WO2022034774A1 - 位相差層付偏光板およびそれを用いた画像表示装置 - Google Patents

位相差層付偏光板およびそれを用いた画像表示装置 Download PDF

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Publication number
WO2022034774A1
WO2022034774A1 PCT/JP2021/026860 JP2021026860W WO2022034774A1 WO 2022034774 A1 WO2022034774 A1 WO 2022034774A1 JP 2021026860 W JP2021026860 W JP 2021026860W WO 2022034774 A1 WO2022034774 A1 WO 2022034774A1
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Prior art keywords
layer
retardation layer
polarizing plate
resin
group
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PCT/JP2021/026860
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English (en)
French (fr)
Japanese (ja)
Inventor
聡司 三田
夏紀 村上
結子 石川
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日東電工株式会社
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Priority to KR1020237002469A priority Critical patent/KR20230028464A/ko
Priority to CN202180056593.1A priority patent/CN116057609A/zh
Publication of WO2022034774A1 publication Critical patent/WO2022034774A1/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
    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8793—Arrangements for polarized light emission
    • 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
    • C08J2329/00—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
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a polarizing plate with a retardation layer and an image display device using the same.
  • image display devices represented by liquid crystal displays and electroluminescence (EL) display devices for example, organic EL display devices and inorganic EL display devices
  • EL electroluminescence
  • a polarizing plate and a retardation plate are typically used in an image display device.
  • a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1), and recently, there is a strong demand for thinner image display devices. As a result, there is an increasing demand for thinner polarizing plates with a retardation layer.
  • the thickness of the protective layer of the polarizing element which greatly contributes to the thickness, is being reduced (or omitted), and the thickness of the retardation film is being reduced.
  • metal members for example, electrodes, sensors, wiring, metal layers
  • Such corrosion of metal members is remarkable in a high temperature and high humidity environment.
  • the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to suppress corrosion of metal members when applied to an image display device, and to prevent peeling between a retardation layer and an adjacent layer. It is an object of the present invention to provide a thin polarizing plate with a retardation layer in which the above is suppressed.
  • the polarizing plate with a retardation layer of the present invention has a polarizing plate containing a polarizing element, a retardation layer, and an adhesive layer in this order from the viewing side.
  • At least one iodine permeation suppressing layer which is a solidified or thermosetting film of a coating film of an organic solvent solution of a resin, is provided between the polarizing element and the pressure-sensitive adhesive layer.
  • the iodine permeation inhibitory layer adjacent to the retardation layer contains a resin and an isocyanate compound; the glass transition temperature of the resin is 85 ° C.
  • the iodine permeation suppressing layer is provided with two or more layers. In one embodiment, the two or more iodine permeation suppressing layers are all provided adjacent to the retardation layer. In another embodiment, one of the two or more iodine permeation inhibitory layers is provided adjacent to the polarizing element.
  • the iodine permeation inhibitory layer has a thickness of 0.05 ⁇ m to 10 ⁇ m.
  • the resin constituting the iodine permeation suppressing layer includes an epoxy resin.
  • the resin constituting the iodine permeation inhibitory layer is represented by the formula (1) of more than 50 parts by weight of the (meth) acrylic monomer and more than 0 parts by weight and less than 50 parts by weight.
  • X is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
  • R 1 and R 2 each independently have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and a substituent.
  • the retardation layer is an oriented solidified layer of a liquid crystal compound having a circular polarization function or an elliptically polarizing function.
  • the retardation layer is a single layer.
  • the Re (550) of the retardation layer is 100 nm to 190 nm, and the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizing element is 40 ° to 50 °.
  • the retardation layer has a laminated structure of an oriented solidified layer of a first liquid crystal compound and an oriented solidified layer of a second liquid crystal compound.
  • the Re (550) of the oriented solidified layer of the first liquid crystal compound is 200 nm to 300 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizing element is 10 ° to 20 °;
  • the second The Re (550) of the oriented solidified layer of the liquid crystal compound is 100 nm to 190 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizing element is 70 ° to 80 °.
  • the polarizing plate with a retardation layer has a total thickness of 60 ⁇ m or less.
  • an image display device is provided. This image display device includes the above-mentioned polarizing plate with a retardation layer. In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.
  • the polarizing plate with a retardation layer is applied to an image display device by providing at least one specific iodine permeation suppression layer at a predetermined position of the polarizing plate with a thin retardation layer.
  • corrosion of the metal member can be suppressed.
  • the iodine permeation suppressing layer adjacent to the retardation layer contains a resin and an isocyanate compound; the glass transition temperature of the resin is 85 ° C. or higher, and the weight average molecular weight Mw.
  • Isocyanate compound is at least one selected from tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and derivatives thereof; the content ratio (resin / isocyanate compound) of the resin and the isocyanate compound is It is 95/5 to 10/90.
  • Refractive index (nx, ny, nz) "Nx" is the refractive index in the direction in which the refractive index in the plane is maximized (that is, the slow-phase axis direction), and "ny” is the direction orthogonal to the slow-phase axis in the plane (that is, the phase-advancing axis direction). Is the refractive index of, and "nz” is the refractive index in the thickness direction.
  • In-plane phase difference (Re) “Re ( ⁇ )” is an in-plane phase difference measured with light having a wavelength of ⁇ nm at 23 ° C.
  • Re (550) is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C.
  • Phase difference in the thickness direction (Rth) is a phase difference in the thickness direction measured with light having a wavelength of ⁇ nm at 23 ° C.
  • Rth (550) is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C.
  • FIG. 1A is a schematic cross-sectional view of the polarizing plate with a retardation layer according to one embodiment of the present invention.
  • the polarizing plate 100 with a retardation layer in the illustrated example has a polarizing plate 10, a retardation layer 20, and a pressure-sensitive adhesive layer 30 in this order from the visual recognition side.
  • the polarizing plate 10 typically includes a polarizing element 11 and a protective layer 12 arranged on the visual side of the polarizing element 11.
  • another protective layer may be provided on the side opposite to the visible side (protective layer 12) of the polarizing element 11.
  • the retardation layer 20 is typically an oriented solidified layer of a liquid crystal compound having a circular polarization function or an elliptically polarized function (hereinafter, may be simply referred to as a liquid crystal oriented solidified layer).
  • the pressure-sensitive adhesive layer 30 is provided as an outermost layer, and the polarizing plate with a retardation layer can be attached to an image display device (substantially, an image display cell).
