperature by utilizing a difference in roll speed. Then, a method in which the film is stretched in the transverse direction by a tenter and subjected to heat treatment can be mentioned.
- a publicly known method can be used as a method of providing an easy adhesion layer.
- a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire bar coating method, a pipe doctor method and the like can be mentioned. These methods can be performed alone or in combination.
- An easy-adhesion layer can be provided by apply
- the polyester film of the present invention may be a uniaxially stretched film or a biaxially stretched film, but when the biaxially stretched film is used as a polarizer protective film, the rainbow is not observed even when observed from directly above the film surface. However, it should be noted that a rainbow-like color spot may be observed when observed from an oblique direction.
- This phenomenon is that a biaxially stretched film is composed of refractive index ellipsoids having different refractive indexes in the running direction, width direction, and thickness direction, and the retardation becomes zero depending on the light transmission direction inside the film (refractive index ellipse). This is because there is a direction in which the body appears to be a perfect circle. Therefore, when the liquid crystal display screen is observed from a specific oblique direction, a point where the retardation becomes zero may be generated, and a rainbow-like color spot is generated concentrically around that point.
- the angle ⁇ increases as the birefringence in the film increases, and the rainbow-like color increases. Spots are difficult to see.
- the biaxially stretched film tends to reduce the angle ⁇ , and therefore the uniaxially stretched film is more preferable because rainbow-like color spots are less visible.
- the present invention has biaxiality (biaxiality) in a range that does not substantially cause rainbow-like color spots or a range that does not cause rainbow-like color spots in a viewing angle range required for a liquid crystal display screen. It is preferable.
- This thickness direction retardation means an average of the phase differences obtained by multiplying the two birefringences ⁇ Nxz and ⁇ Nyz by the film thickness d when viewed from the cross section in the thickness direction of the film.
- the smaller the difference between the in-plane retardation and the thickness direction retardation the more isotropic the birefringence action due to the observation angle, and the smaller the change in retardation due to the observation angle. Therefore, it is considered that the occurrence of rainbow-like color spots due to the observation angle is suppressed.
- the ratio of the retardation of the polyester film of the present invention to the retardation in the thickness direction (Re / Rth) is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 0.6 or more.
- the ratio of the retardation to the retardation in the thickness direction (Re / Rth) is larger, the birefringence action is more isotropic, and the occurrence of iridescent color spots due to the observation angle is suppressed.
- the ratio of the retardation to the retardation in the thickness direction (Re / Rth) is 2.0.
- the mechanical strength in the direction orthogonal to the orientation direction is significantly lowered as the film approaches a complete uniaxial (uniaxial symmetry) film.
- the ratio of the retardation of the polyester film of the present invention to the retardation in the thickness direction is preferably 1.2 or less, more preferably 1.0 or less.
- the ratio of the retardation to the thickness direction retardation (Re / Rth) does not have to be 2.0, and 1.2 or less is sufficient. is there. Even if the ratio is 1.0 or less, it is possible to satisfy the viewing angle characteristics (180 degrees left and right, 120 degrees up and down) required for the liquid crystal display device.
- the longitudinal stretching temperature and the transverse stretching temperature are preferably 80 to 130 ° C, particularly preferably 90 to 120 ° C.
- the longitudinal draw ratio is preferably 1.0 to 3.5 times, particularly preferably 1.0 to 3.0 times.
- the transverse draw ratio is preferably 2.5 to 6.0 times, and particularly preferably 3.0 to 5.5 times.
- the stretching temperature low is a preferable measure for increasing the retardation.
- the treatment temperature is preferably from 100 to 250 ° C., particularly preferably from 180 to 245 ° C.
- the thickness unevenness of the film is small. Since the stretching temperature and the stretching ratio greatly affect the thickness variation of the film, it is necessary to optimize the film forming conditions from the viewpoint of the thickness variation. In particular, when the longitudinal stretching ratio is lowered to make a retardation difference, the longitudinal thickness unevenness may be deteriorated. Since there is a region where the vertical thickness unevenness becomes very bad in a specific range of the draw ratio, it is desirable to set the film forming conditions outside this range.
- the thickness unevenness of the film of the present invention is preferably 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, and 3.0% or less. It is particularly preferred.
- the film thickness unevenness can be measured, for example, as follows. A tape-like sample (length 3 m) continuous in the longitudinal stretching direction is collected, and the thickness at 100 points is measured at a pitch of 1 cm. The thickness can be measured using, for example, an electronic micrometer (Millitron 1240) manufactured by Seiko EM Co., Ltd. And the maximum value (dmax), minimum value (dmin), and average value (d) of thickness are calculated
- required from a measured value, and thickness spots (%) can be calculated by a following formula. Thickness unevenness (%) ((dmax ⁇ dmin) / d) ⁇ 100
- the stretching ratio, the stretching temperature, and the thickness of the film can be appropriately set.
- the higher the stretching ratio, the lower the stretching temperature, and the thicker the film the higher the retardation.
- the lower the stretching ratio, the higher the stretching temperature, and the thinner the film the lower the retardation.
- the thickness of the polyester film of the present invention is arbitrary, but it is preferably in the range of 15 to 300 ⁇ m, more preferably in the range of 15 to 200 ⁇ m. In principle, it is possible to obtain a retardation of 3000 nm or more even with a film having a thickness of less than 15 ⁇ m. However, in that case, the anisotropy of the mechanical properties of the film becomes remarkable, and it becomes easy to cause tearing, tearing, etc., and the practicality as an industrial material is remarkably lowered. A particularly preferable lower limit of the thickness is 25 ⁇ m. On the other hand, if the upper limit of the thickness of the polarizer protective film exceeds 300 ⁇ m, the thickness of the polarizing plate becomes too thick.
