WO2013100041A1 - Dispositif d'affichage à cristaux liquides, polariseur et film de protection d'élément polarisant - Google Patents

Dispositif d'affichage à cristaux liquides, polariseur et film de protection d'élément polarisant Download PDF

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Publication number
WO2013100041A1
WO2013100041A1 PCT/JP2012/083848 JP2012083848W WO2013100041A1 WO 2013100041 A1 WO2013100041 A1 WO 2013100041A1 JP 2012083848 W JP2012083848 W JP 2012083848W WO 2013100041 A1 WO2013100041 A1 WO 2013100041A1
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film
polyester
polyvinyl alcohol
protective film
resin
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PCT/JP2012/083848
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English (en)
Japanese (ja)
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充晴 中谷
量之 鷹矢
東浦　真哉
晴信 黒岩
村田　浩一
佐々木　靖
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東洋紡株式会社
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Priority to JP2013551786A priority Critical patent/JP6201755B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G02B1/105—
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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

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, a polarizing plate, and a polarizer protective film that have good visibility and are suitable for thinning.
  • a polarizing plate used in a liquid crystal display usually 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.
  • a triacetyl cellulose (TAC) film is usually used.
  • TAC film used as the protective film is reduced for this purpose, sufficient mechanical strength cannot be obtained, and the moisture permeability becomes high and the polarizer is likely to deteriorate. Further, TAC films are very expensive, and there is a strong demand for inexpensive alternative materials.
  • Patent Documents 1 to 3 it has been proposed to use a polyester film instead of the TAC film so that the polarizing plate can be made thin so that high durability can be maintained even if the thickness is small as a polarizer protective film.
  • the triacetyl cellulose film used as a polarizer protective film is subjected to alkali treatment on the surface, and has an extremely high affinity with a hydrophilic adhesive. Therefore, the protective film made of a triacetyl cellulose film has extremely high adhesiveness with a polarizer coated with a hydrophilic adhesive.
  • the polyester film has insufficient adhesion to the hydrophilic adhesive, and this tendency becomes more prominent particularly in the case of a polyester film having orientation by a stretching treatment. Therefore, it has been proposed to provide an easy-adhesion layer on the polyester film in order to improve the adhesion with the polarizer or the hydrophilic adhesive applied to the polarizer (Patent Documents 4 to 7).
  • the polyester film is superior to the TAC film in durability, but unlike the TAC film, it has birefringence. Therefore, when it is used as a polarizer protective film, there is a problem that the image quality is deteriorated due to optical distortion. That is, since the polyester film having birefringence has a predetermined optical anisotropy (retardation), when used as a polarizer protective film, a rainbow-like color spot is generated when observed from an oblique direction, and the image quality is deteriorated. . 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 this tendency is particularly remarkable in the polyester film having an aromatic dicarboxylic acid as a dicarboxylic acid component. Moreover, the polyester film which has crystal orientation by extending
  • the polarizer and the adhesive applied on the polarizer are generally composed mainly of a polyvinyl alcohol resin and have high hydrophilicity. Due to such a difference in properties, the polyester film and the polarizer or the polyvinyl alcohol-based adhesive have low affinity, and it has been difficult to firmly bond the two.
  • the present invention has been made to solve such problems, and its purpose is excellent in adhesion between a polyester film and a polarizer or a polyvinyl alcohol-based resin layer such as an adhesive applied on the polarizer, and a liquid crystal.
  • An object of the present invention is to provide a liquid crystal display device and a polarizer protective film that can cope with a reduction in the thickness of the display device and that does not deteriorate visibility due to rainbow-like color spots.
  • 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 found that the iridescent color spots were caused by the retardation of the polyester film and the emission spectrum of the backlight light source. That is, when a continuous light source having a broad emission spectrum is used as the backlight light source, it has been found that a deterioration in visibility due to rainbow-like color spots can be suppressed if the polyester film has a specific range of retardation.
  • the present inventors include a polyester resin having a high affinity with the polyester film and a polyvinyl alcohol resin having a high affinity with the polyvinyl alcohol resin layer.
  • the idea was to provide a layer on the polyester film.
  • the present inventors have found that the function of closely adhering the polyester film and the polyvinyl alcohol-based resin layer due to each component cannot be sufficiently exhibited by simply combining these components. Therefore, as a result of repeated day and night studies, the present inventors have controlled the presence of the binder resin in the coating layer provided on the surface of the polyester film in the above concept, and the phase in which the polyester resin is aggregated and the polyvinyl alcohol resin. It has been found that by forming a nanophase separation structure composed of an aggregated phase on the surface of the coating layer, the adhesive action with the polarizer can be more effectively exhibited.
  • the present inventors use a combination of a specific backlight light source and a polyester film having a specific retardation, and further form a nanophase separation structure on the surface of the coating layer.
  • the inventors have found that the above problem can be solved, and have completed the present invention.
  • Representative examples of the present invention are the following (1) to (12).
  • the surface of the coating layer has a nanophase separation structure composed of a phase in which a polyvinyl alcohol resin is aggregated and a phase in which a polyester resin is aggregated, and the area ratio of the polyvinyl alcohol phase is 30% or more and less than 99%.
  • Polarizer protective film Polarizer protective film.
  • the polarizer protective film according to any one of (1) to (6), wherein a ratio (Re / Rth) of retardation of the polyester film to thickness direction retardation is 0.2 or more and 1.2 or less.
  • a ratio (Re / Rth) of retardation of the polyester film to thickness direction retardation is 0.2 or more and 1.2 or less.
  • the polyester film comprises at least three layers, contains an ultraviolet absorber in a layer other than the outermost layer, and has a light transmittance of 380 nm of 20% or less.
  • the polarizer protective film according to any one of (1) to (8) which has one or more layers selected from the group consisting of: (10) A polarizing plate in which the polarizer protective film according to any one of (1) to (9) is laminated on at least one surface of the polarizer.
  • the polarizer protective film of the present invention is excellent in adhesion between the polarizer protective film and a polarizer typified by a polyvinyl alcohol-based resin layer or an adhesive applied thereon. Therefore, the polarizing plate using the polarizer protective film of the present invention is unlikely to float or peel between the protective film and the polarizer, and the polarization characteristics are not easily lowered due to a change in the amount of moisture in the polarizer. Therefore, in the liquid crystal display device using the polarizing plate of the present invention, the deterioration of visibility such as white spots due to the deterioration of the characteristics over time in the conventional polarizing plate is reduced. Moreover, the liquid crystal display device produced using the polarizer protective film of the present invention has good visibility with no noticeable rainbow-like color spots even when the display is observed from any viewing angle.
  • the polarizer protective film of the present invention is a phase in which a polyester resin is agglomerated on the surface of the coating layer (hereinafter referred to as “PEs phase” as appropriate). ) And a phase in which the polyvinyl alcohol-based resin is aggregated (hereinafter, referred to as “PVA phase” as appropriate) is formed, so that a polarizer caused by the PVA phase or on the polarizer It is considered that strong adhesiveness with the provided adhesive is exhibited.
  • the nanophase separation structure of the coating layer surface of the polarizer protective film of Example 14 is shown.
  • the scale unit is ⁇ m, and the actual size is 1 ⁇ m ⁇ 1 ⁇ m.
  • the liquid crystal panel includes a rear module, a liquid crystal cell, and a front module in order from the backlight source side toward the image display side (viewing side or emission 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 backlight source side in the rear module, and is disposed on the image display side (viewing side or emission light side) in the front module.
  • the liquid crystal display device of the present invention includes at least a backlight light source and a liquid crystal cell disposed between two polarizing plates. Moreover, you may have suitably other structures other than these, for example, a color filter, a lens film, a diffusion sheet, an antireflection film etc. suitably.
