WO2020209222A1 - 偏光子保護用積層体および該積層体を用いた偏光板 - Google Patents

偏光子保護用積層体および該積層体を用いた偏光板 Download PDF

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Publication number
WO2020209222A1
WO2020209222A1 PCT/JP2020/015515 JP2020015515W WO2020209222A1 WO 2020209222 A1 WO2020209222 A1 WO 2020209222A1 JP 2020015515 W JP2020015515 W JP 2020015515W WO 2020209222 A1 WO2020209222 A1 WO 2020209222A1
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Prior art keywords
layer
polarizer
laminate
polarizing plate
resin
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PCT/JP2020/015515
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English (en)
French (fr)
Japanese (ja)
Inventor
和哉 三輪
卓史 上条
大介 濱本
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日東電工株式会社
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Priority to JP2021513623A priority Critical patent/JPWO2020209222A1/ja
Priority to KR1020217031928A priority patent/KR20210151803A/ko
Priority to CN202080027555.9A priority patent/CN113711093A/zh
Publication of WO2020209222A1 publication Critical patent/WO2020209222A1/ja

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    • 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
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical 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
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

Definitions

  • the present invention relates to a laminate for protecting a polarizer and a polarizing plate using the laminate.
  • a polarizing plate is often arranged on at least one side of a display cell due to the image forming method.
  • image display devices have become thinner and more flexible, and along with this, there is a strong demand for thinner polarizing plates and their constituent films (for example, polarizing element protective films).
  • polarizing element protective films the thinner the polarizing element protective film, the more remarkable the problem of durability that the optical characteristics of the polarizing plate deteriorate in a heating and humidifying environment.
  • a polarizer protective film capable of realizing a thin and highly durable polarizing plate a polarizer protective film composed of a solidified coating film of a predetermined resin solution has been studied. Such technologies are in the early stages of development, leaving much room for consideration.
  • the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to realize a thin and highly durable polarizing plate, and further, cracks and / or cracks are suppressed. It is an object of the present invention to provide a laminate for protecting a polarizer.
  • the laminate for protecting a polarizer of the present invention comprises a first layer composed of a solidified coating film of an organic solvent solution of a thermoplastic acrylic resin having a glass transition temperature of 95 ° C. or higher, and a cured product of a curable resin. It has a configured second layer, and the thickness of the second layer is 1.0 ⁇ m or more.
  • the elastic modulus of the second layer is 50 MPa or more, and the elongation rate is 2% or more.
  • the pencil hardness of the second layer is 2H or more.
  • the thickness of the first layer is 10 ⁇ m or less.
  • the in-plane retardation Re (550) of the first layer is 0 nm to 10 nm, and the thickness direction retardation Rth (550) is ⁇ 20 nm to +10 nm.
  • a polarizing plate is provided.
  • the polarizing plate has a polarizing element and the above-mentioned laminate for protecting the polarizer arranged on one side of the polarizing element.
  • the first layer of the laminate for protecting the polarizer is arranged so that the first layer is on the polarizer side.
  • the polarizing plate is arranged on the viewing side of the image display device, and the second layer of the polarizing element protection laminate is arranged on the viewing side.
  • the polarizer protective film has a first layer composed of a solidified coating film of an organic solvent solution of a thermoplastic acrylic resin having a glass transition temperature of 95 ° C. or higher, and a curable resin (typically).
  • Active energy ray-curable resin can be laminated with a second layer composed of a cured product to realize a thin and durable polarizing plate, and further crack and / or crack. It is possible to realize a polarizer protective film (laminated body for protecting a polarizer) in which the amount is suppressed.
  • FIG. 1 of a laminate for protecting a polarizer is a schematic cross-sectional view of a laminate for protecting a polarizer according to one embodiment of the present invention.
  • the polarizing element protection laminate 100 of the illustrated example has a first layer 10 and a second layer 20.
  • the first layer 10 is composed of a solidified coating film of an organic solvent solution of a thermoplastic acrylic resin having a glass transition temperature of 95 ° C. or higher.
  • the second layer 20 is composed of a cured product of a curable resin.
  • the thickness of the second layer is 1.0 ⁇ m or more.
  • the first layer and the second layer will be specifically described.
  • the first layer can typically function as a protective layer for the polarizer.
  • the first layer is composed of a solidified coating film of an organic solvent solution of a thermoplastic acrylic resin (hereinafter, simply referred to as an acrylic resin).
  • an acrylic resin a thermoplastic acrylic resin
  • the acrylic resin has a glass transition temperature (Tg) of 95 ° C. or higher as described above. As a result, the Tg of the first layer becomes 95 ° C. or higher.
  • Tg of the acrylic resin is typically 100 ° C. or higher, preferably 110 ° C. or higher, more preferably 115 ° C. or higher, still more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher.
  • the Tg of the acrylic resin is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, still more preferably 200 ° C. or lower, and particularly preferably 160 ° C. or lower. When the Tg of the acrylic resin is in such a range, the moldability can be excellent.
  • any suitable acrylic resin can be adopted as long as it has Tg as described above.
  • Acrylic resins typically contain an alkyl (meth) acrylate as a main component as a monomer unit (repeating unit).
  • (meth) acrylic means acrylic and / or methacrylic.