- the upper limit of the thickness is preferably 200 ⁇ m.
- a particularly preferable upper limit of the thickness is 100 ⁇ m, which is about the same as a general TAC film.
- the polyester used as the film substrate is preferably polyethylene terephthalate.
- a method of blending the ultraviolet absorber with the polyester film in the present invention known methods can be combined.
- a master batch obtained by blending a dried ultraviolet absorber and a polymer raw material in advance using a kneading extruder is used.
- the concentration of the UV absorber in the masterbatch is preferably 5 to 30% by mass in order to uniformly disperse the UV absorber and mix it economically.
- a kneading extruder is used, and the extrusion temperature is preferably from 1 to 15 minutes at a temperature not lower than the melting point of the polyester raw material and not higher than 290 ° C. Above 290 ° C, the weight loss of the UV absorber is large, and the viscosity of the master batch is greatly reduced. When the extrusion temperature is 1 minute or less, uniform mixing of the UV absorber becomes difficult.
- a stabilizer, a color tone adjusting agent, and an antistatic agent may be added.
- the film has a multilayer structure of at least three layers and an ultraviolet absorber is added to the intermediate layer of the film.
- a film having a three-layer structure containing an ultraviolet absorber in the intermediate layer can be specifically produced as follows. Polyester pellets alone for the outer layer, master batches containing UV absorbers for the intermediate layer and polyester pellets are mixed at a predetermined ratio, dried, and then supplied to a known melt laminating extruder, which is slit-shaped. Extruded into a sheet form from a die and cooled and solidified on a casting roll to make an unstretched film.
- a three-layer manifold or a merging block for example, a merging block having a square merging portion
- a film layer constituting both outer layers and a film layer constituting an intermediate layer are laminated
- An unstretched film is formed by extruding a three-layer sheet from the die and cooling with a casting roll.
- the filter particle size (initial filtration efficiency 95%) of the filter medium used for high-precision filtration of the molten resin is preferably 15 ⁇ m or less. When the filter particle size of the filter medium exceeds 15 ⁇ m, removal of foreign matters of 20 ⁇ m or more tends to be insufficient.
- Glass transition temperature In accordance with JIS K7121, a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC6200) was used to raise 10 mg of a resin sample at a rate of 20 ° C / min over a temperature range of 25 to 300 ° C. The extrapolated glass transition start temperature obtained from the curve was defined as the glass transition temperature.
- Acid value 1 g (solid content) of a sample was dissolved in 30 ml of chloroform or dimethylformamide, and titrated with 0.1 N potassium hydroxide ethanol solution using phenolphthalein as an indicator to determine the carboxyl groups per gram of the sample. The amount (mg) of KOH required for neutralization was determined.
- Saponification degree Residual acetic acid groups (mol%) of the polyvinyl alcohol resin were quantified using sodium hydroxide according to JIS-K6726, and the value was defined as the saponification degree (mol%). The sample was measured three times, and the average value was defined as the saponification degree (mol%).
- the biaxial refractive index anisotropy ( ⁇ Nxy) is determined by the following method. Using two polarizing plates, the orientation axis direction of the film was determined, and a 4 cm ⁇ 2 cm rectangle was cut out so that the orientation axis directions were perpendicular to each other, and used as a measurement sample.
- the biaxial refractive index (Nx, Ny) perpendicular to each other and the refractive index (Nz) in the thickness direction were determined by an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd.).
- ) was defined as the refractive index anisotropy ( ⁇ Nxy).
- the thickness d (nm) of the film was measured using an electric micrometer (manufactured by Fine Reef, Millitron 1245D), and the unit was converted to nm.
- Retardation (Re) was determined from the product ( ⁇ Nxy ⁇ d) of refractive index anisotropy ( ⁇ Nxy) and film thickness d (nm).
- ) and ⁇ Nyz (
- the polyester film of the present invention is attached to one side of a polarizer made of PVA and iodine so that the absorption axis of the polarizing film and the main axis of orientation of the film are perpendicular, and the TAC film (Fuji A polarizing plate was prepared by attaching a film (trade name, 80 ⁇ m thickness).
- the obtained polarizing plate is a liquid crystal display device (light source side of the liquid crystal cell) using a white LED composed of a light emitting element combining a blue light emitting diode and a yttrium / aluminum / garnet yellow phosphor as a light source (Nichia Chemical, NSPW500CS).
- the polyester film is placed on the outgoing light side of the polarizing plate having two TAC films as a polarizer protective film).
- the polarizing plate of the liquid crystal display device was visually observed from the front and oblique directions, and the presence or absence of the occurrence of rainbow spots was determined as follows.
- a backlight light source using a cold cathode tube as a light source instead of the white LED was used.
- ⁇ No rainbow spots from any direction. ⁇ : When observed from an oblique direction, a partly extremely thin rainbow can be observed. X: When observing from an oblique direction, rainbow spots can be clearly observed.
- Tear strength The tear strength of each film was measured according to JIS P-8116 using an Elmendorf tear tester manufactured by Toyo Seiki Seisakusho. The tear direction was set to be parallel to the orientation axis direction of the film, and the determination was made as follows. The measurement in the direction of the orientation axis was performed with a molecular orientation meter (MOA-6004 type molecular orientation meter, manufactured by Oji Scientific Instruments). ⁇ : Tear strength is 50 mN or more ⁇ : Tear strength is less than 50 mN
- the PVA adhesion rate was 100, and when all the PVA layer was peeled off, the PVA adhesion rate was 0. Therefore, for example, when peeling is observed in five squares, the PVA adhesion rate is 95. In addition, what was partially peeled within one square was also included in the number of peeled.