  • the configuration of the backlight light source may be an edge light method using a light guide plate or a reflection plate as a constituent member, or a direct type, but a white light source having a continuous and broad emission spectrum is used. It is preferable.
  • the continuous and broad emission spectrum means an emission spectrum in which there is no wavelength at which the light intensity becomes zero in the wavelength region of at least 450 nm to 650 nm, preferably in the visible light region. Examples of such a white light source having a continuous and broad emission spectrum include a white light emitting diode (white LED).
  • White LEDs include phosphors, that is, elements that emit white light by combining a phosphor that emits blue light or ultraviolet light using a compound semiconductor, and organic light-emitting diodes (Organic light-emitting diodes: OLEDs). Etc. are included.
  • white LEDs white light-emitting diodes consisting of a light-emitting element that combines a blue light-emitting diode using a compound semiconductor and a yttrium, aluminum, and garnet yellow phosphor have a continuous and broad emission spectrum and luminous efficiency. Therefore, it is suitable as the backlight light source of the present invention. Using a white LED or the like with lower power consumption as the light source is also effective for energy saving.
  • Fluorescent tubes such as cold cathode tubes and hot cathode tubes that have been widely used as backlight light sources conventionally have only a discontinuous emission spectrum whose emission spectrum has a peak at a specific wavelength. It is difficult to obtain the effects of the present invention.
  • the polarizing plate has a configuration in which both sides of a polarizer in which iodine is dyed on PVA or the like are sandwiched between two polarizer protective films.
  • at least one of the polarizer protective films constituting the polarizing plate is used.
  • a polyester film having a specific range of retardation can be used.
  • a mechanism that suppresses the occurrence of rainbow-like color spots according to the above-described aspect is considered as follows.
  • a polyester film having birefringence is disposed on one side of the polarizer, 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, and a rainbow-like color spot is generated (see: 15th Micro Optical Conference Proceedings, No. 1). 30-31).
  • a fluorescent tube such as a cold cathode tube or a hot cathode tube is 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 transmitted light intensity varies depending on the wavelength. For this reason, only a specific wavelength is strongly transmitted, and it is considered that a rainbow-like color spot occurs.
  • white light emitting diodes usually have a continuous and broad emission spectrum in a wavelength region of at least 450 nm to 650 nm, preferably in the visible light region.
  • transmitted the birefringent body becomes an envelope shape, it becomes possible to obtain the spectrum similar to the light emission spectrum of a light source by controlling the retardation of a polyester film. In this way, by making the emission spectrum of the light source similar to the envelope shape of the interference color spectrum by the transmitted light that has passed through the birefringent body, visibility is not noticeable without rainbow-like color spots. It is thought to improve.
  • a white light emitting diode having a broad emission spectrum is used as a light source, so that the envelope shape of the spectrum of transmitted light can be approximated to the emission spectrum of the light source with only a relatively simple configuration, and as a result, liquid crystal It is thought that it is possible to suppress rainbow spots on the display.
  • the polyester film used for the polarizer protective film preferably has 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.
  • the lower limit of the preferable retardation is 4500 nm or more, more preferably 6000 nm or more, further preferably 8000 nm or more, and still more preferably 10,000 nm or more.
  • 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 present invention can be obtained by measuring the refractive index and thickness in the biaxial direction, or by using a commercially available automatic birefringence measuring device such as KOBRA-21ADH (Oji Scientific Instruments). it can.
  • retardation means in-plane retardation.
  • 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 is not particularly limited, but the polarizer protective film on the incident light side of the polarizing plate arranged on the incident light side of the liquid crystal display device, or the polarized light arranged on the emission light side
  • a polarizer protective film on the emission light side of the plate is preferred.
  • a particularly preferred embodiment is an embodiment in which the polarizer protective film on the exit light side of the polarizing plate disposed on the exit light side is a polyester film having the specific retardation. When the polyester film is disposed at a position other than the above, the polarization characteristics of the liquid crystal cell may be changed.
  • the polarizing plate of the present invention has a configuration in which both sides of a polarizer in which polyvinyl alcohol (PVA) is dyed with iodine are sandwiched between two polarizer protective films, and any one of the polarizer protective films is specified above. It is a polarizing plate protective film which has this 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 polarizer examples include a polyvinyl alcohol film containing a dichroic material such as iodine.
  • the polarizer protective film is bonded to the polarizer directly or via an adhesive layer, but is preferably bonded via an adhesive from the viewpoint of improving the adhesiveness. In that case, it is preferable to arrange
  • a preferable polarizer for bonding the polyester film of the present invention for example, iodine or dichroic material is dyed and adsorbed on a polyvinyl alcohol film, uniaxially stretched in a boric acid aqueous solution, and the stretched state is maintained.
  • cleaning and drying is mentioned.
  • the stretching ratio of uniaxial stretching is usually about 4 to 8 times.
  • Polyvinyl alcohol is suitable as the polyvinyl alcohol film.
  • “Kuraray Vinylon” [manufactured by Kuraray Co., Ltd.]
  • “Tosero Vinylon” [manufactured by Tosero Co., Ltd.]
  • “Nippon Vinylon” [Nippon Synthetic Chemical Co., Ltd.]
  • Commercial products such as “made” can be used.
  • Examples of the dichroic material include iodine, a disazo compound, and a polymethine dye.
  • the adhesive applied to the polarizer is preferably an aqueous one, that is, an adhesive component dissolved in water or dispersed in water.
  • a polyvinyl alcohol resin, a urethane resin, or the like is used as a main component, and a composition containing an isocyanate compound, an epoxy compound, or the like can be used as necessary in order to improve adhesiveness.
  • the thickness of the adhesive layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • polyvinyl alcohol resin As the main component of the adhesive, in addition to partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, amino group-modified A modified polyvinyl alcohol resin such as polyvinyl alcohol may be used.
  • the concentration of the polyvinyl alcohol resin in the adhesive is preferably 1 to 10% by mass, and more preferably 2 to 7% by mass.
  • the polarizing plate used in the present invention has various functional layers such as a hard coat layer, an antiglare layer, an antireflection layer, a low reflection layer, and a low reflection antiglare layer for the purpose of preventing reflection, suppressing glare, and suppressing scratches.
  • the polyester film surface preferably has one or more layers selected from the group consisting of a layer, an antireflection antiglare layer and an antistatic layer.
  • Such a functional layer can be provided on the surface opposite to the surface on which the coating layer of the polarizer protective film of the present invention is provided.
  • the oriented polyester film preferably has an easy adhesion layer on the surface thereof.
  • the refractive index of the easy-adhesion layer it is preferable to adjust the refractive index of the easy-adhesion layer so that it is close to the geometric mean of the refractive index of the functional layer and the refractive index of the polyester film.
  • the refractive index of the easy-adhesion layer can be adjusted by a known method.
  • the refractive index of the easy-adhesion layer can be easily adjusted by adding titanium, zirconium, or other metal species to the binder resin.
  • the polyester film used as the polarizer protective film of the present invention can be obtained by condensing dicarboxylic acid and diol.
  • the dicarboxylic acid component that can be used for producing the polyester film include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, , 5-Naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfonecarboxylic acid, anthracenedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Hexahydroterephthalic acid, hexahydroisophthalic acid, malonic
  • diol component 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. Can be mentioned.
  • the dicarboxylic acid component and the diol component constituting the polyester film may each be used alone or in combination of two or more.
  • Specific polyester resins constituting the polyester film include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and preferably polyethylene terephthalate and polyethylene naphthalate. 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 the most suitable material because it has a large intrinsic birefringence and a large retardation can be obtained relatively easily even if the film is thin.
  • the film of the present invention preferably has a light transmittance of 380 nm or less of 20% or less.
  • 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 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 polyester film is preferably composed of three or more layers, and the ultraviolet absorber is blended with a layer other than the outermost layer (that is, the intermediate layer).