  • At least one iodine permeation suppressing layer 40 is provided between the polarizing element 11 and the pressure-sensitive adhesive layer 30.
  • the iodine permeation inhibitory layer is a solidified product or a thermosetting product of a coating film of an organic solvent solution of a resin.
  • the resin typically has a glass transition temperature of 85 ° C. or higher and a weight average molecular weight Mw of 25,000 or higher.
  • Such a metal corrosion suppressing effect is an effect peculiar to a thin polarizing plate with a retardation layer (typically, a polarizing plate with a retardation layer in which the retardation layer is a liquid crystal oriented solidified layer).
  • the present inventors have newly discovered a problem that when a thin polarizing plate with a retardation layer is applied to an image display device, the metal member of the image display device may be corroded, and iodine is added to the corroded portion. From its presence, it has been clarified that such corrosion of metal parts can be caused by iodine. Then, as a result of trial and error, as a means for preventing the transfer of iodine to the image display device (substantially, the image display cell), the above-mentioned iodine permeation suppressing layer (organic resin having specific Tg and Mw) is used.
  • the iodine permeation suppressing layer can be formed very thinly, and by providing the iodine permeation suppressing layer, the protective layer on the side opposite to the visual recognition side can be omitted. This effect can contribute to further thinning of the polarizing plate with a retardation layer.
  • the iodine permeation suppressing layer 40 may be provided with only one layer, or may be provided with two or more layers (for example, two layers, three layers, four layers). In the embodiment shown in FIG. 1A, the iodine permeation suppressing layer 40 is provided with only one layer between the polarizing element 11 and the retardation layer 20. The iodine permeation suppressing layer 40 may be provided with only one layer between the retardation layer 20 and the pressure-sensitive adhesive layer 30 as in the polarizing plate 101 with a retardation layer shown in FIG. 1B; the position shown in FIG. 1C.
  • Two layers may be provided between the polarizing element 11 and the retardation layer 20 and between the retardation layer 20 and the pressure-sensitive adhesive layer 30 as in the polarizing plate 102 with a retardation layer; the retardation shown in FIG. 1D.
  • a total of three layers may be provided, two layers between the polarizing element 11 and the retardation layer 20, and one layer between the retardation layer 20 and the pressure-sensitive adhesive layer 30.
  • the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer (particularly when the iodine permeation suppressing layer is adjacent to the pressure-sensitive adhesive layer), components that are considered to affect metal corrosion other than iodine (for example). , Residual monomer component in the ultraviolet curable adhesive, decomposition product of the photoinitiator) can also be prevented from migrating into the pressure-sensitive adhesive at the same time, and has the advantage of further enhancing the effect of suppressing metal corrosion. By providing two or more iodine permeation suppressing layers, the metal corrosion suppressing effect can be remarkably enhanced.
  • the number of iodine permeation suppressing layers can be set in consideration of cost, manufacturing efficiency, total thickness of the polarizing plate with a retardation layer, and the like.
  • the iodine permeation suppressing layer adjacent to the retardation layer contains a resin and an isocyanate compound;
  • the glass transition temperature of the resin is The temperature is 85 ° C. or higher, and the weight average molecular weight Mw is 25,000 or higher;
  • the isocyanate compound is a tolylene diisocyanate, a diphenylmethane diisocyanate, a xylylene diisocyanate, and / or a derivative thereof (for example, a modified product, an adduct).
  • the content ratio (resin / isocyanate compound) of the resin and the isocyanate compound is 95/5 to 10/90.
  • the iodine permeation suppression layer is arranged adjacent to the retardation layer (liquid crystal alignment solidification layer), the iodine permeation suppression layer and the retardation layer (liquid crystal alignment solidification layer) may be peeled off in a high humidity environment. rice field.
  • the present inventors have found that the peeling can be remarkably suppressed by adding a specific amount of a specific isocyanate compound to the resin constituting the iodine permeation suppressing layer, and complete the present invention. It came to. That is, such an effect solves a new problem that has not been known in the past, and is an unexpectedly excellent effect.
  • the retardation layer 20 is a liquid crystal oriented solidifying layer.
  • the retardation layer 20 may be a single layer as shown in FIGS. 1A to 1D, and the first liquid crystal alignment solidification layer 21 and the second liquid crystal alignment solidification layer 22 as shown in FIGS. 2A to 2F. It may have a laminated structure.
  • the iodine permeation suppression layer 40 is 1 between the polarizing element 11 and the first liquid crystal alignment solidification layer 21, as in the polarizing plate 104 with the retardation layer shown in FIG. 2A.
  • Only one layer may be provided; only one layer may be provided between the second liquid crystal oriented solidified layer 22 and the pressure-sensitive adhesive layer 30 (not shown); with the first liquid crystal oriented solidified layer 21. Only one layer may be provided between the second liquid crystal oriented solidified layer 22 (not shown); the polarizing element 11 and the first liquid crystal like the polarizing plate 105 with a retardation layer shown in FIG. 2B. Two layers may be provided between the oriented solidified layer 21 and between the second liquid crystal oriented solidified layer 22 and the pressure-sensitive adhesive layer 30; polarized light as in the polarizing plate 106 with a retardation layer shown in FIG. 2C.
  • Two layers may be provided between the child 11 and the first liquid crystal oriented solidified layer 21 and between the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22; as shown in FIG. 2D.
  • Two layers such as the polarizing plate with a retardation layer 107, between the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 and between the second liquid crystal oriented solidified layer 22 and the pressure-sensitive adhesive layer 30.
  • Three layers may be provided between the liquid crystal oriented solidified layer 22 and between the second liquid crystal oriented solidified layer 22 and the pressure-sensitive adhesive layer 30; as in the polarizing plate with a retardation layer 109 shown in FIG. 2F.
  • the polarizing element 11 and the first liquid crystal oriented solidified layer 21 there are two layers between the polarizing element 11 and the first liquid crystal oriented solidified layer 21, one layer between the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22, and a second layer.
  • a total of four layers may be provided between the liquid crystal oriented solidified layer 22 and the pressure-sensitive adhesive layer 30.
  • 1A-1D and 2A-2F are exemplary, where the iodine permeation inhibitory layer 40 is optionally located at any suitable position between the polarizing element 11 and the pressure-sensitive adhesive layer 30, depending on the intended purpose.
  • the above embodiments may be combined as appropriate, and the components in the above embodiments may be modified in a manner obvious in the art. Further, for example, five or more iodine permeation suppressing layers may be provided.