- copolyester resin (A-1) was light yellow and transparent.
- the reduced viscosity of the copolyester resin (A-1) was measured and found to be 0.70 dl / g.
- the glass transition temperature by DSC was 40 ° C.
- copolymer polyester resins (A-2) to (A-3) having different compositions were obtained.
- Table 1 shows the composition (mole% ratio) and other characteristics of these copolyester resins measured by 1 H-NMR.
- polyvinyl alcohol resins (B-2) to (B-6) were used in place of the polyvinyl alcohol resin (B-1) to prepare aqueous solutions, which were designated as (Bw-2) to (Bw-6), respectively.
- Table 2 shows the degree of saponification of the polyvinyl alcohol resins (B-1) to (B-6).
- reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise.
- the infrared spectrum of the reaction solution was measured to confirm that the absorption of isocyanate groups had disappeared, and a block polyisocyanate aqueous dispersion (C-1) having a solid content of 75% by mass was obtained.
- PET (Y) 10 parts by weight of a dried UV absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), PET (X) containing no particles (inherent viscosity Was 0.62 dl / g) and 90 parts by mass were mixed, and a polyethylene terephthalate resin (Y) containing an ultraviolet absorber was obtained using a kneading extruder (hereinafter abbreviated as PET (Y)).
- Y polyethylene terephthalate resin
- Example 1 The following coating agent was mixed and the coating liquid from which the mass ratio of polyester-type resin (A) / polyvinyl alcohol-type resin (B) became 70/30 was created.
- the polyester aqueous dispersion uses an aqueous dispersion (Aw-1) in which a polyester resin having an acid value of 2 KOH mg / g is dispersed, and the polyvinyl alcohol aqueous solution is an aqueous solution in which polyvinyl alcohol having a saponification degree of 74 mol% is dissolved. (Bw-4) was used.
- PET (X) resin pellets containing no particles as a raw material for the polarizer protective film intermediate layer and 10 parts by mass of PET (Y) resin pellets containing an ultraviolet absorber were dried at 135 ° C. under reduced pressure (1 Torr) for 6 hours. Thereafter, PET (X) was dried by an ordinary method to the extruder 2 (for the intermediate layer II layer) and supplied to the extruder 1 (for the outer layer I layer and the outer layer III), and dissolved at 285 ° C.
- the above coating solution was applied on both surfaces of the unstretched PET film by a reverse roll method so that the coating amount after drying was 0.12 g / m 2, and then dried at 80 ° C. for 20 seconds.
- the unstretched film on which this coating layer was formed was guided to a tenter stretching machine, guided to a hot air zone at a temperature of 125 ° C. while being gripped by a clip, and stretched 4.0 times in the width direction.
- the film was treated at a temperature of 225 ° C. for 30 seconds and further subjected to a relaxation treatment of 3% in the width direction to obtain a uniaxially oriented PET film having a film thickness of about 50 ⁇ m.
- Example 2 A uniaxially oriented PET film having a thickness of about 100 ⁇ m was obtained by changing the thickness of the unstretched film using the same method as in Example 1 except that the coating solution was applied to one side of the unstretched PET film.
- Example 3 The unstretched film is heated to 105 ° C. using a heated roll group and an infrared heater, and then stretched 1.5 times in the running direction with a roll group having a difference in peripheral speed, and then stretched 4.0 times in the width direction.
- a biaxially oriented PET film having a film thickness of about 50 ⁇ m was obtained in the same manner as in Example 1 except that.
- Example 4 A biaxially oriented PET film having a film thickness of about 50 ⁇ m was obtained in the same manner as in Example 3 except that the film was stretched 2.0 times in the running direction and 4.0 times in the width direction.
- Example 5 A biaxially oriented PET film having a film thickness of about 75 ⁇ m was obtained in the same manner as in Example 3 except that the film was stretched 3.3 times in the running direction and 4.0 times in the width direction.
- Example 6 A uniaxially oriented PET film having a film thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that the PET resin (Y) containing an ultraviolet absorber was not used in the intermediate layer. Although the resulting film was free from iridescent color spots, it has a high light transmittance of 380 nm, and there is a concern of deteriorating the optical functional dye.
- Example 7 A uniaxially oriented PET film having a film thickness of about 100 ⁇ m was obtained in the same manner as in Example 3 except that the film was stretched 4.0 times in the running direction and 1.0 times in the width direction. The obtained film had Re of 3000 nm or more and good visibility, but the mechanical strength was slightly inferior.
- Example 8 A biaxially oriented PET film having a film thickness of about 250 ⁇ m was obtained in the same manner as in Example 3 except that the film was stretched 3.5 times in the running direction and 3.7 times in the width direction.
- the obtained film had Re of 4500 nm or more, but the Re / Rth ratio was less than 0.2. Therefore, an extremely thin rainbow was observed in an oblique direction.
- Example 9 A uniaxially oriented PET film having a film thickness of about 75 ⁇ m was obtained in the same manner as in Example 1 except that the film was stretched 1.0 times in the running direction and 3.5 times in the width direction.
- Example 10 A uniaxially oriented PET film having a thickness of about 275 ⁇ m was obtained in the same manner as in Example 1 except that the thickness of the unstretched film was changed.
- Example 11 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-2) in which a polyester resin having an acid value of 4 KOH mg / g was dispersed.
- Example 12 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-3) in which a polyester resin having an acid value of 6 KOHmg / g was dispersed.