  • 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, cyclic imino ester, and combinations thereof, but are not particularly limited as long as the absorbance is within the range defined by the present invention.
  • benzotoazole and cyclic imino ester are particularly preferable.
  • ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.
  • 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 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, when the inorganic element is quantified by fluorescent X-ray analysis, the content is 50 ppm or less, preferably 10 ppm or less, particularly preferably the detection limit or less. Means quantity.
  • the polarizer protective film of the present invention has a polyester resin (on at least one surface of a polyester film) in order to improve the adhesion with a polarizer or a polyvinyl alcohol resin layer such as a water-based adhesive provided on one or both surfaces of the polarizer.
  • the easy-adhesion layer (coating layer) which consists of a resin composition containing A) and polyvinyl alcohol-type resin (B) is laminated
  • the coating layer is provided on at least one side of the polyester film, and may be provided on both sides. A different kind of resin coating layer may be provided on the other surface, and the functional layer described above may be provided on the coating layer.
  • Adhesiveness to the base film is achieved with the polyester resin (A), and adhesion to the polarizer / water-based adhesive is achieved with the polyvinyl alcohol resin (B), thereby favoring the adhesion between these two layers. Can be compatible.
  • the coating layer contains a polyvinyl alcohol resin and a polyester resin as a binder resin, and the surface of the coating layer has a phase in which the polyvinyl alcohol resin is aggregated (PVA phase) and a phase in which the polyester resin is aggregated (PEs phase).
  • PVA phase phase in which the polyvinyl alcohol resin is aggregated
  • PEs phase phase in which the polyester resin is aggregated
  • a nanophase separation structure in the present invention, the phrase “the coating layer contains a polyvinyl alcohol resin and a polyester resin” means that the coating layer is a resin layer formed using a polyvinyl alcohol resin and a polyester resin as raw material components.
  • a component other than these resins for example, a crosslinking agent
  • it is a coating layer formed using these resins and other components (for example, a crosslinking agent) as raw materials.
  • the nanophase separation structure on the surface of the coating layer refers to two types of nanoscale phases (or regions) of PVA phase and PEs phase that are clearly distinguished by detection of the surface of the coating layer using a scanning probe microscope described later. It means existing on the surface of the coating layer.
  • the PVA phase is a phase formed by aggregation of polyvinyl alcohol-based resins. Therefore, although the PVA phase is mainly composed of a polyvinyl alcohol-based resin, as long as it can be distinguished from the PEs phase by a scanning probe microscope, the component constituting the other coating layer mixed with aggregation (for example, Crosslinkers and trace amounts of PEs) may be included.
  • the PEs phase is a phase formed by aggregating polyester resins.
  • the PEs phase is mainly composed of a polyester resin, but as long as it can be distinguished from the PVA phase by a scanning probe microscope, other components (for example, a cross-linking agent and a small amount of PVA) are mixed. You may do it.
  • the size and shape of the PVA phase and the PEs phase are not particularly limited as long as the structure satisfies the surface fraction of the PVA phase described later and is recognized as a nanophase separation structure in the technical field.
  • Specific examples of the nanophase separation structure include a sea-island structure, a core / shell structure, and a laminated structure (lamella structure) in which each phase is regularly arranged.
  • the sea-island structure may be an independent “island” -like form or may be a form in which “islands” are continuous.
  • the size of the sea-island structure is not particularly limited.
  • the sea-island structure is mainly an island-shaped structure having a width in the minor axis direction of 20 nm to 500 nm at the maximum and a length in the major axis direction exceeding 50 nm.
  • the core-shell structure which is one of the nanophase separation structures, is a structure in which, for example, the PVA phase is surrounded by the PEs phase, and further, the PEs phase is surrounded by the PVA phase.
  • a phase recognized as an aggregate of a polyvinyl alcohol resin and a phase recognized as an aggregate of a polyester resin it is preferable from the viewpoint of exhibiting excellent adhesiveness that it is dispersed without significant deviation.
  • the coating layer surface having the nanophase separation structure as described above preferably has an area ratio of the PVA phase defined by the following formula of 30% or more and less than 99%.
  • PVA phase surface fraction (%) (PVA phase area / measurement area) ⁇ 100
  • the area of the PVA phase is measured by using a phase measurement mode of a scanning probe microscope, which will be described later. In that case, the polyvinyl alcohol phase shows a dark hue in a phase image, for example.
  • the measurement area is not particularly limited, for example, it can be performed at 1 ⁇ m ⁇ 1 ⁇ m.
  • the PVA surface fraction is preferably 30 to 99%. If it is less than 30%, the surface fraction of the PEs phase on the surface of the coating layer becomes relatively large, and the adhesion to the polarizer / water-based adhesive may decrease. On the other hand, when the PVA surface fraction is 99% or more, the adhesion to the polyester film (base material) may be lowered.
  • the lower limit of the PVA surface fraction on the surface of the coating layer is preferably 30%, more preferably 35%, and even more preferably 40%.
  • the upper limit of the PVA surface fraction is more preferably 99%, further preferably 95%, and still more preferably 90%.
  • the PVA surface fraction of the nanophase separation structure can be measured by a paper weight method or an image analysis method described in Examples described later.
  • nanoseparation structure improves the adhesion.
  • Polyvinyl alcohol resins are rich in hydrophilicity, and polyester resins are rich in hydrophobicity. For this reason, simply mixing and applying the two resins causes the two resins to be completely separated and cannot exhibit sufficient adhesion.
  • both resins can be forcibly mixed with a surfactant or the like, sufficient adhesiveness cannot be exhibited in this case because the properties of both resins are impaired.
  • both resins form a nanophase separation structure, and a predetermined proportion of PVA phase is present on the surface of the coating layer, so that adhesion with the polarizer or the adhesive provided thereon is caused by the PVA resin. And the adhesiveness with the polyester film due to the PEs resin can be efficiently exhibited at the same time.
  • phase mode phase measurement mode
  • DFM mode normal dynamic force mode
  • phase mode the phase delay of the cantilever vibration when the DFM operation is performed is detected.
  • the shape is measured by controlling the distance between the probe and the sample so that the vibration amplitude of the resonated cantilever is constant.
  • the signal that vibrates the bimorph (piezoelectric element) for vibrating the cantilever is called an “input signal”
  • the phase delay of the effective cantilever vibration signal with respect to this “input signal” Is detected simultaneously with the vibration amplitude.
  • the phase delay responds sensitively to the influence of surface properties, and the softer the sample surface, the greater the delay.
  • phase image By imaging the magnitude of this phase lag, it becomes possible to observe the distribution of surface physical properties (referred to as phase image or phase image).
  • phase image By using the phase measurement mode of the scanning probe microscope (SPM), it is possible to measure and confirm a phase separation structure in which a plurality of resin phases having different physical properties exist on the surface.
  • SPM scanning probe microscope
  • the phase separation structure of the coating layer can be evaluated in the surface property distribution evaluation mode using a scanning probe microscope, in addition to the phase measurement mode, it can be performed in other modes such as the friction force measurement mode and viscoelasticity measurement mode. It is preferable to select an observation mode in which the phase separation structure can be evaluated well. In the phase measurement mode, not only the phase lag due to the difference in viscoelasticity of the coating layer but also the phase lag due to the difference in surface physical properties such as the magnitude of the adsorption force can be detected.
  • the coating layer of the present invention has a nanophase separation structure, it can exhibit high adhesiveness equal to or higher than that of triacetyl cellulose to polarizers and water-based adhesives, particularly polyvinyl alcohol-based polarizers and water-based adhesives. Is possible.
  • the coating layer preferably has a residual area after peeling once of 90% or more, more preferably 95% or more, and further preferably 100% in the adhesion test shown in the examples described later.
  • the remaining area after continuous peeling is preferably 75% or more, more preferably 85% or more, further preferably 95% or more, and the remaining area after 10 continuous peelings is preferably 50% or more, more preferably 80% or more. More preferably, it is 90% or more, still more preferably 93% or more, and particularly preferably 95% or more.