  • another retardation layer and / or a conductive layer or an isotropic substrate with a conductive layer may be further provided (neither is shown).
  • Another retardation layer is typically provided between the retardation 20 and the pressure-sensitive adhesive layer 30 (ie, outside the retardation layer 20).
  • the conductive layer or the isotropic base material with the conductive layer is typically provided between the iodine permeation suppressing layer 40 and the pressure-sensitive adhesive layer 30 (that is, outside the iodine permeation suppressing layer 40).
  • the polarizing plate with a retardation layer is a so-called inner touch panel type in which a touch sensor is incorporated between an image display cell (for example, an organic EL cell) and the polarizing plate. Can be applied to input display devices.
  • the conductive layer or the isotropic base material with the conductive layer on the outside of the iodine permeation suppressing layer 40, the corrosion of the conductive layer can be remarkably suppressed.
  • the polarizing plate with a retardation layer may further include other retardation layers.
  • the optical characteristics for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient
  • thickness, arrangement position, and the like of the other retardation layers can be appropriately set according to the purpose.
  • a release film is temporarily attached to the surface of the pressure-sensitive adhesive layer 30 until a polarizing plate with a retardation layer is used.
  • the pressure-sensitive adhesive layer can be protected and a roll of the polarizing plate with a retardation layer can be formed.
  • the total thickness of the polarizing plate with a retardation layer is preferably 60 ⁇ m or less, more preferably 55 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 40 ⁇ m or less.
  • the lower limit of the total thickness can be, for example, 28 ⁇ m. According to the embodiment of the present invention, it is possible to realize such an extremely thin polarizing plate with a retardation layer, and further, when such a polarizing plate with an extremely thin retardation layer is applied to an image display device. However, corrosion of metal members (for example, electrodes, sensors, wirings, metal layers) of the image display device can be remarkably suppressed.
  • a polarizing plate with an extremely thin retardation layer peeling between the retardation layer and the adjacent layer (substantially, an iodine permeation suppression layer) is remarkably suppressed.
  • a polarizing plate with a retardation layer may have extremely excellent flexibility and bending durability. Therefore, such a polarizing plate with a retardation layer may be particularly preferably applied to a curved image display device and / or a bendable or foldable image display device.
  • the total thickness of the polarizing plate with a retardation layer includes the polarizing plate, the retardation layer (if another retardation layer exists, the retardation layer and another retardation layer), the iodine permeation suppression layer, and these.
  • the total thickness of the adhesive layer or the pressure-sensitive adhesive layer for laminating that is, the total thickness of the polarizing plate with the retardation layer is the conductive layer or the isotropic substrate with the conductive layer, and the pressure-sensitive adhesive layer 30 and its thereof. Does not include the thickness of the release film that can be temporarily attached to the surface).
  • the polarizing plate with a retardation layer may be single-wafer-shaped or long-shaped.
  • the term "long” means an elongated shape having a length sufficiently long with respect to the width, and for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. include.
  • the long polarizing plate with a retardation layer can be wound in a roll shape.
  • the components of the polarizing plate with a retardation layer will be described in more detail. Since a structure well known in the industry can be adopted for the pressure-sensitive adhesive layer 30, the detailed structure of the pressure-sensitive adhesive layer will be omitted.
  • the splitter is typically composed of a polyvinyl alcohol (PVA) -based resin film containing a dichroic substance.
  • the thickness of the splitter is preferably 1 ⁇ m to 8 ⁇ m, more preferably 1 ⁇ m to 7 ⁇ m, and further preferably 2 ⁇ m to 5 ⁇ m. If the thickness of the polarizing element is within such a range, it can greatly contribute to the thinning of the polarizing plate with a retardation layer. Further, the effect of the present invention is remarkable in a thin polarizing plate with a retardation layer using such a polarizing element.
  • the boric acid content of the stator is preferably 10% by weight or more, more preferably 13% by weight to 25% by weight.
  • the boric acid content of the stator 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 iodine content described later, 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 boric acid content can be calculated, for example, as the amount of boric acid contained in the polarizing element per unit weight by using the following formula from the neutralization method.
  • the iodine content of the modulator is preferably 2% by weight or more, more preferably 2% by weight to 10% by weight.
  • the iodine content of the stator 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 polarizing element (PVA-based resin film).
  • iodine exists in the form of iodine ion (I ⁇ ), iodine molecule (I 2 ), polyiodide ion (I 3 ⁇ , I 5 ⁇ ), etc., as used herein.
  • Iodine content means the amount of iodine that includes all of these forms.
  • the iodine content can be calculated, for example, by a calibration curve method for fluorescent X-ray analysis.
  • the polyiodine ion exists in a state where the PVA-iodine complex is formed in the polarizing element. By forming such a complex, absorption dichroism can be exhibited in the wavelength range of visible light.
  • the complex of PVA and triiodide ion (PVA ⁇ I 3- ) has an absorption peak near 470 nm, and the complex of PVA and triiodide ion (PVA ⁇ I 5- ) is around 600 nm. Has an absorptive peak.
  • polyiodide ions can absorb light over 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, polyiodide ions present in the form of a complex with PVA may mainly contribute to the absorption performance of the polarizing element.
  • the splitter preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the simple substance transmittance Ts of the polarizing element is preferably 40% to 48%, more preferably 41% to 46%.
  • the degree of polarization P of the polarizing element is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more.
  • the single transmittance is typically a Y value measured with an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
  • the degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured by using an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
  • Degree of polarization (%) ⁇ (Tp-Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • the modulator can be typically made of a laminate of two or more layers.
  • Specific examples of the polarizing element obtained by using the laminated body include a polarizing element obtained by using a laminated body of a resin base material and a PVA-based resin layer coated and formed on the resin base material.
  • the polarizing element obtained by using the laminate of the resin base material and the PVA-based resin layer coated and formed on the resin base material is, for example, a resin base material obtained by applying a PVA-based resin solution to the resin base material and drying it.
  • Stretching typically involves immersing the laminate in an aqueous boric acid solution for stretching. Further, stretching may further comprise, if necessary, stretching the laminate in the air at a high temperature (eg, 95 ° C. or higher) prior to stretching in boric acid aqueous solution.
  • the obtained resin base material / polarizing element laminate may be used as it is (that is, the resin base material may be used as a protective layer for the polarizing element), and the resin base material is peeled off from the resin base material / polarizing element laminate. Then, an arbitrary appropriate protective layer according to the purpose may be laminated on the peeled surface and used. Details of the method for producing such a polarizing element are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The entire description of these publications is incorporated herein by reference.