  • alkyl (meth) acrylate constituting the main skeleton of the acrylic resin include those having a linear or branched alkyl group having 1 to 18 carbon atoms. These can be used alone or in combination.
  • any suitable copolymerization monomer may be introduced into the acrylic resin by copolymerization.
  • the repeating unit derived from alkyl (meth) acrylate is typically represented by the following general formula (1):
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents a hydrogen atom or an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms which may be substituted. Shown.
  • the substituent include halogens and hydroxyl groups.
  • alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate.
  • R 5 is preferably a hydrogen atom or
  • Acrylic resins may also include only a single alkyl (meth) acrylate units, even if R 4 and R 5 include a plurality of different alkyl (meth) acrylate unit in the above general formula (1) Good.
  • the content ratio of the alkyl (meth) acrylate unit in the acrylic resin is preferably 50 mol% to 98 mol%, more preferably 55 mol% to 98 mol%, still more preferably 60 mol% to 98 mol%, and particularly preferably. It is 65 mol% to 98 mol%, most preferably 70 mol% to 97 mol%. If the content ratio is less than 50 mol%, the effects expressed from the alkyl (meth) acrylate unit (for example, high heat resistance and high transparency) may not be sufficiently exhibited. If the content ratio is more than 98 mol%, the resin is brittle and easily cracked, high mechanical strength cannot be sufficiently exhibited, and productivity may be inferior.
  • the acrylic resin may have a repeating unit including a ring structure.
  • the repeating unit including the ring structure include a lactone ring unit, a glutaric anhydride unit, a glutarimide unit, a maleic anhydride unit, and a maleimide (N-substituted maleimide) unit. Only one type of the repeating unit including the ring structure may be contained in the repeating unit of the acrylic resin, or two or more types may be contained.
  • the lactone ring unit is preferably represented by the following general formula (2):
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the organic residue may contain an oxygen atom.
  • the acrylic resin may be contained only a single lactone ring units may be R 1, R 2 and R 3 in the general formula (2) is contains different lactone ring unit ..
  • Acrylic resins having a lactone ring unit are described in, for example, Japanese Patent Application Laid-Open No. 2008-181078, and the description in this publication is incorporated herein by reference.
  • the glutarimide unit is preferably represented by the following general formula (3):
  • R 11 and R 12 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms
  • R 13 is an alkyl group having 1 to 18 carbon atoms and 3 to 12 carbon atoms.
  • the cycloalkyl group of the above, or an aryl group having 6 to 10 carbon atoms is shown.
  • R 11 and R 12 are independently hydrogen or methyl groups
  • R 13 is a hydrogen, methyl group, butyl group or cyclohexyl group, respectively. More preferably, R 11 is a methyl group, R 12 is a hydrogen, and R 13 is a methyl group.
  • the acrylic resin may contain only a single glutarimide unit, or may contain a plurality of glutarimide units having different R 11 , R 12 and R 13 in the above general formula (3). ..
  • Acrylic resins having a glutarimide unit are, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328334, JP-A-2006-337491, JP-A-2006-337492. It is described in Japanese Patent Application Laid-Open No. 2006-337493 and Japanese Patent Application Laid-Open No. 2006-337569, and the description of the relevant publication is incorporated herein by reference. Note that the glutaric anhydride units, nitrogen atom substituted by R 13 in the general formula (3), except that the oxygen atom, the above description is applied about the glutarimide units.
  • the structure of the maleic anhydride unit and the maleimide (N-substituted maleimide) unit is specified from the name, so specific description thereof will be omitted.
  • the content ratio of the repeating unit including the ring structure in the acrylic resin is preferably 1 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, and further preferably 20 mol% to 30 mol%. If the content ratio is too small, Tg may be less than 110 ° C., and the heat resistance, solvent resistance and surface hardness of the obtained first layer may be insufficient. If the content is too high, moldability and transparency may be insufficient.
  • the acrylic resin may contain a repeating unit other than the alkyl (meth) acrylate unit and the repeating unit including the ring structure.
  • a repeating unit include a repeating unit derived from a vinyl-based monomer copolymerizable with the monomer constituting the above unit (another vinyl-based monomer unit).
  • other vinyl-based monomers include acrylic acid, methacrylic acid, crotonic acid, 2- (hydroxymethyl) acrylic acid, 2- (hydroxyethyl) acrylic acid, acrylonitrile, methacrylonitrile, etacrylonitrile, and allyl.
  • Glycidyl ether maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, methacryl Cyclohexylaminoethyl acid, N-vinyldiethylamine, N-acetylvinylamine, allylamine, metaallylamine, N-methylallylamine, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acroyl-oxazoline, N-phenylmaleimide, Examples thereof include phenylaminoethyl methacrylate, styrene, ⁇ -methylstyrene, p-glycidylstyrene, p-amin
  • the weight average molecular weight of the acrylic resin is preferably 1,000,000 to 2000000, more preferably 5000 to 1,000,000, further preferably 10000 to 500000, particularly preferably 50,000 to 500000, and most preferably 60000 to 150,000.
  • the weight average molecular weight can be determined by polystyrene conversion using, for example, a gel permeation chromatograph (GPC system, manufactured by Tosoh). Tetrahydrofuran can be used as the solvent.
  • the acrylic resin can be polymerized by any suitable polymerization method using the above-mentioned monomer units in an appropriate combination.