  • phase separation structure as described above can be obtained by controlling the resin concentration, selection of the resin type, drying / heating conditions and the like as described later.
  • the polyvinyl alcohol resin used as a component of the coating layer is not particularly limited as long as it is recognized as a polyvinyl alcohol resin. Specific examples thereof include polyvinyl alcohol obtained by saponifying polyvinyl acetate; a derivative thereof; a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability; Modified polyvinyl alcohol which has been converted to ether, ether, graft, phosphoric ester or the like.
  • Examples of the monomer 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.
  • suitable polyvinyl alcohol resins used in the present invention include vinyl alcohol-vinyl acetate copolymers, vinyl alcohol-vinyl butyral copolymers, and ethylene-vinyl alcohol copolymers.
  • vinyl alcohol-vinyl acetate copolymers are exemplified.
  • a polymer and an ethylene-vinyl alcohol copolymer are preferred.
  • the degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but the degree of polymerization 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 degree of saponification of the polyvinyl alcohol resin of the present invention is not particularly limited as long as excellent adhesiveness is exhibited, but it is preferably 60 mol% or more. More preferably, the upper limit of the saponification degree of the polyvinyl alcohol-based resin is 95 mol% or less, and preferably 85 mol% or less. More preferably, the degree of saponification is 65 mol% or more and 83 mol% or less, more preferably 68 mol% or more and 80 mol% or less, still more preferably 70 mol% or more and less than 80 mol%, and 71 mol% or more and 78 mol% or less.
  • % Or less is even more preferable, and 73 mol% or more and 75 mol% or less is particularly preferable.
  • the degree of saponification of the polyvinyl alcohol-based resin is equal to or higher than the above lower limit, the water-based adhesive or the polarizer is suitably adhered, and the phase separation from the polyester-based resin can be suitably performed. Further, when the degree of saponification of the polyvinyl alcohol-based resin is not more than the above upper limit (or less), a nanophase separation structure can be formed more suitably with the polyester-based resin.
  • the degree of saponification of the vinyl alcohol resin can be determined by alkali consumption required for hydrolysis of copolymer units such as vinyl acetate or composition analysis by NMR.
  • the content of the polyvinyl alcohol resin 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 further preferably 20% by mass or more and 50% by mass or less in the coating layer.
  • the content of the polyvinyl alcohol-based resin is equal to or more than the above lower limit, the PVA surface fraction increases, which is suitable for adhesiveness with a polarizer / water-based resin.
  • it is suitable for adhesiveness with a polyester film base material that it is below the upper limit.
  • polyester resin used in the coating layer of the present invention is a copolymer formed by polycondensation of a dicarboxylic acid component and a diol component, and the dicarboxylic acid component and the diol component are described as a polyester film used as the above-mentioned substrate. Can be used. 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.
  • 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.
  • an aromatic dicarboxylic acid component terephthalic acid and isophthalic acid are most preferred.
  • another aromatic dicarboxylic acid may be added and copolymerized within a range of 10 mol% or less with respect to the total dicarboxylic acid component.
  • the glass transition temperature of the polyester-based resin is preferably 25 ° C or higher, more preferably 30 ° C or higher, and further preferably 35 ° C or higher.
  • the upper limit of the glass transition temperature is preferably 110 ° C. or less, more preferably 100 ° C. or less, and further preferably 90 ° C. or less.
  • the glass transition temperature of the polyester-based resin can be controlled by introducing a copolymer component, particularly a branched glycol component, as will be described later.
  • glycol component of the polyester resin ethylene glycol and branched glycol are preferably used as constituent components.
  • 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 used as a component of the coating layer in the present invention is preferably a water-soluble or water-dispersible resin from the viewpoint of forming a suitable nanophase separation structure with a polyvinyl alcohol resin.
  • 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 a low acid value of the polyester-based resin 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 or an alkali thereof.
  • the 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 further preferably 2 to 10 mol% in the dicarboxylic acid component of the polyester resin.
  • 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.
  • 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 when a crosslinking agent is used in combination, the polyester resin preferably has fewer carboxylic acid groups that are reactive groups with the crosslinking agent in order to form a suitable phase separation structure.
  • the reactivity with the cross-linking agent decreases, and as a result, the cross-linked polyvinyl alcohol resin does not completely mix with the polyvinyl alcohol resin. It is believed that the phase separation structure can be suitably maintained.
  • the acid value of the polyester-based resin is preferably 20 KOHmg / g or less, more preferably 15 KOHmg / g or less, further preferably 10 KOHmg / g or less, still more preferably 8 KOHmg / g or less, and even more preferably. Is 5 KOHmg / g or less.
  • the acid value of the polyester resin 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 a hydrophilic group other than the carboxylic acid base is employed, It is preferable to lower the carboxylic acid terminal concentration of the polyester resin.
  • a method for lowering the carboxylic acid terminal concentration of the polyester resin it is preferable to employ a polyester resin in which the carboxylic acid terminal group is modified, or a polyester resin having a large number average molecular weight of the polyester resin.
  • the number average molecular weight of the polyester-based resin is preferably 5000 or more, more preferably 6000 or more, and further preferably 10,000 or more.
  • the content of the polyester resin in the coating layer is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less.
  • the content of the polyester resin is not less than the above lower limit, it is suitable for adhesiveness with a polyester film substrate, and when it is not more than the above upper limit, it is suitable for adhesiveness with a polarizer or a water-based adhesive provided thereon. is there.
  • a nanophase separation structure can be more suitably formed by using a crosslinking agent in the coating layer. This is presumably because the polyvinyl alcohol resin easily aggregates due to crosslinking of the hydroxyl groups of the polyvinyl alcohol resin, and as a result, a suitable separation structure is formed.
  • a crosslinking agent if it has a hydroxyl group and crosslinking property, Compounds, such as a melamine type, an isocyanate type, a carbodiimide type, an oxazoline type, an epoxy type, are mentioned.
  • the crosslinking agent is preferably a melamine compound or an isocyanate compound that suitably crosslinks with the hydroxyl group of the polyvinyl alcohol resin.
  • a carbodiimide-based crosslinking agent reacts with a carboxyl group
  • a melamine compound or an isocyanate-based compound reacts with a hydroxyl group, and thus forms a crosslinked structure more suitably with a polyvinyl alcohol-based resin having a hydroxyl group as a functional group. This is probably because of this.
  • the polyvinyl alcohol in the coating layer suitably forms a cross-linked structure, and easily moves to the surface opposite to the polyester film, so that the surface fraction of PVA is increased.
  • 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 isocyanate compound low molecular or high molecular diisocyanate or trivalent or higher polyisocyanate can be used.
  • the 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'-dd
  • Examples thereof include aliphatic diisocyanates such as alicyclic diisocyanates, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, and trimers of these isocyanate compounds. Furthermore, 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.
  • a blocked isocyanate compound is also preferable. 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 above isocyanate compound and blocking agent to an addition reaction by a conventionally 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.
  • a melamine compound substituted with a substituent-(CH2) n-O-R (wherein n is an integer of 1 to 3 and R is an alkyl group having 1 to 4 carbon atoms) R in the above formula is preferably methyl.
  • the number of the above substituents in one melamine structure is preferably 3-6.
  • 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 melamine compound and an epoxy compound or an oxazoline compound may be used in combination, but the content of the epoxy compound or oxazoline compound in that case is preferably less than 10% by weight, more preferably less than 5% by weight, More preferably, it is less than 2% by weight, particularly preferably less than 1% by weight. If the content of the epoxy compound or oxazoline compound is larger than the above upper limit, depending on the ratio of polyester and polyvinyl alcohol in the coating layer, the PVA surface fraction cannot be kept high, and the adhesiveness may be inferior. .