- Example 13 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to a polyvinyl alcohol aqueous solution (Bw-3) having a saponification degree of polyvinyl alcohol of 79 mol%.
- Example 14 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to a polyvinyl alcohol aqueous solution (Bw-2) having a saponification degree of 83 mol%.
- Example 15 A uniaxially oriented PET film was prepared in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 60/40. Obtained.
- Example 16 A uniaxially oriented PET film was prepared in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 80/20. Obtained. 43.95% by weight of water Isopropanol 30.00% by mass Polyester aqueous dispersion (Aw-1) 13.33% by mass Polyvinyl alcohol aqueous solution (Bw-4) 10.00% by mass Block isocyanate-based crosslinking agent (C-1) 0.67% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 17 A uniaxially oriented PET film was prepared in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 50/50. Obtained.
- Example 18 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the composition of the coating solution was changed as follows. 40.87% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 11.67% by mass Polyvinyl alcohol aqueous solution (Bw-4) 15.00% by mass Melamine-based crosslinking agent (C-2) 0.71% by mass (Nicarac MX-042, manufactured by Sanwa Chemical Co., Ltd., solid content 70%) 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 19 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to an aqueous solution (Bw-5) in which polyvinyl alcohol having a saponification degree of 70 mol% was dissolved.
- Example 20 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to an aqueous solution (Bw-6) in which polyvinyl alcohol having a saponification degree of 67 mol% was dissolved.
- Example 21 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the composition of the coating solution was changed as follows. 40.33% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 11.67% by mass Polyvinyl alcohol aqueous solution (Bw-2) 15.00% by mass Oxazoline-based crosslinking agent (C-3) 1.25% by mass (Epocross WS-500, manufactured by Nippon Shokubai, solid concentration 40% by mass) 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 22 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was changed to an aqueous solution (Bw-1) in which polyvinyl alcohol having a saponification degree of 88 mol% was dissolved.
- Example 23 A uniaxially oriented PET film was obtained in the same manner as in Example 1 except that the following coating agent was mixed and the crosslinking agent was not mixed. 41.58% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 11.67% by mass Polyvinyl alcohol aqueous solution (Bw-4) 15.00% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 24 An antiglare layer was provided on the surface opposite to the surface having the coating layer of the uniaxially oriented polyester film of Example 2. As in Example 2, no rainbow spots were observed from any direction, and good results were obtained.
- Example 1 A biaxially oriented PET film having a film thickness of about 38 ⁇ m was obtained in the same manner as in Example 3 except that the film was stretched 3.6 times in the running direction and 4.0 times in the width direction. The obtained film had low retardation, and rainbow-like color spots were observed when observed from an oblique direction.
- Comparative Example 2 Using the same method as in Example 1, the thickness of the unstretched film was changed to obtain a uniaxially oriented PET film having a thickness of about 10 ⁇ m. Since the obtained film was very easy to tear and there was no stiffness, it could not be used as a polarizer protective film. Moreover, the retardation was low and iridescent colored spots were observed.
- Example 3 A uniaxially oriented PET film was prepared in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 100/0. Obtained.
- Polyester water dispersion (Aw-1) 16.66 mass%
- Block isocyanate-based crosslinking agent (C-1) 0.67% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
- Catalyst Organic tin compound, solid content concentration 14% by mass
- Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 4 A uniaxially oriented PET film was prepared in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 0/100. Obtained.
- Block isocyanate-based crosslinking agent (C-1) 0.67% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
- Catalyst Organic tin compound, solid content concentration 14% by mass
- Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 1 was performed except that the light source of the liquid crystal display device was a cold cathode tube.
- liquid crystal display device polarizing plate and polarizer protective film of the present invention, it has excellent adhesion and contributes to thinning and cost reduction of LCD without reducing visibility due to iridescent color spots.
- the industrial applicability is extremely high.
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Abstract
Description
項1.
バックライト光源、2つの偏光板、及び前記2つの偏光板の間に配置された液晶セルを有する液晶表示装置であって、
前記バックライト光源は、白色発光ダイオード光源であり、
前記2つの偏光板は、偏光子の両側に偏光子保護フィルムが積層された構造を有し、
前記偏光子保護フィルムの少なくとも1つは、易接着層を有するポリエステルフィルムであり、
前記ポリエステルフィルムは、3000~30000nmのリタデーションを有し、
前記易接着層は、ポリエステル系樹脂(A)及びポリビニルアルコール系樹脂(B)を含む、液晶表示装置。
項2.
前記液晶セルに対して出射光側に配される偏光板の出射光側の偏光子保護フィルムが、前記易接着層を有するポリエステルフィルムである、
項1に記載の液晶表示装置。
項3.
前記ポリエステルフィルムのリタデーションと厚さ方向リタデーションの比(Re/Rth)が0.2以上1.2以下である項1または2に記載の液晶表示装置。
項4.
前記ポリエステルフィルムが、偏光子と接する側とは反対側の面に、ハードコート層、防眩層、反射防止層、低反射層、低反射防眩層、及び反射防止防眩層から成る群より選択される1種以上の層を有する項1~3のいずれかに記載の液晶表示装置。
項5.
偏光子の両側に偏光子保護フィルムが積層された構造を有し、
前記偏光子保護フィルムの少なくとも一方は、易接着層を有するポリエステルフィルムであり、
前記ポリエステルフィルムは、3000~30000nmのリタデーションを有し、
前記易接着層は、ポリエステル系樹脂(A)及びポリビニルアルコール系樹脂(B)を含む、
白色発光ダイオードをバックライト光源とする液晶表示装置用偏光板。
項6.