  • the acrylic resin and another resin may be used in combination. That is, the monomer component constituting the acrylic resin and the monomer component constituting the other resin may be copolymerized, and the copolymer may be used for molding the first layer described later; the acrylic resin and the other resin.
  • the blend with may be subjected to the molding of the first layer.
  • other resins include thermoplastic resins such as styrene resin, polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, and polyetherimide.
  • the type and blending amount of the resin to be used in combination can be appropriately set according to the purpose and the properties desired for the obtained film.
  • a styrene resin preferably an acrylonitrile-styrene copolymer
  • a retardation control agent preferably an acrylonitrile-styrene copolymer
  • the content of the acrylic resin in the blend of the acrylic resin and the other resin is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight. By weight%, more preferably 70% by weight to 100% by weight, particularly preferably 80% by weight to 100% by weight. If the content is less than 50% by weight, the high heat resistance and high transparency inherent in the acrylic resin may not be sufficiently reflected.
  • the first layer is composed of a solidified coating film of an organic solvent solution of an acrylic resin having a glass transition temperature of 95 ° C. or higher. With such a solidified coating film, the thickness can be significantly reduced as compared with the extrusion-molded film.
  • the thickness of the first layer is, for example, 10 ⁇ m or less, preferably 7 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 3 ⁇ m or less.
  • the lower limit of the thickness of the first layer can be, for example, 1 ⁇ m.
  • such a solidified coating film is compared with a cured product of a thermosetting resin or an active energy ray-curable resin (for example, an ultraviolet curable resin) at the time of film molding. Since the shrinkage is small and the residual monomer or the like is not contained, the deterioration of the film itself can be suppressed, and the adverse effect on the polarizing plate (polarizer) caused by the residual monomer or the like can be suppressed. Further, it has an advantage that it is excellent in humidification durability because it has low hygroscopicity and moisture permeability as compared with a solidified water-based coating film such as an aqueous solution or an aqueous dispersion. As a result, it is possible to realize a polarizing plate having excellent durability that can maintain the optical characteristics even in a heating and humidifying environment.
  • a solidified water-based coating film such as an aqueous solution or an aqueous dispersion.
  • the Tg of the first layer is as described in Section A-2-1 above regarding the acrylic resin.
  • the first layer is preferably substantially optically isotropic.
  • substantially optically isotropic means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is ⁇ 20 nm to +10 nm. Say something.
  • the in-plane retardation Re (550) is more preferably 0 nm to 5 nm, further preferably 0 nm to 3 nm, and particularly preferably 0 nm to 2 nm.
  • the phase difference Rth (550) in the thickness direction is more preferably ⁇ 5 nm to + 5 nm, further preferably -3 nm to + 3 nm, and particularly preferably -2 nm to + 2 nm.
  • Re (550) and Rth (550) of the first layer are in such a range, it is possible to prevent an adverse effect on the display characteristics when the polarizing plate including the first layer is applied to an image display device.
  • Rth (550) is a phase difference in the thickness direction of the film measured with light having a wavelength of 550 nm at 23 ° C.
  • nx is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction)
  • ny is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advancing axis direction).
  • nz is the refractive index in the thickness direction
  • d is the thickness (nm) of the film.
  • the light transmittance is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more. When the light transmittance is in such a range, the desired transparency can be ensured.
  • the light transmittance can be measured, for example, by a method according to ASTM-D-1003.
  • the haze of the first layer is preferably 5% or less, more preferably 3% or less, still more preferably 1.5% or less, and particularly preferably 1% or less.
  • the haze is 5% or less, a good clear feeling can be given to the film. Further, even when the polarizing plate on the visual side of the image display device is used, the displayed contents can be visually recognized satisfactorily.
  • the YI of the first layer at a thickness of 3 ⁇ m is preferably 1.27 or less, more preferably 1.25 or less, still more preferably 1.23 or less, and particularly preferably 1.20 or less. If the YI exceeds 1.3, the optical transparency may be insufficient.
  • the b value (a measure of hue according to the hunter's color system) at a thickness of 3 ⁇ m of the first layer is preferably less than 1.5, more preferably 1.0 or less. When the b value is 1.5 or more, an undesired color may appear.
  • a sample of the film constituting the first layer is cut into 3 cm squares, and a high-speed integrating sphere type spectral transmittance measuring machine (trade name: DOT-3C: manufactured by Murakami Color Technology Laboratory) is used. It can be obtained by measuring the hue and evaluating the hue according to the hunter's color system.
  • the first layer may contain any suitable additive depending on the purpose.
  • the additives include ultraviolet absorbers; leveling agents; antioxidants such as hindered phenol-based, phosphorus-based and sulfur-based; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers and heat stabilizers; glass fibers, Reinforcing materials such as carbon fibers; Near infrared absorbers; Flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; Antistatic agents such as anionic, cationic and nonionic surfactants; Inorganic pigments , Organic pigments, colorants such as dyes; organic fillers or inorganic fillers; resin modifiers; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants; and the like.
  • the additive may be added at the time of polymerization of the acrylic resin, or may be added to the solution at the time of film formation.
  • An easy-adhesion layer may be formed on the side of the first layer opposite to the second layer (typically, the polarizer side when used for a polarizing plate).
  • the easy-adhesion layer contains, for example, an aqueous polyurethane and an oxazoline-based cross-linking agent.