  • an isocyanate compound and an epoxy compound or an oxazoline compound may be used in combination, but the content of the epoxy compound or oxazoline compound in that case is preferably less than 10% by weight, more preferably less than 5% by weight. Even more preferably, it is desired to be less than 2% by weight, particularly preferably less than 1% by weight. If the content of the epoxy compound or oxazoline compound is larger than the above upper limit, depending on the ratio of polyester and polyvinyl alcohol in the coating layer, the PVA surface fraction cannot be kept high, and the adhesiveness may be inferior. .
  • content of a crosslinking agent 2 mass% or more and 50 mass% or less are preferable in a coating layer, 5 mass% or more and 40% mass% or less are more preferable, and 8 mass% or more and 30 mass% or less are more preferable.
  • content of the cross-linking agent is not less than the above lower limit, it is suitable for forming a cross-linked polyvinyl alcohol resin, and when it is not more than the above upper limit, it is suitable for the expression of the adhesive effect by the binder resin.
  • the blending ratio (B) / (A) of the polyester resin (A) and the polyvinyl alcohol resin (B) is preferably 0.2 to 1.25, more preferably 0.25 to 1, by mass ratio. More preferably, it is 0.25 to 0.5, more preferably 0.25 to 0.45.
  • (B) / (A) is at least the above lower limit, it is suitable for adhesion to a polyester film substrate, and when it is at most 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. .
  • additives such as surfactants, antioxidants, catalysts, heat stabilizers, weathering stabilizers, ultraviolet absorbers are used as long as the effects of the present invention are not impaired.
  • Agents, organic lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, and the like may be added.
  • the particles to be contained in the coating layer in the present invention include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof.
  • Inorganic particles such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, etc., and inorganic particles such as styrene, acrylic, melamine, benzoguanamine, and silicone Examples thereof include polymer-based particles.
  • the average particle size of the particles in the coating 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 deteriorated and the film is stuck. The workability at the time of alignment may deteriorate. On the other hand, if it exceeds 2.0 ⁇ m, the particles are likely to fall off, which is not preferable.
  • the particle concentration in the coating layer is preferably 1 to 20% by mass, more preferably 5 to 15% by mass in the solid component.
  • the thickness of the coating layer can be appropriately set in the range of 0.01 to 2 ⁇ m, but in order to achieve both workability and adhesiveness, the range of 0.03 to 0.25 ⁇ m is preferable.
  • the thickness is preferably 0.05 to 0.25 ⁇ m, more preferably 0.05 to 0.2 ⁇ m. Adhesiveness will become inadequate that the thickness of a coating layer is less than 0.03 micrometer. When the thickness of the coating layer exceeds 0.25 ⁇ m, blocking may occur.
  • the most common production method for producing a polyester film is that a non-oriented polyester obtained by melting a polyester resin and extruding into a sheet is formed in the machine direction at a temperature equal to or higher than the glass transition temperature by utilizing the difference in roll speed.
  • An example is a method in which after stretching, the film is stretched in the transverse direction by a tenter and subjected to heat treatment.
  • 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, it may be observed from directly above the film surface. Although rainbow-like color spots are not seen, caution is necessary because rainbow-like color spots 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 direction, a point where the retardation is zero may be generated, and a rainbow-like color spot is generated concentrically around the point. When the angle from the position directly above the film surface (normal direction) to the position where the rainbow-like color spots are visible is ⁇ , 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 (biaxial symmetry) 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 film thickness direction.
  • 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 rainbow-like color spots due to the observation angle are less likely to occur.
  • the ratio of the retardation of the polyester film of the present invention to the retardation in the thickness direction (Re / Rth) is preferably 0.200 or more, more preferably 0.500 or more, and further preferably 0.600 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 less likely to occur.
  • 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 from 80 to 130 ° C, particularly preferably from 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 ratio of the longitudinal draw ratio and the transverse draw ratio In order to control the retardation within the above range, it is preferable to control the ratio of the longitudinal draw ratio and the transverse draw ratio. If the difference between the vertical and horizontal draw ratios is too small, it is difficult to make a retardation difference, which is not preferable.
  • setting the stretching temperature low is a preferable measure for increasing the retardation.
  • the treatment temperature is preferably 140 to 240 ° C, particularly preferably 180 to 240 ° C.
  • the coating layer can be provided after the production of the film or in the production process.
  • any known method can be used as a method for applying this coating solution to the PET film.
  • reverse roll coating method gravure coating method, kiss coating method, die coater method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, curtain coating method, etc. It is done. These methods are applied alone or in combination.
  • the finally obtained coating layer preferably has a thickness of 0.04 to 0.33 g / m 2 . If it is less than 0.04 g / m 2 , the adhesiveness is lowered, and if it is thicker than 0.33 g / m 2 , the blocking property and the slipping property are lowered, which is not preferable.
  • the temperature of the drying air hitting the coated surface is preferably 80 ° C. or higher and lower than 150 ° C.
  • the wind speed is preferably 30 m / second or more.
  • a more preferable drying temperature is 100 ° C. or higher and lower than 150 ° C.
  • a suitable phase separation state can be formed by temporarily improving the flow state of the binder in the coating layer.
  • a polyester resin with a lot of hydrophobic groups and a polyvinyl alcohol resin with a lot of hydrophilic groups are aggregated in a self-organized manner to form a suitable phase separation state. I think so. It is also considered that the cross-linking reaction of the cross-linking agent proceeds and the phase separation state can be accelerated.
  • the temperature in each heat setting zone in the heat setting treatment step is slightly different depending on the type of the constituent resin of the thermoplastic resin film of the base material, but is within a temperature range of 140 to 240 ° C., more preferably 180 to 240 ° C. What is necessary is just to set suitably.
  • the maximum temperature in the heat setting treatment step is less than 140 ° C.
  • the fluidity of the binder resin is insufficient and it is difficult to form a nanophase separation structure in the coating layer. Furthermore, the thermal contraction rate of the obtained laminated film becomes large, which is not preferable.
  • the time required to reach the maximum temperature of the heat setting treatment from the temperature at which the phase separation of the coating layer starts to proceed remarkably is preferably 3 seconds or more and less than 20 seconds, and particularly preferably 4 seconds or more and less than 15 seconds.
  • 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 value of the longitudinal thickness unevenness may be increased. Since there is a region in which the value of the vertical thickness unevenness becomes very high 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 retardation of the film can be controlled within a specific range by appropriately setting the stretching ratio, the stretching temperature, and the thickness of the film. For example, it becomes easier to obtain a higher retardation as the stretching ratio between the longitudinal stretching and the lateral stretching is higher, the stretching temperature is lower, and the film is thicker. On the contrary, it becomes easier to obtain a lower retardation as the stretching ratio between the longitudinal stretching and the lateral stretching is lower, the stretching temperature is higher, and the film thickness is thinner. Moreover, the higher the stretching temperature and the lower the total stretching ratio, the easier it is to obtain a film having a lower ratio of retardation to thickness direction (Re / Rth).
  • the lower the stretching temperature and the higher the total stretching ratio the easier it is to obtain a film with a higher ratio of retardation to thickness direction retardation (Re / Rth).
  • the final film forming conditions must be set in consideration of the physical properties necessary for processing in addition to the retardation control.
  • 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, which is not preferable.
  • 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.
  • Polyethylene terephthalate is preferable as the polyester used as the film substrate in order to control the retardation within the range of the present invention even in the above thickness range.
  • a known method can be used in combination.
  • a preliminarily kneaded extruder is used to blend the dried ultraviolet absorber and the polymer raw material.
  • a master batch can be prepared and blended by, for example, a method of mixing the predetermined master batch and a polymer raw material during film formation.
  • the addition weight of the ultraviolet absorber added to the film is preferably 0.3 to 1.5%, more preferably 0.4 to 1.0%.