前記ポリエステルフィルムが、偏光子と接する側とは反対側の面に、ハードコート層、防眩層、反射防止層、低反射層、低反射防眩層、及び反射防止防眩層から成る群より選択される1種以上の層を有する、
項5に記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光板。
項7.
ポリエステル系樹脂(A)及びポリビニルアルコール系樹脂(B)を含む易接着層を有し、且つ、3000~30000nmのリタデーションを有するポリエステルフィルムからなる、白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
項8.
前記ポリエステルフィルムのリタデーションと厚さ方向リタデーションの比(Re/Rth)が0.2以上1.2以下である、項7に記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
項9.
前記ポリエステルフィルムが少なくとも3層以上からなり、
最外層以外の層に紫外線吸収剤を含有し、
380nmの光線透過率が20%以下である、
項7または8に記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
項10.
前記ポリエステルフィルムが、偏光子と接する側とは反対側の面に、ハードコート層、防眩層、反射防止層、低反射層、低反射防眩層、及び反射防止防眩層から成る群から選択される1種以上の層を有するポリエステルフィルムであることを特徴とする項7~9のいずれかに記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
厚み斑(%)=((dmax-dmin)/d)×100
JIS K7121に準拠し、示差走査熱量計(セイコーインスツルメンツ製、DSC6200)を使用して、樹脂サンプル10mgを25~300℃の温度範囲にわたって20℃/minで昇温させ、DSC曲線から得られた補外ガラス転移開始温度をガラス転移温度とした。
樹脂0.03gをテトラヒドロフラン 10ml に溶かし、GPC-LALLS装置低角度光散乱光度計 LS-8000(東ソー株式会社製、テトラヒドロフラン溶媒、リファレンス:ポリスチレン)を用い、カラム温度30℃、流量1ml/分、カラム(昭和電工社製shodex KF-802、804、806)を用い、数平均分子量を測定した。
樹脂を重クロロホルムに溶解し、ヴァリアン社製核磁気共鳴分析計(NMR)ジェミニ-200を用いて、1H-NMR分析を行ってその積分比より各組成のモル%比を決定した。
1g(固形分)の試料を30mlのクロロホルムまたはジメチルホルムアミドに溶解し、フェノールフタレインを指示薬として0.1Nの水酸化カリウムエタノール溶液で滴定して、試料1g当たりのカルボキシル基を中和するのに必要なKOHの量(mg)を求めた。
JIS-K6726に準じて水酸化ナトリウムを用いて、ポリビニルアルコール樹脂の残存酢酸基(モル%)を定量し、その値をけん化度(モル%)とした。同サンプルについて3度測定し、その平均値をけん化度(モル%)とした。
フィルム上の直交する二軸の屈折率の異方性(△Nxy=|Nx-Ny|)とフィルム厚みd(nm)との積(△Nxy×d)で定義されるパラメーターであり、光学的等方性、異方性を示す尺度である。二軸の屈折率の異方性(△Nxy)は、以下の方法により求める。二枚の偏光板を用いて、フィルムの配向軸方向を求め、配向軸方向が直交するように4cm×2cmの長方形を切り出し、測定用サンプルとした。このサンプルについて、直交する二軸の屈折率(Nx,Ny)、及び厚さ方向の屈折率(Nz)をアッベ屈折率計(アタゴ社製、NAR-4T)によって求め、前記二軸の屈折率差の絶対値(|Nx-Ny|)を屈折率の異方性(△Nxy)とした。フィルムの厚みd(nm)は電気マイクロメータ(ファインリューフ社製、ミリトロン1245D)を用いて測定し、単位をnmに換算した。屈折率の異方性(△Nxy)とフィルムの厚みd(nm)の積(△Nxy×d)より、リタデーション(Re)を求めた。
フィルム厚さ方向断面から見たときの2つの複屈折△Nxz(=|Nx-Nz|)、△Nyz(=|Ny-Nz|)にそれぞれフィルム厚さdを掛けて得られるリタデーションの平均を示すパラメーターである。リタデーションの測定と同様の方法でNx、Ny、Nzとフィルム厚みd(nm)を求め、(△Nxz×d)、(△Nyz×d)の平均値を算出して厚さ方向リタデーション(Rth)を求めた。
分光光度計(日立製作所製、U-3500型)を用い、空気層を標準として波長300~500nm領域の光線透過率を測定し、波長380nmにおける光線透過率を求めた。
PVAとヨウ素からなる偏光子の片側に本発明のポリエステルフィルムを偏光膜の吸収軸とフィルムの配向主軸が垂直になるように貼り付け、その反対の面にTACフィルム(富士フイルム(株)社製、厚み80μm)を貼り付けて偏光板を作成した。得られた偏光板を、青色発光ダイオードとイットリウム・アルミニウム・ガーネット系黄色蛍光体とを組み合わせた発光素子からなる白色LEDを光源(日亜化学、NSPW500CS)とする液晶表示装置(液晶セルの光源側に2枚のTACフィルムを偏光子保護フィルムとする偏光板を有する)の出射光側にポリエステルフィルムが出射光側になるように設置した。液晶表示装置の偏光板を正面、及び斜め方向から目視観察し、虹斑の発生有無について、以下のように判定した。なお、比較例5では白色LEDの代わりに冷陰極管を光源とするバックライト光源を用いた。
○: 斜め方向から観察した時に、一部極薄い虹斑が観察できる。
×: 斜め方向から観察した時に、明確に虹斑が観察できる。
東洋精機製作所製エレメンドルフ引裂試験機を用いて、JIS P-8116に従い、各フィルムの引裂き強度を測定した。引裂き方向はフィルムの配向軸方向と平行となるように行ない、以下のように判定した。なお、配向軸方向の測定は分子配向計(王子計測器株式会社製、MOA-6004型分子配向計)で測定した。
○:引裂き強度が50mN以上
×:引裂き強度が50mN未満
偏光子保護フィルムの易接着層表面に、固形分濃度5質量%に調整したポリビニルアルコール水溶液(クラレ製 PVA117)を、乾燥後のポリビニルアルコール樹脂層の厚みが、2μmになるようにワイヤーバーで塗布し、70℃で5分間乾燥した。ポリビニルアルコール水溶液には、判定が容易となるよう赤色染料を加えたものを使用した。作成した評価対象フィルムを、両面テープを貼り付けた厚さ5mmのガラス板に、ポリビニルアルコール樹脂層が形成された面の反対側が上記両面テープに接するように貼り付けた。次いで、ポリビニルアルコール樹脂層を貫通して、偏光子保護フィルムに達する100個の升目状の切り傷を、隙間間隔2mmのカッターガイドを用いて付けた。次いで、粘着テープ(ニチバン社製セロテープ(登録商標) CT-24;24mm幅)を升目状の切り傷面に貼り付けた。貼り付け時に界面に残った空気を消しゴムで押して、完全に密着させた後、粘着テープを勢いよく垂直に引き剥がす作業を1回、5回、10回実施した。ポリビニルアルコール樹脂層が剥がれていない升目の個数を数え、PVA接着性とした。即ち、PVA層が全く剥がれていない場合を、PVA接着率100とし、PVA層が全て剥がれた場合は、PVA接着率0とした。よって、例えば、5個の升目に剥離が見られた場合は、PVA接着率は95となる。なお、1個の升目内で部分的に剥がれているものも、剥がれた個数に含めた。