  • the second layer can typically function as a hard coat layer.
  • cracks and / or cracks in the first layer can be maintained while maintaining the excellent characteristics of the first layer (a polarizing plate having excellent durability despite being extremely thin) can be realized. Cracking can be suppressed.
  • the second layer is composed of a cured product of a curable resin.
  • the curable resin may be an active energy ray-curable resin or a thermosetting resin. It is preferably an active energy ray-curable resin.
  • the active energy ray-curable resin has the advantages that the reaction can be easily controlled and the operability is excellent.
  • the thickness of the second layer is 1.0 ⁇ m or more, preferably 2.0 ⁇ m or more, and more preferably 2.5 ⁇ m or more as described above.
  • the upper limit of the thickness of the second layer can be, for example, 5.0 ⁇ m. If the thickness of the second layer is too small, the curing reaction may be insufficient and layer formation may be difficult, and the rigidity of the formed layer may be insufficient. If the thickness of the second layer is too large, the flexibility may be insufficient and cracks may easily occur.
  • the elastic modulus of the second layer is 50 MPa or more, and the elongation rate is 2% or more.
  • the elastic modulus of the second layer is more preferably 500 MPa or more, further preferably 1000 MPa or more, particularly preferably 2800 MPa or more, and particularly preferably 2900 MPa or more.
  • the upper limit of the elastic modulus of the second layer can be, for example, 7000 MPa. If the elastic modulus of the second layer is too high, it becomes brittle and may not function as a protective layer.
  • the elongation rate of the second layer is more preferably 5% or more, further preferably 10% or more, particularly preferably 20% or more, and particularly preferably 40% or more.
  • the upper limit of the second layer can be, for example, 300%.
  • the elastic modulus of the second layer is large, the elongation rate can be small, and when the elastic modulus of the second layer is small, the elongation rate can be large.
  • the elastic modulus and elongation can be measured according to, for example, JIS K 7161.
  • the pencil hardness of the second layer is preferably 2H or more, more preferably 3H or more, and further preferably 4H or more.
  • the upper limit of the pencil hardness of the second layer can be, for example, 6H.
  • Pencil hardness can be measured according to, for example, JIS K 5400.
  • the second layer can be typically composed of any suitable active energy ray-curable resin that can satisfy the above characteristics.
  • the active energy ray-curable resin include an ultraviolet curable resin and an electron beam-curable resin.
  • UV curable resin is preferable. This is because the second layer can be efficiently formed by a simple processing operation.
  • the ultraviolet curable resin include various resins such as polyester-based, acrylic-based, urethane-based, amide-based, silicone-based, and epoxy-based resins.
  • the UV curable resin is a urethane acrylate resin. The details of the ultraviolet curable resin are described, for example, in Japanese Patent No. 6199605 as an organic component of the hard coat layer. The description of this publication is incorporated herein by reference.
  • FIG. 2 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention.
  • the polarizing plate 200 of the illustrated example has a polarizer 120 and a polarizing element protection laminate 100 arranged on one side of the polarizer 120.
  • the polarizer 100 is a laminate for protecting a polarizer according to the embodiment of the present invention according to the above item A.
  • the laminate 100 for protecting the polarizer is arranged so that the first layer 10 is on the side of the polarizer 120.
  • the polarizing plate 200 is typically located on the visible side of the display cell. Be placed.
  • the second layer 20 of the polarizing element protection laminate 100 is arranged on the viewing side.
  • the polarizing plate has an adhesive layer as the outermost layer on one side (typically, the side opposite to the polarizing element protection laminate 100 of the polarizer 120), and is bonded to the display cell. Is possible.
  • a surface protective film and / or a carrier film may be temporarily attached to the polarizing plate so as to reinforce and / or support the polarizing plate.
  • a separator is temporarily attached to the surface of the pressure-sensitive adhesive layer so that the pressure-sensitive adhesive layer can be protected and the polarizing plate can be rolled until actual use.
  • the polarizing plate may be long or single-wafered. When the polarizing plate has a long shape, the polarizing plate can be wound preferably in a roll shape.
  • the thickness of the polarizer protective film can be made very thin by adopting the laminate for protecting the polarizer according to the above item A. Further, such a polarizer protective laminate can be formed directly on the polarizer (ie, without the intervention of an adhesive layer or an adhesive layer). As a result, the total thickness of the polarizing plate can be made extremely thin.
  • the total thickness of the polarizing plate is, for example, 40 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and further preferably 15 ⁇ m or less.
  • the lower limit of the total thickness of the polarizing plate can be, for example, 10 ⁇ m.
  • the laminate for protecting the polarizer according to the above item A it is possible to realize a polarizing plate having excellent durability even though it is very thin. Specifically, it is possible to realize a polarizing plate in which deterioration of optical characteristics is suppressed even in a heating and humidifying environment.
  • the amount of change ⁇ Ts of the simple substance transmittance Ts and the amount of change ⁇ P of the degree of polarization P after being left in an environment of 85 ° C. and 85% RH for 48 hours are very small, respectively.
  • the simple substance transmittance Ts can be measured using, for example, an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, product name "V7100").
  • the degree of polarization P is calculated by the following equation from the simple substance transmittance (Ts), the parallel transmittance (Tp) and the orthogonal transmittance (Tc) measured by using an ultraviolet-visible spectrophotometer.