  • the concentration of the UV absorber in the master batch is preferably 5 to 30% by mass in order to uniformly disperse the UV absorber and mix it economically.
  • a condition for producing the master batch it is preferable to use a kneading extruder and to extrude at a temperature not lower than the melting point of the polyester raw material and not higher than 290 ° C. for 1 to 15 minutes. Above 290 ° C, the weight loss of the UV absorber is large, and the viscosity of the master batch is greatly reduced.
  • the residence time is 1 minute or less, uniform mixing of the ultraviolet 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.
  • phase separation structure was evaluated using a scanning probe microscope (manufactured by SII Nanotechnology, NaNoNavi system / SPA300). The mode (phase mode) was performed. In the phase image, the larger the phase lag, the brighter the color image, and the smaller the phase lag, the darker the image. A small phase lag means that it is hard or has a relatively low adsorption force compared to other phases.
  • the dark hue is the polyvinyl alcohol layer ⁇
  • the light hue is the polyester layer ⁇ .
  • the cantilever used for the measurement was mainly DF3 (spring constant: about 1.6 N / m), and a new one was always used in order to prevent a decrease in sensitivity and resolution due to probe contamination.
  • the scanner used was FS-20A. Further, the observation was performed with a resolution of 512 ⁇ 512 pixels or more, and the observation visual field was 1 ⁇ m ⁇ 1 ⁇ m.
  • the measurement parameters such as the amplitude attenuation rate of the cantilever, the scanning speed, and the scanning frequency at the time of measurement were subjected to line scanning, and conditions were set so that observation can be performed with the highest sensitivity and resolution.
  • phase mode image (bitmap format, 512 ⁇ 512 pixels) obtained as described above is read into image processing software (manufactured by Adobe, Photoshop ver. 7.0) and displayed on the display so that the size of the image is 205 mm ⁇ 205 mm. Displayed. Next, a black line was drawn at the boundary between the light hue and the dark hue with the pencil tool (master diameter: 3 px) of the same software to clarify the boundary between both phases. Furthermore, using the paint tool of the same software, the dark hue was painted black and the light hue was painted white to binarize.
  • phase mode image obtained by the method (1-1) above was saved as a digital image in bitmap format.
  • this image was printed out on A4 quality paper using a printer (manufactured by Xerox, Documentent Color a250).
  • the boundary between the light hue and the dark hue in the image was clarified with a 4B pencil in a bright room under 500 lux illumination by visual confirmation.
  • the dark hue having a diameter of 0.1 ⁇ m or less existing in the bright hue is confirmed to be particles contained in the coating layer unevenly distributed in the bright hue, no boundary line is drawn. , Included in light hue.
  • the boundary line that clarifies the light hue and the dark hue is divided by cutting with a cutter knife, and the mass of the paper of the light hue (polyester phase ⁇ ) and the dark hue (polyvinyl alcohol phase ⁇ ) is measured.
  • the ratio of the mass of the dark hue (polyvinyl alcohol phase ⁇ ) to the total mass of the dark hue paper was determined in units of%. This measurement operation was carried out with measurement samples taken from five different locations, and the average value was taken as the PVA surface fraction. In addition, when the phase separation did not occur, it described as x.
  • the PVA surface fraction can also be measured using the following image analysis method.
  • (1-2-2) Image analysis method The binarized image is displayed with the same software, and a histogram is displayed with the luminance (black, white) on the horizontal axis and the frequency on the vertical axis, and the area ratio of the black part is obtained. .
  • This measurement operation is carried out with measurement samples taken from five different locations, and the average value is taken as the PVA surface fraction.
  • nanophase separation has not occurred, it is described as x.
  • Resin composition Dissolve the resin in deuterated chloroform, perform 1H-NMR analysis using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian, and determine the mol% ratio of each composition from the integral ratio. did.
  • NMR nuclear magnetic resonance analyzer
  • 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 as the acid value.
  • PVA adhesive property A polyvinyl alcohol aqueous solution (Kuraray PVA117) adjusted to a solid content concentration of 5% by mass is coated on the surface of the laminated polyester film so that the thickness of the polyvinyl alcohol resin layer after drying is 2 ⁇ m. It apply
  • the polyvinyl alcohol aqueous solution a solution in which a red dye was added so as to facilitate the determination was used.
  • the prepared evaluation target film was attached to a glass plate having a thickness of 5 mm to which a double-sided tape was attached, and the opposite surface of the evaluation target laminated film on which the polyvinyl alcohol resin layer was formed was attached to the double-sided tape.
  • the PVA adhesion rate was 100, and when all the PVA layer was peeled off, the PVA adhesion rate was 0. In addition, what was partially peeled within one square was also included in the number of peeled.
  • PVA coating property A polyvinyl alcohol aqueous solution (Pura 117 manufactured by Kuraray Co., Ltd.) adjusted to a solid content concentration of 5% by mass is coated on the surface of the laminated polyester film so that the thickness of the polyvinyl alcohol resin layer after drying is 2 ⁇ m.
  • ⁇ The coated whole surface is neatly applied without repelling.
  • ⁇ The coated whole surface is completely repelled without repelling.
  • ⁇ The coated portion is repelled.
  • X It almost repels the whole coated surface.
  • 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 (
  • a polyester film produced by a procedure described later 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 to each other, and on the opposite surface
  • a TAC film manufactured by FUJIFILM Corporation, thickness 80 ⁇ m was attached to create a polarizing plate.
  • the obtained polarizing plate is a liquid crystal display device (liquid crystal cell is incident) with a white LED consisting of a light emitting element combining a blue light emitting diode and a yttrium / aluminum / garnet yellow phosphor as a light source (Nichia, NSPW500CS).
  • the polyester film was placed on the light emitting side of the light emitting side of the polarizing plate having two TAC films as polarizer protective films on the light side. Visual observation was performed from the front side and the oblique direction of the polarizing plate of the liquid crystal display device, and the presence or absence of the occurrence of iridescence was determined as follows.
  • 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 tearing direction was performed so as to be parallel to the orientation main axis direction of the film, and was determined 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
  • 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-5) 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-8) are used instead of poly rnyl alcohol resin (B-1) to prepare aqueous solutions, respectively (Bw-2) to (Bw-8) It was.
  • Table 2 shows the degree of saponification of the polyvinyl alcohol resins (B-1) to (B-8).
  • 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.
  • the obtained polyethylene terephthalate resin (A) had an intrinsic viscosity of 0.62 dl / g and contained substantially no inert particles and internally precipitated particles. (Hereafter, abbreviated as PET (A).)
  • PET (B) 10 parts by weight of a dried UV absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), PET (A) containing no particles (inherent viscosity Was 0.62 dl / g) and 90 parts by mass were mixed, and a polyethylene terephthalate resin (B) containing an ultraviolet absorber was obtained using a kneading extruder (hereinafter abbreviated as PET (B)).
  • 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 After drying 90 parts by mass of PET (A) resin pellets containing no particles as a raw material for the base film intermediate layer and 10 parts by mass of PET (B) resin pellets containing an ultraviolet absorber at 135 ° C. for 6 hours under reduced pressure (1 Torr)
  • the extruder 2 (for the intermediate layer II layer) and PET (A) were dried by a conventional method and supplied to the extruder 1 (for the outer layer I layer and the outer layer III), respectively, and dissolved at 285 ° C.
  • the coating layer is dried at 80 ° C. for 15 seconds. Formed.
  • the unstretched film on which the 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.
  • heat treatment was performed at a temperature of 230 ° C. for 0.5 seconds, and further, a relaxation treatment in the width direction of 3% was performed at 230 ° C. for 10 seconds, and the film thickness was about 50 ⁇ m.
  • a polarizer protective film that was an oriented PET film was obtained.