  • a method for producing a polarizing element is to form a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin base material to form a laminate.
  • the above-mentioned laminated body is subjected to an aerial auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. including.
  • the crystallinity of PVA can be enhanced and high optical characteristics can be achieved.
  • by increasing the orientation of PVA in advance it is possible to prevent problems such as deterioration of PVA orientation and dissolution when immersed in water in a subsequent dyeing step or stretching step, and high optical characteristics. Will be possible to achieve.
  • the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecule 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.
  • optical characteristics of the polarizing element obtained through a treatment step of immersing the laminate in a liquid, such as a dyeing treatment and a stretching treatment in water. Further, the optical characteristics can be improved by shrinking the laminated body in the width direction by the drying shrinkage treatment.
  • the protective layer 12 is formed of any suitable film that can be used as a protective layer for the stator.
  • the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based.
  • TAC triacetyl cellulose
  • thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned.
  • glassy polymers such as siloxane-based polymers can also be mentioned.
  • the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used.
  • a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain.
  • the polymer film can be, for example, an extruded product of the above resin composition.
  • the polarizing plate with a retardation layer is typically arranged on the visual recognition side of the image display device, and the protective layer 12 is typically arranged on the visual recognition side. Therefore, the protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, sticking prevention treatment, and antiglare treatment, if necessary. Further / or, if necessary, the protective layer 12 is provided with a process for improving visibility when visually recognizing through polarized sunglasses (typically, a (elliptical) circular polarization function is provided, and an ultra-high phase difference is provided. May be given). By performing such processing, excellent visibility can be realized even when the display screen is visually recognized through a polarizing lens such as polarized sunglasses. Therefore, the polarizing plate with a retardation layer can be suitably applied to an image display device that can be used outdoors.
  • polarized sunglasses typically, a (elliptical) circular polarization function is provided, and an ultra-high phase difference is provided. May be given.
  • the thickness of the protective layer is preferably 10 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 30 ⁇ m.
  • the thickness of the outer protective layer is the thickness including the thickness of the surface treatment layer.
  • the retardation layer 20 is typically a liquid crystal oriented solidifying layer.
  • the difference between nx and ny of the obtained retardation layer can be significantly increased as compared with the non-liquid crystal material, so that the thickness of the retardation layer for obtaining a desired in-plane retardation can be obtained. Can be made much smaller. As a result, it is possible to further reduce the thickness of the polarizing plate with a retardation layer.
  • the term "liquid crystal oriented solidified layer” refers to a layer in which a liquid crystal compound is oriented in a predetermined direction within the layer and the oriented state is fixed.
  • the "oriented solidified layer” is a concept including an oriented cured layer obtained by curing a liquid crystal monomer as described later.
  • the rod-shaped liquid crystal compounds are typically oriented in a state of being aligned in the slow axis direction of the retardation layer (homogeneous orientation).
  • the liquid crystal compound examples include a liquid crystal compound (nematic liquid crystal) in which the liquid crystal phase is a nematic phase.
  • a liquid crystal compound for example, a liquid crystal polymer or a liquid crystal monomer can be used.
  • the liquid crystal expression mechanism of the liquid crystal compound may be either lyotropic or thermotropic.
  • the liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
  • the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the orientation state of the liquid crystal monomer can be fixed by polymerizing or cross-linking (that is, curing) the liquid crystal monomer. After the liquid crystal monomers are oriented, for example, if the liquid crystal monomers are polymerized or crosslinked with each other, the oriented state can be fixed.
  • the polymer is formed by polymerization, and the three-dimensional network structure is formed by crosslinking, but these are non-liquid crystal.
  • the formed retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to a liquid crystal compound, for example.
  • the retardation layer becomes an extremely stable retardation layer that is not affected by temperature changes.
  • the temperature range in which the liquid crystal monomer exhibits liquid crystal properties differs depending on the type. Specifically, the temperature range is preferably 40 ° C. to 120 ° C., more preferably 50 ° C. to 100 ° C., and most preferably 60 ° C. to 90 ° C.
  • any suitable liquid crystal monomer can be adopted as the liquid crystal monomer.
  • the polymerizable mesogen compounds described in Special Tables 2002-533742 WO00 / 37585
  • EP358208 US5211877
  • EP66137 US43884553
  • WO93 / 22397 EP0261712, DE19504224, DE4408171, and GB2280445
  • Specific examples of such a polymerizable mesogen compound include, for example, BASF's trade name LC242, Merck's trade name E7, and Wacker-Chem's trade name LC-Silicon-CC3767.
  • the liquid crystal monomer for example, a nematic liquid crystal monomer is preferable.
  • the surface of a predetermined base material is subjected to an orientation treatment, and a coating liquid containing a liquid crystal compound is applied to the surface to orient the liquid crystal compound in a direction corresponding to the alignment treatment. It can be formed by fixing the state.
  • the substrate is any suitable resin film and the liquid crystal oriented solidified layer formed on the substrate is transferred to the surface of an adjacent layer (eg, a decoder, an iodine permeation inhibitory layer). Can be done.
  • any appropriate orientation treatment can be adopted.
  • Specific examples thereof include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment.
  • Specific examples of the mechanical orientation treatment include a rubbing treatment and a stretching treatment.
  • Specific examples of the physical orientation treatment include magnetic field orientation treatment and electric field orientation treatment.
  • Specific examples of the chemical alignment treatment include an orthorhombic vapor deposition method and a photoalignment treatment.
  • As the treatment conditions for various orientation treatments any appropriate conditions may be adopted depending on the purpose.
  • the orientation of the liquid crystal compound is performed by treating at a temperature indicating the liquid crystal phase according to the type of the liquid crystal compound. By performing such temperature treatment, the liquid crystal compound takes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the surface of the substrate.
  • the alignment state is fixed by cooling the liquid crystal compound oriented as described above.
  • the orientation state is fixed by subjecting the liquid crystal compound oriented as described above to a polymerization treatment or a crosslinking treatment.
  • liquid crystal compound and details of the method for forming the oriented solidified layer are described in Japanese Patent Application Laid-Open No. 2006-163343. The description of this publication is incorporated herein by reference.
  • the retardation layer 20 is a single layer as shown in FIGS. 1A-1D.
  • its thickness is preferably 0.5 ⁇ m to 7 ⁇ m, and more preferably 1 ⁇ m to 5 ⁇ m.
  • the retardation layer typically has a circular polarization function or an elliptically polarizing function.