(ポリエステル樹脂の重合)
攪拌機、温度計、および部分還流式冷却器を具備するステンレススチール製オートクレーブに、ジメチルテレフタレート194.2質量部、ジメチルイソフタレート184.5質量部、ジメチル-5-ナトリウムスルホイソフタレート14.8質量部、ジエチレングリコール233.5質量部、エチレングリコール136.6質量部、およびテトラ-n-ブチルチタネート0.2質量部を仕込み、160℃から220℃の温度で4時間かけてエステル交換反応を行なった。次いで255℃まで昇温し、反応系を徐々に減圧した後、30Paの減圧下で1時間30分反応させ、共重合ポリエステル樹脂(A-1)を得た。得られた共重合ポリエステル樹脂(A-1)は、淡黄色透明であった。共重合ポリエステル樹脂(A-1)の還元粘度を測定したところ0.70dl/gであった。DSCによるガラス転移温度は40℃であった。
攪拌機、温度計と還流装置を備えた反応器に、ポリエステル樹脂(A-1)30質量部、エチレングリコールn-ブチルエーテル15質量部を入れ、110℃で加熱、攪拌し樹脂を溶解した。樹脂が完全に溶解した後、水55質量部をポリエステル溶液に攪拌しつつ徐々に添加した。添加後、液を攪拌しつつ室温まで冷却して、固形分30質量%の乳白色のポリエステル水分散体(Aw-1)を作製した。同様にポリエステル樹脂(A-1)の代わりにポリエステル樹脂(A-2)~(A-3)を使用して、水分散体を作製し、それぞれポリエステル水分散体(Aw-2)~(Aw-3)とした。
攪拌機と温度計を備えた容器に、水90質量部を入れ、攪拌しながら重合度500のポリビニルアルコール樹脂(クラレ製)(B-1)10質量部を徐々に添加した。添加後、液を攪拌しながら、95℃まで加熱し、樹脂を溶解させた。溶解後、攪拌しながら室温まで冷却して、固形分10質量%のポリビニルアルコール水溶液(Bw-1)を作成した。同様に、ポリビニルアルコール樹脂(B-1)の代わりにポリビニルアルコール樹脂(B-2)~(B-6)を使用し水溶液を作成し、それぞれ(Bw-2)~(Bw-6)とした。ポリビニルアルコール樹脂(B-1)~(B-6)のけん化度を表2に示す。
攪拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物(旭化成ケミカルズ製、デュラネートTPA)100質量部、プロピレングリコールモノメチルエーテルアセテート55質量部、ポリエチレングリコールモノメチルエーテル(平均分子量750)30質量部を仕込み、窒素雰囲気下、70℃で4時間保持した。その後、反応液温度を50℃に下げ、メチルエチルケトオキシム47質量部を滴下した。反応液の赤外スペクトルを測定し、イソシアネート基の吸収が消失したことを確認し、固形分75質量%のブロックポリイソシアネート水分散液(C-1)を得た。
(ポリエステルX)
エステル化反応缶を昇温し200℃に到達した時点で、テレフタル酸を86.4質量部およびエチレングリコール64.6質量部を仕込み、撹拌しながら触媒として三酸化アンチモンを0.017質量部、酢酸マグネシウム4水和物を0.064質量部、トリエチルアミン0.16質量部を仕込んだ。ついで、加圧昇温を行いゲージ圧0.34MPa、240℃の条件で加圧エステル化反応を行った後、エステル化反応缶を常圧に戻し、リン酸0.014質量部を添加した。さらに、15分かけて260℃に昇温し、リン酸トリメチル0.012質量部を添加した。次いで15分後に、高圧分散機で分散処理を行い、15分後、得られたエステル化反応生成物を重縮合反応缶に移送し、280℃で減圧下重縮合反応を行った。重縮合反応終了後、95%カット径が5μmのナスロン製フィルターで濾過処理を行い、ノズルからストランド状に押出し、予め濾過処理(孔径:1μm以下)を行った冷却水を用いて冷却、固化させ、ペレット状にカットした。得られたポリエチレンテレフタレート樹脂の固有粘度は0.62dl/gであり、不活性粒子及び内部析出粒子は実質上含有していなかった。(以後、PET(X)と略す。)
乾燥させた紫外線吸収剤(2,2’-(1,4-フェニレン)ビス(4H-3,1-ベンズオキサジノン-4-オン)10質量部、粒子を含有しないPET(X)(固有粘度が0.62dl/g)90質量部を混合し、混練押出機を用い、紫外線吸収剤含有するポリエチレンテレフタレート樹脂(Y)を得た。(以後、PET(Y)と略す。)
下記の塗剤を混合し、ポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が70/30になる塗布液を作成した。ポリエステル水分散体は、酸価が2KOHmg/gであるポリエステル樹脂が分散した水分散体(Aw-1)を使用し、ポリビニルアルコール水溶液は、けん化度が74モル%であるポリビニルアルコールが溶解した水溶液(Bw-4)を使用した。
水 40.61質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-4) 15.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
塗布液を未延伸PETフィルムの片面に塗布した以外は実施例1と同様の方法を用い、未延伸フィルムの厚みを変更することにより、厚み約100μmの一軸配向PETフィルムを得た。
未延伸フィルムを、加熱されたロール群及び赤外線ヒーターを用いて105℃に加熱し、その後周速差のあるロール群で走行方向に1.5倍延伸した後、幅方向に4.0倍延伸した以外は実施例1と同様にして、フィルム厚み約50μmの二軸配向PETフィルムを得た。
走行方向に2.0倍、幅方向に4.0倍延伸した以外は実施例3と同様にしてフィルム厚み約50μmの二軸配向PETフィルムを得た。
走行方向に3.3倍、幅方向に4.0倍延伸した以外は実施例3と同様にして、フィルム厚み約75μmの二軸配向PETフィルムを得た。
中間層に紫外線吸収剤を含有するPET樹脂(Y)を用いなかった以外は実施例1と同様にして、フィルム厚み50μmの一軸配向PETフィルムを得た。得られたフィルムは虹状の色斑は解消されたが、380nmの光線透過率が高く、光学機能性色素を劣化させる懸念がある。
走行方向に4.0倍、幅方向に1.0倍延伸した以外は実施例3と同様にして、フィルム厚み約100μmの一軸配向PETフィルムを得た。得られたフィルムはReが3000nm以上で視認性は良好であるが、機械強度はやや劣っていた。