  • Polarization degree (P) (%) ⁇ (Tp-Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • the Ts, Tp, and Tc are Y values measured by the JIS Z 8701 2 degree field of view (C light source) and corrected for luminosity factor.
  • Ts and P are substantially properties of the polarizer.
  • ⁇ Ts and ⁇ P are calculated by the following formulas, respectively.
  • Ts 0 is the single transmittance before leaving (initial)
  • Ts 48 is the single transmittance after leaving
  • P 0 is the degree of polarization before leaving (initial)
  • P 48 is after leaving.
  • ⁇ Ts is preferably 3.0% or less, more preferably 2.7% or less, still more preferably 2.4% or less.
  • ⁇ P is preferably ⁇ 0.05% to 0%, more preferably ⁇ 0.03% to 0%, and even more preferably ⁇ 0.01% to 0%.
  • the polarizing plate of the present invention is extremely thin as described above, it can be suitably applied to a flexible image display device. More preferably, the image display device has a curved shape (substantially a curved display screen) and / or is bendable or bendable. Specific examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device). Needless to say, the above description does not prevent the polarizing plate of the present invention from being applied to a normal image display device.
  • EL electroluminescence
  • Polarizer As the polarizer, any suitable polarizer can be adopted.
  • the polarizer can typically be made using a laminate of two or more layers. The method for manufacturing the polarizer will be described later in Section B-2 as the method for manufacturing the polarizing plate.
  • the thickness of the polarizer is preferably 1 ⁇ m to 8 ⁇ m, more preferably 1 ⁇ m to 7 ⁇ m, and further preferably 2 ⁇ m to 5 ⁇ m.
  • the boric acid content of the polarizer is preferably 10% by weight or more, more preferably 13% by weight to 25% by weight.
  • the boric acid content can be calculated as the amount of boric acid contained in the polarizer per unit weight, for example, by using the following formula from the neutralization method.
  • the iodine content of the polarizer is preferably 2% by weight or more, more preferably 2% by weight to 10% by weight.
  • the iodine content of the polarizer is in such a range, the ease of curl adjustment at the time of bonding is well maintained due to the synergistic effect with the above boric acid content, and the curl at the time of heating is maintained. It is possible to improve the appearance durability at the time of heating while satisfactorily suppressing the above.
  • the term "iodine content” means the amount of all iodine contained in the polarizer (PVA-based resin film).
  • Iodine content means the amount of iodine that includes all of these forms.
  • the iodine content can be calculated, for example, by the calibration curve method of fluorescent X-ray analysis.
  • the polyiodine ion exists in a state in which a PVA-iodine complex is formed in the polarizer. By forming such a complex, absorption dichroism can be exhibited in the wavelength range of visible light.
  • a complex of PVA and tri-iodide ion (PVA ⁇ I 3 -) has a light absorption peak around 470 nm
  • a complex of PVA and five iodide ion (PVA ⁇ I 5 -) is 600nm near Has an absorptive peak.
  • polyiodine ions can absorb light in a wide range of visible light, depending on their morphology.
  • iodine ion (I ⁇ ) has an absorption peak near 230 nm and is not substantially involved in the absorption of visible light. Therefore, polyiodine ions present in the form of a complex with PVA may be mainly involved in the absorption performance of the polarizer.
  • the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the simple substance transmittance Ts of the polarizer is preferably 40% to 48%, more preferably 41% to 46%.
  • the degree of polarization P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more.
  • B-2 Method for manufacturing polarizing plate B-2-1.
  • Method for producing a polarizer The method for producing a polarizer according to the above item B-1 is a polyvinyl alcohol containing a halide and a polyvinyl alcohol-based resin (PVA-based resin) on one side of a long thermoplastic resin base material.
  • PVA-based resin layer By forming a based resin layer (PVA-based resin layer) to form a laminated body, and by heating the laminated body while carrying it in the longitudinal direction, an aerial auxiliary stretching treatment, a dyeing treatment, and an underwater stretching treatment.
  • the drying shrinkage treatment of shrinking by 2% or more in the width direction and the drying shrinkage treatment are performed in this order.
  • the content of the halide in the PVA-based resin layer is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.
  • the drying shrinkage treatment is preferably carried out using a heating roll, and the temperature of the heating roll is preferably 60 ° C. to 120 ° C. According to such a manufacturing method, the above-mentioned polarizer can be obtained.
  • a laminate containing a PVA-based resin layer containing a halide stretching the laminate to multi-step stretching including aerial auxiliary stretching and underwater stretching, and heating the stretched laminate with a heating roll.
  • a polarizer having excellent optical characteristics typically, simple substance transmittance and degree of polarization
  • the laminated body can be uniformly shrunk over the entire laminated body while being conveyed.
  • a heating roll in the drying shrinkage treatment step the laminated body can be uniformly shrunk over the entire laminated body while being conveyed.
  • a polarizer having excellent optical characteristics can be stably produced, and variations in the optical characteristics of the polarizer (particularly, single transmittance) can be suppressed. can do.
  • the halide and the drying shrinkage treatment will be described. Details of manufacturing methods other than these are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. The entire description of the publication is incorporated herein by reference.
  • a PVA-based resin layer containing a halide and a PVA-based resin can be formed by applying a coating liquid containing a halide and a PVA-based resin onto a thermoplastic resin base material and drying the coating film.