  • the retardation layer is typically provided to impart antireflection characteristics to the polarizing plate, and can function as a ⁇ / 4 plate when the retardation layer is a single layer.
  • the in-plane retardation Re (550) of the retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and even more preferably 130 nm to 160 nm.
  • the Nz coefficient of the retardation layer is preferably 0.9 to 1.5, and more preferably 0.9 to 1.3. By satisfying such a relationship, a very excellent reflected hue can be achieved when the obtained polarizing plate with a retardation layer is used in an image display device.
  • the retardation layer may exhibit a reverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, or may exhibit a positive wavelength dispersion characteristic in which the retardation value decreases according to the wavelength of the measurement light. It is also possible to exhibit a flat wavelength dispersion characteristic in which the phase difference value hardly changes depending on the wavelength of the measured light.
  • the retardation layer exhibits inverse dispersion wavelength characteristics.
  • Re (450) / Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be realized.
  • the angle ⁇ formed by the slow axis of the retardation layer 20 and the absorption axis of the polarizing element 11 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably about 45 °. be. If the angle ⁇ is in such a range, by using the retardation layer as a ⁇ / 4 plate as described above, a very excellent circular polarization characteristic (as a result, a very excellent antireflection characteristic) can be obtained. A polarizing plate with a difference layer can be obtained.
  • the retardation layer 20 may have a laminated structure of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 as shown in FIGS. 2A to 2F.
  • one of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 may function as a ⁇ / 4 plate, and the other may function as a ⁇ / 2 plate. Therefore, the thicknesses of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 can be adjusted so as to obtain a desired in-plane phase difference between the ⁇ / 4 plate or the ⁇ / 2 plate.
  • the thickness of the first liquid crystal oriented solidified layer 21 is, for example, 2.
  • the thickness is 0.0 ⁇ m to 3.0 ⁇ m
  • the thickness of the second liquid crystal oriented solidified layer 22 is, for example, 1.0 ⁇ m to 2.0 ⁇ m.
  • the in-plane retardation Re (550) of the first liquid crystal oriented solidified layer is preferably 200 nm to 300 nm, more preferably 230 nm to 290 nm, and further preferably 250 nm to 280 nm.
  • the in-plane retardation Re (550) of the second liquid crystal oriented solidified layer is as described above with respect to the single layer.
  • the angle formed by the slow axis of the first liquid crystal oriented solidified layer and the absorption axis of the polarizing element is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and further preferably about 15 °. Is.
  • the angle formed by the slow axis of the second liquid crystal oriented solidified layer and the absorption axis of the polarizing element is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and further preferably about 75 °. Is.
  • liquid crystal compounds constituting the first liquid crystal oriented solidified layer and the second liquid crystal oriented solidified layer, the method for forming the first liquid crystal oriented solidified layer and the second liquid crystal oriented solidified layer, the optical characteristics, and the like are described above with respect to the single layer. As explained in.
  • the iodine permeation suppression layer is, as described above, a solidified product or a thermosetting material of a coating film of an organic solvent solution of a resin. With such a configuration, the thickness can be made very thin (for example, 10 ⁇ m or less).
  • the thickness of the iodine permeation inhibitory layer is preferably 0.05 ⁇ m to 10 ⁇ m, more preferably 0.08 ⁇ m to 5 ⁇ m, still more preferably 0.1 ⁇ m to 1 ⁇ m, and particularly preferably 0.2 ⁇ m to 0.7 ⁇ m. Is.
  • the iodine permeation suppressing layer can be formed directly (that is, without an adhesive layer or an adhesive layer) directly on the adjacent layer (for example, a polarizing element or a retardation layer).
  • the polarizing element, the retardation layer and the iodine permeation suppressing layer are very thin, and the adhesive layer or the pressure-sensitive adhesive layer for laminating the iodine permeation suppressing layer is omitted. Therefore, the total thickness of the polarizing plate with a retardation layer can be made extremely thin.
  • such an iodine permeation suppressing layer has an advantage that it is excellent in humidification durability because it has a smaller hygroscopicity and moisture permeability than 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 with a retardation layer having excellent durability, which can maintain optical characteristics even in a high temperature and high humidity environment. Further, such an iodine permeation suppressing layer can suppress an adverse effect on a polarizing plate (polarizer) due to ultraviolet irradiation as compared with, for example, a cured product of an ultraviolet curable resin.
  • polarizing plate polarizer
  • the iodine permeation inhibitory layer is preferably a solidified coating film of an organic solvent solution of a resin.
  • the solidified product has a smaller shrinkage during film molding than the cured product, and since it does not contain residual monomers, deterioration of the film itself is suppressed, and the polarizing plate (polarizer) caused by the residual monomers is suppressed. The adverse effect can be suppressed.
  • the glass transition temperature (Tg) of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25000 or higher.
  • Tg and Mw of the resin are in such a range, the iodine permeation inhibitory layer is very effective due to the synergistic effect with the effect of forming the coating film of the organic solvent solution of the resin as a solidified product or a thermosetting product.
  • the transfer of iodine in the polarizing element to the image display cell can be significantly suppressed.
  • corrosion of the metal member can be remarkably suppressed.
  • the Tg of the resin is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher.
  • the upper limit of Tg can be, for example, 200 ° C.
  • the Mw of the resin is preferably 30,000 or more, more preferably 35,000 or more, and further preferably 40,000 or more.
  • the upper limit of Mw can be, for example, 150,000.
  • the iodine permeation suppressing layer adjacent to the retardation layer further contains an isocyanate compound in addition to the above resin.
  • the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and derivatives thereof (for example, modified products and adducts).
  • the isocyanate compound may be used alone or in combination.
  • the content ratio of the resin and the isocyanate compound (resin / isocyanate compound) is 95/5 to 10/90 as described above.
  • the content ratio (resin / isocyanate compound) is, for example, 95/5 to 50/50, for example 90/10 to 60/40, for example 85/15 to 70/30, and for example 85/15 to 75/25. You may.
  • the content ratio (resin / isocyanate compound) may also be, for example, 40/60 to 5/95, for example, 30/70 to 5/95, or, for example, 20/80 to 10/90.
  • any suitable thermoplastic resin can be formed as long as it can form a solidified or thermosetting material of a coating film of an organic solvent solution and has Tg and Mw as described above.
  • a thermosetting resin can be used.
  • a thermoplastic resin is preferable.
  • the thermoplastic resin include epoxy-based resins and acrylic-based resins.