走行方向に3.5倍、幅方向に3.7倍延伸した以外は実施例3と同様にして、フィルム厚み約250μmの二軸配向PETフィルムを得た。得られたフィルムはReが4500nm以上であるが、Re/Rth比が0.2を下回ったため、斜め方向での極薄い虹斑が認められた。
走行方向に1.0倍、幅方向に3.5倍延伸した以外は実施例1と同様にして、フィルム厚み約75μmの一軸配向PETフィルムを得た。
未延伸フィルムの厚みを変更した以外は実施例1と同様にして、厚み約275μmの一軸配向PETフィルムを得た。
ポリエステル水分散体を、酸価が4KOHmg/gのポリエステル樹脂が分散した水分散体(Aw-2)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
ポリエステル水分散体を、酸価が6KOHmg/gのポリエステル樹脂が分散した水分散体(Aw-3)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
ポリビニルアルコール水溶液を、ポリビニルアルコールのけん化度が79モル%であるポリビニルアルコール水溶液(Bw-3)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
ポリビニルアルコール水溶液を、けん化度が83モル%であるポリビニルアルコール水溶液(Bw-2)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が60/40になるように変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 37.28質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 10.00質量%
ポリビニルアルコール水溶液(Bw-4) 20.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が80/20になるように変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 43.95質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 13.33質量%
ポリビニルアルコール水溶液(Bw-4) 10.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が50/50になるように変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 33.95質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 8.33質量%
ポリビニルアルコール水溶液(Bw-4) 25.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
塗布液の組成を下記の通り変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 40.87質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-4) 15.00質量%
メラミン系架橋剤(C-2) 0.71質量%
(ニカラックMX-042 三和ケミカル製 固形分濃度70%)
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
ポリビニルアルコール水溶液を、けん化度が70モル%であるポリビニルアルコールが溶解した水溶液(Bw-5)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
ポリビニルアルコール水溶液を、けん化度が67モル%であるポリビニルアルコールが溶解した水溶液(Bw-6)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
塗布液の組成を下記の通り変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 40.33質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-2) 15.00質量%
オキサゾリン系架橋剤(C-3) 1.25質量%
(エポクロスWS-500、日本触媒製、固形分濃度40質量%)
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
ポリビニルアルコール水溶液を、けん化度が88モル%であるポリビニルアルコールが溶解した水溶液(Bw-1)に変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
下記の塗剤を混合し架橋剤を混合しないように変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 41.58質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-4) 15.00質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
実施例2の一軸配向ポリエステルフィルムの塗布層を有する面とは反対側の面に防眩層を設けた。実施例2と同様にいずれの方向からも虹斑は観察されず、良好な結果が得られた。
走行方向に3.6倍、幅方向に4.0倍延伸した以外は実施例3と同様にして、フィルム厚み約38μmの二軸配向PETフィルムを得た。得られたフィルムはリタデーションが低く、斜め方向から観察した時に虹状の色斑が観察された。
実施例1と同様の方法を用い、未延伸フィルムの厚みを変更することにより、厚み約10μmの一軸配向PETフィルムを得た。得られたフィルムは非常に裂けやすく、コシ感が無いので偏光子保護フィルムとして用いることが出来なかった。また、リタデーションも低く、虹状の色斑が観察された。
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が100/0になるように変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 50.62質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 16.66質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が0/100になるように変更した以外は、実施例1と同様にして、一軸配向PETフィルムを得た。
水 17.28質量%
イソプロパノール 30.00質量%
ポリビニルアルコール水溶液(Bw-4) 50.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