  • the coating liquid is typically a solution in which the halide and the PVA-based resin are dissolved in a solvent.
  • the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylpropane, and amines such as ethylenediamine and diethylenetriamine. These can be used alone or in combination of two or more. Of these, water is preferred.
  • the PVA-based resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film that adheres to the thermoplastic resin base material can be formed.
  • any suitable halide can be adopted.
  • iodide and sodium chloride examples include potassium iodide, sodium iodide, and lithium iodide. Of these, potassium iodide is preferred.
  • the amount of the halide in the coating liquid is preferably 5 parts by weight to 20 parts by weight, and more preferably 10 parts by weight to 15 parts by weight with respect to 100 parts by weight of the PVA-based resin. If the amount of the halide is too large, the halide may bleed out and the finally obtained polarizer may become cloudy.
  • the orientation of the polyvinyl alcohol molecules in the PVA-based resin is increased.
  • the stretched PVA-based resin layer is immersed in a liquid containing water, the polyvinyl alcohol molecules become more oriented. The orientation may be disturbed and the orientation may decrease.
  • the laminate of the thermoplastic resin base material and the PVA-based resin layer is stretched in boric acid water, the laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin base material. In the case of stretching, the tendency of the degree of orientation to decrease is remarkable.
  • stretching a PVA film alone in boric acid water is generally performed at 60 ° C.
  • stretching of a laminate of A-PET (thermoplastic resin base material) and a PVA-based resin layer is performed. It is carried out at a high temperature of about 70 ° C., and in this case, the orientation of PVA at the initial stage of stretching may decrease before it is increased by stretching in water.
  • a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin base material is prepared, and the laminate is stretched at a high temperature (auxiliary stretching) in air before being stretched in boric acid water.
  • Crystallization of the PVA-based resin in the PVA-based resin layer of the laminated body after the auxiliary stretching can be promoted.
  • the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide.
  • the optical characteristics of the polarizer obtained through a treatment step of immersing the laminate in a liquid such as a dyeing treatment and a stretching treatment in water, can be improved.
  • the dry shrinkage treatment may be carried out by heating the entire zone by zone heating, or by heating the transport roll (using a so-called heating roll) (heating roll drying method). Preferably, both are used.
  • heating roll heating roll drying method
  • the crystallization of the thermoplastic resin base material can be efficiently promoted and the crystallinity can be increased, which is relatively low. Even at the drying temperature, the crystallinity of the thermoplastic resin base material can be satisfactorily increased.
  • the rigidity of the thermoplastic resin base material is increased so that it can withstand the shrinkage of the PVA-based resin layer due to drying, and curling is suppressed.
  • the laminated body can be dried while being maintained in a flat state, so that not only curling but also wrinkles can be suppressed.
  • the laminated body can be improved in optical characteristics by shrinking in the width direction by a drying shrinkage treatment. This is because the orientation of PVA and the PVA / iodine complex can be effectively enhanced.
  • the shrinkage ratio in the width direction of the laminate by the dry shrinkage treatment is preferably 2% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%.
  • FIG. 3 is a schematic view showing an example of the drying shrinkage treatment.
  • the laminate 200 is dried while being transported by the transport rolls R1 to R6 heated to a predetermined temperature and the guide rolls G1 to G4.
  • the transport rolls R1 to R6 are arranged so as to alternately and continuously heat the surface of the PVA resin layer and the surface of the thermoplastic resin base material.
  • one surface of the laminate 200 (for example, thermoplastic) is arranged.
  • the transport rolls R1 to R6 may be arranged so as to continuously heat only the resin base material surface).
  • Drying conditions can be controlled by adjusting the heating temperature of the transport roll (temperature of the heating roll), the number of heating rolls, the contact time with the heating roll, and the like.
  • the temperature of the heating roll is preferably 60 ° C. to 120 ° C., more preferably 65 ° C. to 100 ° C., and particularly preferably 70 ° C. to 80 ° C.
  • the crystallinity of the thermoplastic resin can be satisfactorily increased, curling can be satisfactorily suppressed, and an optical laminate having extremely excellent durability can be produced.
  • the temperature of the heating roll can be measured with a contact thermometer. In the illustrated example, six transport rolls are provided, but there is no particular limitation as long as there are a plurality of transport rolls.
  • the number of transport rolls is usually 2 to 40, preferably 4 to 30.
  • the contact time (total contact time) between the laminate and the heating roll is preferably 1 second to 300 seconds, more preferably 1 to 20 seconds, and further preferably 1 to 10 seconds.
  • the heating roll may be provided in a heating furnace (for example, an oven) or in a normal production line (in a room temperature environment). Preferably, it is provided in a heating furnace provided with a blowing means.
  • a heating furnace provided with a blowing means.
  • the temperature of hot air drying is preferably 30 ° C to 100 ° C.
  • the hot air drying time is preferably 1 second to 300 seconds.
  • the wind speed of hot air is preferably about 10 m / s to 30 m / s. The wind speed is the wind speed in the heating furnace and can be measured by a mini-vane type digital anemometer.
  • a washing treatment is performed after the underwater stretching treatment and before the drying shrinkage treatment.
  • the cleaning treatment is typically performed by immersing a PVA-based resin layer in an aqueous potassium iodide solution.
  • thermoplastic resin base material / polarizer a laminate of a thermoplastic resin base material / polarizer.