  • An epoxy resin and an acrylic resin may be used in combination.
  • typical examples of the epoxy resin and the acrylic resin that can be used for the iodine permeation suppressing layer will be described.
  • an epoxy resin having an aromatic ring is preferably used as the epoxy resin.
  • the adhesion to the polarizing element can be improved when the iodine permeation suppressing layer is arranged adjacent to the polarizing element.
  • the anchoring force of the pressure-sensitive adhesive layer can be improved.
  • the epoxy resin having an aromatic ring include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac epoxy resin, cresol novolak epoxy resin, hydroxybenzaldehyde phenol novolac.
  • Novolak type epoxy resin such as epoxy resin; polyfunctional epoxy resin such as tetrahydroxyphenylmethane glycidyl ether, tetrahydroxybenzophenone glycidyl ether, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type Epoxy resin and the like can be mentioned.
  • a bisphenol A type epoxy resin, a biphenyl type epoxy resin, and a bisphenol F type epoxy resin are used. Only one type of epoxy resin may be used, or two or more types may be used in combination.
  • the acrylic resin typically contains a repeating unit derived from a (meth) acrylic acid ester-based monomer having a linear or branched structure as a main component.
  • (meth) acrylic refers to acrylic and / or methacrylic.
  • the acrylic resin may contain repeating units derived from any suitable copolymerized monomer depending on the intended purpose. Examples of the copolymerized monomer (copolymerized monomer) include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an aromatic ring-containing (meth) acrylate, and a heterocyclic ring-containing vinyl-based monomer.
  • the acrylic resin is a (meth) acrylic monomer having more than 50 parts by weight and a monomer represented by the formula (1) having more than 0 parts by weight and less than 50 parts by weight (hereinafter,). , May be referred to as a copolymerization monomer) and a copolymer obtained by polymerizing a monomer mixture (hereinafter, may be referred to as a boron-containing acrylic resin).
  • X is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
  • R 1 and R 2 each independently have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and a substituent.
  • R 1 and R 2 may be linked to each other to form a ring).
  • the boron-containing acrylic resin typically has a repeating unit represented by the following formula.
  • the boron-containing acrylic resin By polymerizing a monomer mixture containing the copolymerized monomer represented by the formula (1) and the (meth) acrylic monomer, the boron-containing acrylic resin has a substituent containing boron in the side chain (for example,). It has a repeating unit of k in the following formula).
  • the boron-containing substituent may be continuously (that is, in a block shape) contained in the boron-containing acrylic resin, or may be randomly contained. (In the equation, R 6 represents an arbitrary functional group, and j and k represent integers of 1 or more).
  • Any suitable (meth) acrylic monomer can be used as the (meth) acrylic monomer.
  • a (meth) acrylic acid ester-based monomer having a linear or branched structure and a (meth) acrylic acid ester-based monomer having a cyclic structure can be mentioned.
  • Examples of the (meth) acrylic acid ester-based monomer having a linear or branched structure include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include isopropyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like. .. Preferably, methyl (meth) acrylate is used.
  • the (meth) acrylic acid ester-based monomer only one kind may be used, or two or more kinds may be used in combination.
  • Examples of the (meth) acrylate-based monomer having a cyclic structure include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and ( Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, o-biphenyloxyethoxy Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-
  • 1-adamantyl (meth) acrylate and dicyclopentanyl (meth) acrylate are used.
  • these monomers a polymer having a high glass transition temperature can be obtained. Only one kind of these monomers may be used, or two or more kinds thereof may be used in combination.
  • a silsesquioxane compound having a (meth) acryloyl group may be used instead of the above (meth) acrylic acid ester-based monomer.
  • a silsesquioxane compound having a (meth) acryloyl group By using the silsesquioxane compound, an acrylic polymer having a high glass transition temperature can be obtained.
  • the silsesquioxane compound is known to have various skeleton structures such as a cage-type structure, a ladder-type structure, and a random structure.
  • the silsesquioxane compound may have only one of these structures, or may have two or more of these structures. Only one kind of silsesquioxane compound may be used, or two or more kinds may be used in combination.
  • silsesquioxane compound containing a (meth) acryloyl group for example, MAC grade and AC grade of Toagosei Co., Ltd. SQ series can be used.
  • the MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include MAC-SQ TM-100, MAC-SQ SI-20, and MAC-SQ HDM.
  • the AC grade is a silsesquioxane compound containing an acryloyl group, and specific examples thereof include AC-SQ TA-100 and AC-SQ SI-20.
  • the (meth) acrylic monomer is used in an amount of more than 50 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • ⁇ Copolymerization monomer> As the copolymerization monomer, a monomer represented by the above formula (1) is used. By using such a copolymerized monomer, a substituent containing boron is introduced into the side chain of the obtained polymer. Only one type of copolymerization monomer may be used, or two or more types may be used in combination.
  • the aliphatic hydrocarbon group in the above formula (1) may have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and may have a substituent and may have 3 to 3 carbon atoms.
  • Examples thereof include a cyclic alkyl group of 20 and an alkenyl group having 2 to 20 carbon atoms.
  • Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent and a naphthyl group having 10 to 20 carbon atoms which may have a substituent.
  • the heterocyclic group include a 5-membered ring group or a 6-membered ring group containing at least one heteroatom which may have a substituent.
  • R 1 and R 2 may be connected to each other to form a ring.
  • R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
  • the reactive group contained in the functional group represented by X is a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and the like. And at least one selected from the group consisting of carboxyl groups.
  • the reactive group is a (meth) acrylic group and / or a (meth) acrylamide group.
  • the functional group represented by X is preferably a functional group represented by ZZ.
  • Z is selected from the group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
  • the following compounds can be used as the copolymerization monomer.
  • the copolymerized monomer is used in an amount of more than 0 parts by weight and less than 50 parts by weight with respect to 100 parts by weight of the monomer mixture. It is preferably 0.01 parts by weight or more and less than 50 parts by weight, more preferably 0.05 parts by weight to 20 parts by weight, still more preferably 0.1 parts by weight to 10 parts by weight, and particularly preferably 0. It is 5 parts by weight to 5 parts by weight.
  • the acrylic resin has a repeating unit including a ring structure selected from 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 2 , R 3 and R 4 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 contain only a single lactone ring unit, or may contain a plurality of lactone ring units having different R2 , R3 and R4 in the above general formula (2). ..
  • 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 each 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). ..
  • Examples of the acrylic resin having a glutarimide unit include JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328334, JP-A-2006-337491, and 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 this publication is incorporated herein by reference.