  • Example 2 A polarizer protective film that is a uniaxially oriented PET film having a thickness of about 100 ⁇ m is obtained by changing the thickness of the unstretched film using the same method as in Example 1 except that the coating solution is applied to one side of the unstretched PET film. Obtained.
  • Example 3 An unstretched film produced by the same method as in Example 1 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. After that, the film was stretched 4.0 times in the width direction in the same manner as in Example 1 to obtain a polarizer protective film which is a biaxially oriented PET film having a film thickness of about 50 ⁇ m.
  • Example 4 In the same manner as in Example 3, the film was stretched 2.0 times in the running direction and 4.0 times in the width direction to obtain a polarizer protective film which is a biaxially oriented PET film having a film thickness of about 50 ⁇ m.
  • Example 5 In the same manner as in Example 3, the film was stretched 3.3 times in the running direction and 4.0 times in the width direction to obtain a polarizer protective film which is a biaxially oriented PET film having a film thickness of about 75 ⁇ m.
  • Example 6 A polarizer protective film, which is a uniaxially oriented PET film having a film thickness of 50 ⁇ m, was obtained in the same manner as in Example 1 without using a PET resin (B) containing an ultraviolet absorber 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 In the same manner as in Example 3, the film was stretched 4.0 times in the running direction and 1.0 times in the width direction to obtain a polarizer protective film which is a uniaxially oriented PET film having a film thickness of about 100 ⁇ m.
  • the obtained film had Re of 3000 nm or more and good visibility, but the mechanical strength was slightly inferior.
  • Example 8 In the same manner as in Example 3, the film was stretched 3.5 times in the running direction and 3.7 times in the width direction to obtain a polarizer protective film which is a biaxially oriented PET film having a film thickness of about 250 ⁇ m.
  • 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 In the same manner as in Example 1, the film was stretched 1.0 times in the running direction and 3.5 times in the width direction to obtain a polarizer protective film which is a uniaxially oriented PET film having a film thickness of about 75 ⁇ m.
  • Example 10 A polarizer protective film, which is a uniaxially oriented PET film having a thickness of about 275 ⁇ m, was obtained by using the same method as in Example 1 and changing the thickness of the unstretched film.
  • Example 11 A polarizer protective film, which is a laminated polyester film, was obtained in the same manner as in Example 1 except that the temperature of the heat treatment and relaxation treatment after tenter stretching was changed to 180 ° C.
  • Example 12 A polarizer protective film, which is a laminated polyester film, was obtained in the same manner as in Example 1 except that the temperature of the heat treatment and relaxation treatment after tenter stretching was changed to 140 ° C.
  • Example 13 A polarizer protective film, which is a laminated polyester film, is obtained in the same manner as in Example 1 except that the following coating agent is mixed and the mass ratio of polyester resin / polyvinyl alcohol resin is changed to 60/40. It was. Water 37.28% by mass Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 10.00% by mass Polyvinyl alcohol aqueous solution (Bw-4) 20.00% 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 14 It is a laminated polyester film in the same manner as in Example 1 except that the following coating agent is mixed and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) is changed to 80/20.
  • a polarizer protective film was 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 15 It is a laminated polyester film in the same manner as in Example 1 except that the following coating agent is mixed and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) is changed to 50/50. A polarizer protective film was obtained.
  • Example 16 A polarizer protective film which is a laminated polyester film is obtained in the same manner as in Example 1 except that the polyester aqueous dispersion is changed to an aqueous dispersion (Aw-2) in which a polyester resin having an acid value of 4 KOHmg / g is dispersed. It was.
  • Example 17 A polarizer protective film that is a laminated polyester film is obtained in the same manner as in Example 1 except that the polyester aqueous dispersion is changed to an aqueous dispersion (Aw-3) in which a polyester resin having an acid value of 6 KOHmg / g is dispersed. It was.
  • Example 18 A polarizer protective film that is a laminated polyester film is obtained in the same manner as in Example 1 except that the polyester aqueous dispersion is changed to an aqueous dispersion (Aw-5) in which a polyester resin having an acid value of 10 KOHmg / g is dispersed. It was.
  • Example 19 A polarizer protective film which is a laminated polyester film in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was changed to an aqueous solution (Bw-6) in which polyvinyl alcohol having a saponification degree of polyvinyl alcohol of 67 mol% was dissolved.
  • Example 20 A polarizer protective film which is a laminated polyester film in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was changed to an aqueous solution (Bw-5) in which polyvinyl alcohol having a saponification degree of polyvinyl alcohol of 70 mol% was dissolved.
  • Example 21 A polarizer protective film, which is a laminated polyester 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) in which the saponification degree of polyvinyl alcohol was 79 mol%. .
  • Example 22 A polarizer protective film, which is a laminated polyester film, was obtained in the same manner as in Example 1, except that the polyvinyl alcohol aqueous solution (Bw-2) had a saponification degree of polyvinyl alcohol of 83 mol%.
  • Example 23 A polarizer protective film as a laminated polyester 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 24 A polarizer protective film, which is a laminated polyester 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 25 A polarizer protective film, which is a laminated polyester 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 26 A polarizer protective film, which is a laminated polyester film, was obtained in the same manner as in Example 1 except that the composition of the coating solution was changed as follows. 40.58% 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 Epoxy crosslinking agent (C-4) 1.00% by mass (Adeka Resin EM-051R ADEKA solid content 50% 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 27 A polarizer protective film, which is a laminated polyester film, was obtained in the same manner as in Example 2 except that an antiglare layer was provided on the surface opposite to the surface having the coating layer. Iris observation was performed by changing the light source of the liquid crystal display device to an organic light emitting diode (OLED).
  • OLED organic light emitting diode
  • Comparative Example 1 In the same manner as in Example 3, the film was stretched 3.6 times in the running direction and 4.0 times in the width direction to obtain a polarizer protective film which is a biaxially oriented PET film having a film thickness of about 38 ⁇ m. The obtained film had low retardation, and rainbow-like color spots were observed when observed from an oblique direction.
  • Comparative Example 2 A polarizer protective film, which is a uniaxially oriented PET film having a thickness of about 10 ⁇ m, was obtained by using the same method as in Example 1 and changing the thickness of the unstretched film. 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.
  • Comparative Example 3 It is a laminated polyester film in the same manner as in Example 1 except that the following coating agent is mixed and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) is changed to 100/0. A polarizer protective film was 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)
  • Comparative Example 4 It is a laminated polyester film in the same manner as in Example 1 except that the following coating agent is mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) is changed to 0/100. A polarizer protective film was 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)
  • Comparative Example 5 It is a laminated polyester film 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 90/10. A polarizer protective film was obtained.
  • Comparative Example 6 A polarizer protective film, which is a laminated polyester film, was obtained in the same manner as in Example 1 except that the temperature of the heat treatment and relaxation treatment after tenter stretching was changed to 100 ° C.
  • Comparative Example 7 A polarizer protective film that is a laminated polyester 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-8) in which polyvinyl alcohol having a saponification degree of 99 mol% was dissolved. .
  • Comparative Example 8 A polarizer protective film, which is a laminated polyester 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-7) in which polyvinyl alcohol having a saponification degree of 40 mol% was dissolved. .
  • Comparative Example 9 A polarizer protective film that is a laminated polyester film is obtained in the same manner as in Example 1 except that the polyester aqueous dispersion is changed to an aqueous dispersion (Aw-4) in which a polyester resin having an acid value of 25 KOHmg / g is dispersed. It was.
  • Example 1 was performed except that the light source of the liquid crystal display device was a cold cathode tube.
  • Reference example 1 The adhesion test was conducted using a TAC film (manufactured by Fuji Film Co., Ltd., thickness 80 ⁇ m, saponified) as a laminated polyester film.
  • polarizer protective films of Examples 1 to 27 a nanophase separation structure was observed.
  • a phase contrast micrograph of the surface of the coating layer of the polarizer protective film of Example 14 is shown in FIG.