  • a coating film is formed by applying an organic solvent solution of an acrylic resin to the surface of the laminate obtained in Section B-2-1 above, and the coating film is solidified to protect a polarizer.
  • the first layer of the laminate is formed.
  • the acrylic resin is as described in Section A-2-1 above.
  • any suitable organic solvent capable of dissolving or uniformly dispersing the acrylic resin can be used.
  • the organic solvent include ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone.
  • the acrylic resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film in close contact with the polarizer can be formed.
  • the solution may be applied to any suitable substrate or to a polarizer.
  • the solution When the solution is applied to the base material, the solidified material of the coating film formed on the base material is transferred to the polarizer.
  • the solution When the solution is applied to the polarizer, the first layer is directly formed on the polarizer by drying (solidifying) the coating film.
  • the solution is applied to the polarizer and a first layer is formed directly on the polarizer.
  • the adhesive layer or the adhesive layer required for transfer can be omitted, so that the polarizing plate can be further thinned.
  • Any suitable method can be adopted as the method for applying the solution. Specific examples include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, and a knife coating method (comma coating method, etc.).
  • the first layer can be formed by drying (solidifying) the coating film of the solution.
  • the drying temperature is preferably 100 ° C. or lower, more preferably 50 ° C. to 70 ° C. When the drying temperature is in such a range, it is possible to prevent an adverse effect on the polarizer.
  • the drying time can vary depending on the drying temperature. The drying time can be, for example, 1 to 10 minutes.
  • the active energy ray-curable resin may contain a leveling agent.
  • the leveling agent include a fluorine-based leveling agent and a silicone-based leveling agent.
  • the active energy ray-curable resin (resin composition) may contain an additive. Examples of the additive include fine particles, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antioxidants, thixotropy agents and the like.
  • the curing conditions can be appropriately set according to the type of the active energy ray-curable resin.
  • the laminate for protecting the polarizer is formed.
  • the laminate for protecting the polarizer may be transferred to the polarizer.
  • a second layer and a first layer are formed in this order on an arbitrary suitable base material to prepare a laminated body having a base material / polarizer protection laminate (second layer / first layer).
  • the laminate for protecting the polarizer may be transferred from this laminate to the polarizer.
  • thermoplastic resin base material / a polarizer / a laminate for protecting a polarizer.
  • a polarizing plate 200 having a polarizing element 120 and a polarizing element protection laminate 100 as shown in FIG. 2 can be obtained.
  • a resin film forming another protective layer is attached to the polarizing element surface of the thermoplastic resin base material / polarizer laminate, then the thermoplastic resin base material is peeled off, and the polarizer protective laminate is laminated on the peeled surface. You may form a body. In this case, a polarizing plate having another protective layer can be obtained.
  • Glass transition temperature Tg The film constituting the first layer of the polarizing element protection laminate used in Examples and Comparative Examples was measured using a heated TMA analyzer (manufactured by Hitachi High-Tech Science Corporation, product name “TMA-7100C”). The measurement conditions were as follows: load 2 g; nitrogen atmosphere (200 ml / min); temperature rise from 25 ° C to 150 ° C, held at 150 ° C for 5 minutes, then lowered to 25 ° C and again to 150 ° C. Heat up and hold at 150 ° C. for 5 minutes; temperature rise rate 2 ° C./min.
  • Polarization degree (P) (%) ⁇ (Tp-Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • the Ts, Tp, and Tc are Y values measured by the JIS Z 8701 2 degree field of view (C light source) and corrected for luminosity factor. Also, Ts and P are substantially properties of the polarizer.
  • the polarizing plate was left in an oven at 85 ° C. and 85% RH for 48 hours to heat and humidify (heating test), and from the simple substance transmittance Ts 0 before the heating test and the simple substance transmittance Ts 48 after the heating test, The amount of change in single transmittance ⁇ Ts was determined using the following formula.
  • ⁇ Ts (%) Ts 48 -Ts 0
  • the amount of change in degree of polarization ⁇ P was determined using the following formula.
  • ⁇ P (%) P 48 ⁇ P 0
  • the heating test was carried out by preparing a test sample in the same manner as in the case of the above-mentioned crack.
  • a resin base material an amorphous isophthal copolymer polyethylene terephthalate film (thickness: 100 ⁇ m) having a long shape, a water absorption rate of 0.75%, and a Tg of about 75 ° C. was used.
  • One side of the resin base material was corona-treated.
  • PVA-based resin 100 weight of PVA-based resin in which polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimer Z410" are mixed at a ratio of 9: 1. 13 parts by weight of potassium iodide was added to the part to prepare a PVA aqueous solution (coating liquid). A PVA-based resin layer having a thickness of 13 ⁇ m was formed by applying the above PVA aqueous solution to the corona-treated surface of the resin base material and drying at 60 ° C. to prepare a laminate.
  • the obtained laminate was uniaxially stretched at the free end 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (aerial auxiliary stretching treatment).
  • the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
  • insolubilizing bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
  • a dyeing bath having a liquid temperature of 30 ° C.
  • Polarizing Plate A cycloolefin-based film (Zeon Corporation, ZT-12, thickness 23 ⁇ m) as a film constituting another protective layer is applied to the surface of the polarizing element obtained above via an ultraviolet curable adhesive. And pasted together. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 ⁇ m, and bonded using a roll machine. Then, a UV ray was irradiated from the film side to cure the adhesive. Then, the resin base material was peeled off to obtain a polarizing plate having another protective layer (ZT-12) / polarizer configuration.