  • the glutaric anhydride unit the above description regarding the glutarimide unit is applied except that the nitrogen atom substituted with R13 in the general formula (3) becomes an oxygen atom.
  • 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%.
  • the acrylic resin contains the above-mentioned (meth) acrylic monomer-derived repeating unit as the main repeating unit.
  • the iodine permeation inhibitory layer can be formed by applying an organic solvent solution of a resin as described above to form a coating film, and solidifying or thermosetting the coating film.
  • the organic solvent 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 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 can be formed.
  • the solution may be applied to any suitable substrate or to an adjacent layer (eg, a polarizing element, a retardation layer).
  • the solidified product (iodine permeation inhibitory layer) of the coating film formed on the substrate is transferred to the adjacent layer.
  • the protective layer is directly formed on the adjacent layer by drying (solidifying) the coating film.
  • the solution is applied to the adjacent layer and a protective layer is formed directly on the adjacent layer.
  • the adhesive layer or the pressure-sensitive adhesive layer required for transfer can be omitted, so that the polarizing plate with a retardation layer 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.).
  • An iodine permeation inhibitory layer can be formed by solidifying or thermosetting the coating film of the solution.
  • the heating temperature for solidification or thermosetting is preferably 100 ° C. or lower, more preferably 50 ° C. to 70 ° C. When the heating temperature is in such a range, it is possible to prevent an adverse effect on the polarizing element.
  • the heating time can vary depending on the heating temperature. The heating time can be, for example, 1 minute to 10 minutes.
  • the iodine permeation suppressing layer may contain any suitable additive depending on the purpose.
  • the additive 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-stabilizing agents; 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 type, number, combination, amount of additive, etc. of the additive can be appropriately set according
  • the phase difference Rth (550) in the thickness direction of another retardation layer is preferably ⁇ 50 nm to ⁇ 300 nm, more preferably ⁇ 70 nm to ⁇ 250 nm, still more preferably ⁇ 90 nm to ⁇ 200 nm, and particularly preferably ⁇ . It is 100 nm to ⁇ 180 nm.
  • Another retardation layer preferably consists of a film containing a liquid crystal material fixed in a homeotropic orientation.
  • the liquid crystal material (liquid crystal compound) that can be homeotropically oriented may be a liquid crystal monomer or a liquid crystal polymer.
  • Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compound and the method for forming the retardation layer described in [0020] to [0028] of JP-A-2002-333642.
  • the thickness of the other retardation layer is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 8 ⁇ m, and even more preferably 0.5 ⁇ m to 5 ⁇ m.
  • the conductive layer is an arbitrary suitable base material by any suitable film forming method (for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.). It can be formed by forming a metal oxide film on top of it.
  • suitable film forming method for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.
  • the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimon composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Of these, indium-tin composite oxide (ITO) is preferable.
  • the thickness of the conductive layer is preferably 50 nm or less, more preferably 35 nm or less.
  • the lower limit of the thickness of the conductive layer is preferably 10 nm.
  • the conductive layer is transferred from the base material to a retardation layer (or an iodine permeation suppression layer or another retardation layer if present), and the conductive layer alone is used as a constituent layer of a polarizing plate with a retardation layer.
  • a retardation layer or an iodine permeation suppression layer or another retardation layer if present
  • the substrate is optically isotropic, and therefore the conductive layer can be used as an isotropic substrate with a conductive layer in a polarizing plate with a retardation layer.
  • any suitable isotropic base material can be adopted as the optically isotropic base material (isotropic base material).
  • the material constituting the isotropic base material for example, a material having a resin having no conjugate system such as a norbornene resin or an olefin resin as a main skeleton, or an acrylic resin having a cyclic structure such as a lactone ring or a glutarimide ring. Examples include the material contained in the main chain. When such a material is used, when an isotropic base material is formed, the expression of the phase difference due to the orientation of the molecular chains can be suppressed to be small.
  • the thickness of the isotropic substrate is preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less. The lower limit of the thickness of the isotropic substrate is, for example, 20 ⁇ m.
  • the conductive layer and / or the conductive layer of the isotropic base material with the conductive layer can be patterned as needed. By patterning, a conductive portion and an insulating portion can be formed. As a result, electrodes can be formed.
  • the electrode can function as a touch sensor electrode that senses contact with the touch panel.
  • any suitable method may be adopted. Specific examples of the patterning method include a wet etching method and a screen printing method.
  • an embodiment of the present invention includes an image display device using such a polarizing plate with a retardation layer.
  • Typical 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).
  • the image display device according to the embodiment of the present invention includes the polarizing plate with a retardation layer according to the above items A to F on the visual recognition side thereof.
  • the polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display cell side (for example, a liquid crystal cell, an organic EL cell, an inorganic EL cell) (so that the polarizing element is on the visual recognition side).
  • the image display device has a curved shape (substantially a curved display screen) and / or is bendable or foldable.
  • Thickness The thickness of 10 ⁇ m or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). Thicknesses exceeding 10 ⁇ m were measured using a digital micrometer (manufactured by Anritsu, product name “KC-351C”).
  • an overcoat solution (solid content) containing 99 parts of methyl isobutyl ketone (MIBK), 1 part of pentaerythritol tetraacrylate (PETA), and 0.03 part of a photopolymerization initiator (manufactured by BASF, product name "Irgacure 907"). Concentration: about 1%) was applied to the surface of the silver nanowire coating film using a wire bar so that the wet film thickness was 10 ⁇ m, and dried in an oven at 100 ° C. for 5 minutes.
  • MIBK methyl isobutyl ketone
  • PETA pentaerythritol tetraacrylate
  • a photopolymerization initiator manufactured by BASF, product name "Irgacure 907”
  • the overcoat coating film was cured by irradiating with active energy rays to prepare a metal film having a composition of PET film / silver nanowire layer / overcoat layer (thickness 100 nm).
  • This metal film was attached to a glass plate having a thickness of 0.5 mm using an adhesive (15 ⁇ m) to obtain a metal film / adhesive / glass plate laminate.
  • a non-contact resistance measuring instrument manufactured by Napson, product name "EC-80"
  • the polarizing plates with a retardation layer obtained in Examples and Comparative Examples were bonded to the surface of the overcoat layer of the metal film of the laminated body to prepare a test sample.