液晶表示装置の光源を冷陰極管とする以外は、実施例1と同様にした。
Claims (10)
- バックライト光源、2つの偏光板、及び前記2つの偏光板の間に配置された液晶セルを有する液晶表示装置であって、
前記バックライト光源は、白色発光ダイオード光源であり、
前記2つの偏光板は、偏光子の両側に偏光子保護フィルムが積層された構造を有し、
前記偏光子保護フィルムの少なくとも1つは、易接着層を有するポリエステルフィルムであり、
前記ポリエステルフィルムは、3000~30000nmのリタデーションを有し、
前記易接着層は、ポリエステル系樹脂(A)及びポリビニルアルコール系樹脂(B)を含む、液晶表示装置。 - 前記液晶セルに対して出射光側に配される偏光板の出射光側の偏光子保護フィルムが、前記易接着層を有するポリエステルフィルムである、
請求項1に記載の液晶表示装置。 - 前記ポリエステルフィルムのリタデーションと厚さ方向リタデーションの比(Re/Rth)が0.2以上1.2以下である請求項1または2に記載の液晶表示装置。
- 前記ポリエステルフィルムが、偏光子と接する側とは反対側の面に、ハードコート層、防眩層、反射防止層、低反射層、低反射防眩層、及び反射防止防眩層から成る群より選択される1種以上の層を有する請求項1~3のいずれかに記載の液晶表示装置。
- 偏光子の両側に偏光子保護フィルムが積層された構造を有し、
前記偏光子保護フィルムの少なくとも一方は、易接着層を有するポリエステルフィルムであり、
前記ポリエステルフィルムは、3000~30000nmのリタデーションを有し、
前記易接着層は、ポリエステル系樹脂(A)及びポリビニルアルコール系樹脂(B)を含む、
白色発光ダイオードをバックライト光源とする液晶表示装置用偏光板。 - 前記ポリエステルフィルムが、偏光子と接する側とは反対側の面に、ハードコート層、防眩層、反射防止層、低反射層、低反射防眩層、及び反射防止防眩層から成る群より選択される1種以上の層を有する、
請求項5に記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光板。 - ポリエステル系樹脂(A)及びポリビニルアルコール系樹脂(B)を含む易接着層を有し、且つ、3000~30000nmのリタデーションを有するポリエステルフィルムからなる、白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
- 前記ポリエステルフィルムのリタデーションと厚さ方向リタデーションの比(Re/Rth)が0.2以上1.2以下である、請求項7に記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
- 前記ポリエステルフィルムが少なくとも3層以上からなり、
最外層以外の層に紫外線吸収剤を含有し、
380nmの光線透過率が20%以下である、
請求項7または8に記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。 - 前記ポリエステルフィルムが、偏光子と接する側とは反対側の面に、ハードコート層、防眩層、反射防止層、低反射層、低反射防眩層、及び反射防止防眩層から成る群から選択される1種以上の層を有するポリエステルフィルムであることを特徴とする請求項7~9のいずれかに記載の白色発光ダイオードをバックライト光源とする液晶表示装置用偏光子保護フィルム。
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JP2012524432A JP5472464B2 (ja) | 2011-05-18 | 2012-05-16 | 液晶表示装置、偏光板および偏光子保護フィルム |
EP12785180.6A EP2711765B1 (en) | 2011-05-18 | 2012-05-16 | Liquid crystal display device, use of polarizer, use of protective film |
KR1020137032409A KR101719862B1 (ko) | 2011-05-18 | 2012-05-16 | 액정표시장치, 편광판 및 편광자 보호 필름 |
US14/118,169 US10180597B2 (en) | 2011-05-18 | 2012-05-16 | Liquid crystal display device, polarizing plate, and polarizer protection film |
CN201280024048.5A CN103547961B (zh) | 2011-05-18 | 2012-05-16 | 液晶显示装置、偏光板和偏振片保护膜 |
US16/246,255 US20190146280A1 (en) | 2011-05-18 | 2019-01-11 | Liquid crystal display device, polarizing plate, and polarizer protection film |
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US (2) | US10180597B2 (ja) |
EP (1) | EP2711765B1 (ja) |
JP (1) | JP5472464B2 (ja) |
KR (1) | KR101719862B1 (ja) |
CN (2) | CN106094091B (ja) |
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WO (1) | WO2012157663A1 (ja) |
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CN103547961B (zh) | 2017-07-14 |
US20190146280A1 (en) | 2019-05-16 |
JP5472464B2 (ja) | 2014-04-16 |
KR20140034813A (ko) | 2014-03-20 |
KR101719862B1 (ko) | 2017-03-24 |
CN106094091B (zh) | 2019-03-15 |
JPWO2012157663A1 (ja) | 2014-07-31 |
CN103547961A (zh) | 2014-01-29 |
US20140098325A1 (en) | 2014-04-10 |
TW201303392A (zh) | 2013-01-16 |
EP2711765A1 (en) | 2014-03-26 |
US10180597B2 (en) | 2019-01-15 |
EP2711765A4 (en) | 2015-03-04 |
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