  • the polarizer protective film of Examples 1 to 27 having a surface fraction of the PVA phase of 30% or more has no problem in coating properties and is an excellent PVA film that can be evaluated as equivalent to a TAC film in a single peel test And showed adhesiveness.
  • 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.

Abstract

L'invention concerne un film de protection d'éléments polarisants qui présente une excellente adhésion du film en polyester sur une couche de résine d'alcool polyvinylique, par exemple un élément polarisant ou un adhésif appliqué sur l'élément polarisant, qui est capable de supporter la réduction d'épaisseur des dispositifs d'affichage à cristaux liquides et qui ne provoque pas de détérioration de la visibilité à cause d'irrégularités provoquant une irisation. Le film de protection d'éléments polarisants comprend un film en polyester et une couche de revêtement formée sur au moins une surface de celui-ci, et il est caractérisé en ce que le film en polyester a un retard optique entre 3 000 et 30 000 nm et la couche de revêtement comprend une résine d'alcool polyvinylique et une résine de polyester, et la surface de la couche de revêtement a une structure de nano-séparation de phase qui contient une phase constituée de la résine d'alcool polyvinylique qui s'est agrégée et une phase constituée de la résine de polyester qui s'est agrégée et dans laquelle l'aire de la phase d'alcool de polyvinyle constitue une proportion d'au moins 30 % mais inférieure à 99 %.
PCT/JP2012/083848 2011-12-28 2012-12-27 Dispositif d'affichage à cristaux liquides, polariseur et film de protection d'élément polarisant WO2013100041A1 (fr)

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JP2014032275A (ja) * 2012-08-02 2014-02-20 Toyobo Co Ltd 液晶表示装置、偏光板及び偏光子保護フィルム
JP2015041529A (ja) * 2013-08-22 2015-03-02 帝人デュポンフィルム株式会社 透明電極用フィルム
JP2015087694A (ja) * 2013-11-01 2015-05-07 東洋紡株式会社 偏光子保護フィルム、偏光板及び液晶表示装置
JP2015102636A (ja) * 2013-11-22 2015-06-04 富士フイルム株式会社 偏光子保護フィルム、偏光板及び画像表示装置
JP2015143758A (ja) * 2014-01-31 2015-08-06 富士フイルム株式会社 光学用ポリエステルフィルム、偏光板、画像表示装置、光学用ポリエステルフィルムの製造方法、および易接着層用組成物
WO2015146883A1 (fr) * 2014-03-26 2015-10-01 富士フイルム株式会社 Film de résine polyester, procédé de production de film de résine polyester, plaque polarisante, dispositif d'affichage d'image, film de revêtement dur, film de détection pour panneaux tactiles, film de prévention de diffusion de verre et panneau tactile
JP2015189194A (ja) * 2014-03-28 2015-11-02 富士フイルム株式会社 ポリエステルフィルム、ポリエステルフィルムの製造方法、偏光板、画像表示装置、ハードコートフィルムおよびタッチパネル
JP2016030331A (ja) * 2014-07-25 2016-03-07 富士フイルム株式会社 積層フィルム、光学フィルム、偏光子保護フィルム、偏光板、画像表示装置及び積層フィルムの製造方法
CN107636753A (zh) * 2016-01-08 2018-01-26 大日本印刷株式会社 图像显示装置
WO2018110625A1 (fr) * 2016-12-14 2018-06-21 東洋紡株式会社 Dispositif d'affichage à cristaux liquides, plaque de polarisation, et film protecteur de polariseur
JP2018124572A (ja) * 2018-04-16 2018-08-09 東洋紡株式会社 偏光子保護フィルム、偏光板及び液晶表示装置
WO2019142615A1 (fr) * 2018-01-19 2019-07-25 東洋紡株式会社 Film polyester à adhésion facile

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JP2014032275A (ja) * 2012-08-02 2014-02-20 Toyobo Co Ltd 液晶表示装置、偏光板及び偏光子保護フィルム
JP2015041529A (ja) * 2013-08-22 2015-03-02 帝人デュポンフィルム株式会社 透明電極用フィルム
JP2015087694A (ja) * 2013-11-01 2015-05-07 東洋紡株式会社 偏光子保護フィルム、偏光板及び液晶表示装置
JP2015102636A (ja) * 2013-11-22 2015-06-04 富士フイルム株式会社 偏光子保護フィルム、偏光板及び画像表示装置
JP2015143758A (ja) * 2014-01-31 2015-08-06 富士フイルム株式会社 光学用ポリエステルフィルム、偏光板、画像表示装置、光学用ポリエステルフィルムの製造方法、および易接着層用組成物
WO2015146883A1 (fr) * 2014-03-26 2015-10-01 富士フイルム株式会社 Film de résine polyester, procédé de production de film de résine polyester, plaque polarisante, dispositif d'affichage d'image, film de revêtement dur, film de détection pour panneaux tactiles, film de prévention de diffusion de verre et panneau tactile
JP2015184664A (ja) * 2014-03-26 2015-10-22 富士フイルム株式会社 ポリエステル樹脂フィルム、ポリエステル樹脂フィルムの製造方法、偏光板、画像表示装置、ハードコートフィルム、タッチパネル用センサーフィルム、ガラス飛散防止フィルム、およびタッチパネル
JP2015189194A (ja) * 2014-03-28 2015-11-02 富士フイルム株式会社 ポリエステルフィルム、ポリエステルフィルムの製造方法、偏光板、画像表示装置、ハードコートフィルムおよびタッチパネル
JP2016030331A (ja) * 2014-07-25 2016-03-07 富士フイルム株式会社 積層フィルム、光学フィルム、偏光子保護フィルム、偏光板、画像表示装置及び積層フィルムの製造方法
US11204524B2 (en) 2016-01-08 2021-12-21 Dai Nippon Printing Co., Ltd. Image display device
CN107636753A (zh) * 2016-01-08 2018-01-26 大日本印刷株式会社 图像显示装置
WO2018110625A1 (fr) * 2016-12-14 2018-06-21 東洋紡株式会社 Dispositif d'affichage à cristaux liquides, plaque de polarisation, et film protecteur de polariseur
CN110050208A (zh) * 2016-12-14 2019-07-23 东洋纺株式会社 液晶显示装置、偏光板和偏振片保护膜
KR20190087619A (ko) * 2016-12-14 2019-07-24 도요보 가부시키가이샤 액정 표시 장치, 편광판 및 편광자 보호 필름
JPWO2018110625A1 (ja) * 2016-12-14 2019-10-24 東洋紡株式会社 液晶表示装置、偏光板および偏光子保護フィルム
KR102216520B1 (ko) * 2016-12-14 2021-02-17 도요보 가부시키가이샤 액정 표시 장치, 편광판 및 편광자 보호 필름
CN110050208B (zh) * 2016-12-14 2021-09-28 东洋纺株式会社 液晶显示装置、偏光板和偏振片保护膜
CN113912994A (zh) * 2016-12-14 2022-01-11 东洋纺株式会社 聚对苯二甲酸乙二醇酯系树脂薄膜、液晶显示装置和偏光板
JP7156034B2 (ja) 2016-12-14 2022-10-19 東洋紡株式会社 液晶表示装置、偏光板および偏光子保護フィルム
JP7396402B2 (ja) 2016-12-14 2023-12-12 東洋紡株式会社 液晶表示装置、偏光板および偏光子保護フィルム
WO2019142615A1 (fr) * 2018-01-19 2019-07-25 東洋紡株式会社 Film polyester à adhésion facile
JP6597930B1 (ja) * 2018-01-19 2019-10-30 東洋紡株式会社 易接着性ポリエステルフィルム
JP2018124572A (ja) * 2018-04-16 2018-08-09 東洋紡株式会社 偏光子保護フィルム、偏光板及び液晶表示装置

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