  • ZT-12 another protective layer
  • the composition for forming the second layer is 100 parts of an ultraviolet curable urethane acrylate resin for a hard coat layer (manufactured by DIC, product name "Unidic 17-806"), a leveling agent (manufactured by DIC, product name "GRANDIC PC4100”). ) 0.01 part and 3 parts of a photopolymerization initiator (manufactured by IGM Resins B.V., product name "Omnirad 907").
  • the coating film is dried at 90 ° C. for 1 minute, and then irradiated with ultraviolet rays having an integrated light intensity of 200 mW / cm 2 with a high-pressure mercury lamp to form a cured product of the coating film.
  • a photopolymerization initiator manufactured by IGM Resins B.V.
  • the thickness of the second layer was 3 ⁇ m, the elastic modulus was 5000 MPa, and the elongation rate was larger than 3%.
  • a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained.
  • the obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • Example 2 Same as Example 1 except that the second layer was formed by using "Unidic ELS-888" (manufactured by DIC) instead of "Unidic 17-806" as the ultraviolet curable urethane acrylate resin for the hard coat layer. Then, a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained. The thickness of the second layer was 3 ⁇ m, the elastic modulus was 3000 MPa, and the elongation rate was 40%. The obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • Example 3 Same as Example 1 except that the second layer was formed by using "Unidic V-4221" (manufactured by DIC) instead of "Unidic 17-806" as the ultraviolet curable urethane acrylate resin for the hard coat layer. Then, a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained. The thickness of the second layer was 3 ⁇ m, the elastic modulus was 60 MPa, and the elongation rate was 200%.
  • Example 4 For protecting the polarizer in the same manner as in Example 1 except that the first layer was formed by using a copolymer of methyl acrylate / butyl acrylate (molar ratio 80/20) instead of "B728" as the acrylic resin.
  • a polarizing plate having a structure of a laminate (second layer / first layer) / polarizer / another protective layer (ZT-12) was obtained.
  • the thickness of the first layer was 2 ⁇ m, and the Tg was 95 ° C.
  • the obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • Example 5 Same as Example 4 except that the second layer was formed by using "Unidic ELS-888" (manufactured by DIC) instead of "Unidic 17-806" as the ultraviolet curable urethane acrylate resin for the hard coat layer. Then, a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained. The thickness of the second layer was 3 ⁇ m, the elastic modulus was 3000 MPa, and the elongation rate was 40%. The obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • Example 6 Same as Example 4 except that the second layer was formed by using "Unidic V-4221" (manufactured by DIC) instead of "Unidic 17-806" as the ultraviolet curable urethane acrylate resin for the hard coat layer. Then, a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained. The thickness of the second layer was 3 ⁇ m, the elastic modulus was 60 MPa, and the elongation rate was 200%. The obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • ⁇ Comparative example 2> Similar to Comparative Example 1 except that the second layer was formed by using "Unidic ELS-888" (manufactured by DIC) instead of "Unidic 17-806" as the ultraviolet curable urethane acrylate resin for the hard coat layer. Then, a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained. The thickness of the second layer was 3 ⁇ m, the elastic modulus was 3000 MPa, and the elongation rate was 40%. The obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • ⁇ Comparative example 5> Similar to Comparative Example 4 except that the second layer was formed by using "Unidic ELS-888" (manufactured by DIC) instead of "Unidic 17-806" as the ultraviolet curable urethane acrylate resin for the hard coat layer. Then, a polarizing plate having a structure of a laminate for protecting a polarizer (second layer / first layer) / a polarizer / another protective layer (ZT-12) was obtained. The thickness of the second layer was 3 ⁇ m, the elastic modulus was 3000 MPa, and the elongation rate was 40%. The obtained polarizing plate was used for the evaluation of (3) and (4) above. The results are shown in Table 1.
  • Example 7 A polarizing plate was produced in the same manner as in Example 1 except that the second layer was not formed (that is, the protective layer was formed only by the first layer). The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 8 A polarizing plate was produced in the same manner as in Example 4 except that the second layer was not formed (that is, the protective layer was formed only by the first layer). The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • the laminate for protecting the polarizer of the embodiment of the present invention is suppressed from cracking even in a heating and humidifying environment.
  • a laminate for protecting a polarizer it is possible to realize a polarizing plate having excellent durability by suppressing deterioration of optical characteristics even in a heating and humidifying environment, even though it is very thin.
  • the polarizing plate of the present invention is suitably used for an image display device.
  • image display devices include portable devices such as mobile information terminals (PDAs), smartphones, mobile phones, clocks, digital cameras, and portable game machines; OA devices such as personal computer monitors, laptop computers, and copiers; video cameras and televisions.
  • PDAs mobile information terminals
  • OA devices such as personal computer monitors, laptop computers, and copiers
  • video cameras and televisions Household electrical equipment such as microwave ovens; In-vehicle equipment such as back monitors, car navigation system monitors, car audio; Exhibition equipment such as digital signage and commercial store information monitors; Security equipment such as monitoring monitors; Nursing care Nursing care / medical equipment such as monitors for medical use and monitors for medical use;

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