  • the resistance value of this test sample was measured with a non-contact resistance measuring instrument and used as the initial resistance value. Further, after subjecting the test sample to a reliability test (putting it in an environment of 85 ° C. and 85% RH for 48 hours and then leaving it in an environment of 23 ° C. and 55% RH for 2 hours), the resistance value is the same as above. Was measured.
  • the resistance value increase rate was calculated by the following formula.
  • thermoplastic resin base material an amorphous isophthal copolymer polyethylene terephthalate film (thickness: 100 ⁇ m) having a long shape, a water absorption 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.
  • a PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water. The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, and a laminate was prepared.
  • the obtained laminate was stretched 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. (a boric acid aqueous 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. an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water
  • the uniaxial stretching was performed so that the total stretching ratio was 5.5 times (underwater stretching treatment).
  • the laminate was immersed in a washing bath having a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
  • cleaning treatment an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water
  • cleaning treatment a liquid temperature of 20 ° C.
  • cleaning treatment an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water
  • dry shrinkage treatment dry shrinkage treatment
  • the shrinkage rate in the width direction of the laminated body by the dry shrinkage treatment was 5.2%. In this way, a substituent having a thickness of 5 ⁇ m was formed on the resin substrate.
  • HC-COP film as a protective layer was attached to the surface of the polarizing element obtained above (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 ⁇ m, and bonded using a roll machine. Then, UV light was irradiated from the protective layer side to cure the adhesive.
  • the HC-COP film is a cycloolefin (COP) film (manufactured by Zeon Corporation, product name "ZF12", thickness 25 ⁇ m) in which a hard coat (HC) layer (thickness 2 ⁇ m) is formed, and is a COP film. Was pasted together so that it was on the modulator side. Next, the resin base material was peeled off to obtain a polarizing plate having a protective layer (HC layer / COP film) / adhesive layer / polarizing element.
  • COP cycloolefin
  • the surface of a polyethylene terephthalate (PET) film was rubbed with a rubbing cloth and subjected to an orientation treatment.
  • the direction of the alignment treatment was set to be 15 ° when viewed from the visual recognition side with respect to the direction of the absorption axis of the polarizing element when the polarizing plate was attached.
  • the liquid crystal coating liquid was applied to the alignment-treated surface with a bar coater, and the liquid crystal compound was oriented by heating and drying at 90 ° C. for 2 minutes.
  • the liquid crystal layer thus formed was irradiated with light of 1 mJ / cm 2 using a metal halide lamp, and the liquid crystal layer was cured to form a liquid crystal oriented solidified layer A on the PET film.
  • Example 1 The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B obtained in Production Example 3 were transferred in this order to the polarizing element surface of the polarizing plate obtained in Production Example 2. At this time, the angle formed by the absorption axis of the splitter and the slow axis of the liquid crystal oriented solidified layer A is 15 °, and the angle formed by the absorption axis of the splitter and the slow axis of the liquid crystal oriented solidified layer B is 75 °. The transfer (bonding) was performed in this way. Each transfer (bonding) was performed via the ultraviolet curable adhesive (thickness 1.0 ⁇ m) used in Production Example 2.
  • the protective layer (HC layer / COP film) / adhesive layer / modulator / adhesive layer / retardation layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer).
  • This mixture was dissolved in 80 parts of a mixed solvent of ethyl acetate / cyclopentanone (70/30) to obtain a resin solution (20%).
  • This resin solution is applied to the surface of the second liquid crystal oriented solidified layer of the above-mentioned laminate using a wire bar, the coating film is dried at 60 ° C. for 5 minutes, and the coating film of the organic solvent solution of the resin is applied.
  • an adhesive layer (thickness 15 ⁇ m) is provided on the surface of the iodine permeation suppressing layer, and a protective layer (HC layer / COP film) / adhesive layer / polarizing element / adhesive layer / retardation layer (first liquid crystal oriented solidified layer) is provided.
  • a polarizing plate with a retardation layer having the composition of / adhesive layer / second liquid crystal alignment solidification layer) / iodine permeation suppression layer / pressure-sensitive adhesive layer was obtained.
  • the total thickness of the obtained polarizing plate with a retardation layer was 39.5 ⁇ m.
  • the obtained polarizing plate with a retardation layer was subjected to the evaluations (2) to (4) above. The results are shown in Table 1.
  • Example 2 A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that an iodine permeation inhibitory layer was formed using a mixture of 10 parts of the resin blend and 90 parts of the isocyanate compound. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 3 An iodine permeation suppressing layer was formed by using a mixture of 80 parts of a resin blend and 20 parts of an isocyanate compound, and the iodine permeation suppressing layer was formed between a polarizing element and a first liquid crystal oriented solidifying layer.
  • Protective layer HC layer / COP film
  • adhesive layer / polarizing element / adhesive layer / iodine permeation suppression layer / retardation layer
  • the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 4 A polarizing plate with a retardation layer in the same manner as in Example 1 except that an iodine permeation suppressing layer was formed by using a mixture of 80 parts of copolymer 1 (boron-containing acrylic resin) and 20 parts of an isocyanate compound. was produced. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 5 Examples except that an iodine permeation inhibitory layer was formed using a mixture of 80 parts of a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name “jER® YX6954BH30”) and 20 parts of an isocyanate compound. A polarizing plate with a retardation layer was produced in the same manner as in 1. The Tg of this epoxy resin was 130 ° C., and the weight average molecular weight was 38,000. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 6 The retardation layer is the same as in Example 5 except that the iodine permeation suppressing layer is formed by using the trade name "jER (registered trademark) YX7200B35" manufactured by Mitsubishi Chemical Corporation instead of "YX6954BH30" as the thermoplastic epoxy resin.
  • An attached polarizing plate was prepared.
  • the Tg of this epoxy resin was 150 ° C., and the weight average molecular weight was 30,000.
  • the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 7 Example 1 except that an iodine permeation inhibitory layer was formed using a mixture in which 20 parts of an isocyanate compound (“Coronate 2067” manufactured by Tosoh Corporation: trimethylolpropane adduct of diphenylmethane diisocyanate) was added to 80 parts of a resin blend. A polarizing plate with a retardation layer was produced in the same manner as in the above. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 8 Except for forming an iodine permeation inhibitory layer using a mixture of 80 parts of a resin blend and 20 parts of an isocyanate compound (“Takenate D110N” manufactured by Mitsui Chemicals, Inc .: trimethylolpropane adduct of m-xylylene diisocyanate). Made a polarizing plate with a retardation layer in the same manner as in Example 1. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 9 In the same manner as in Example 3 except that an iodine permeation inhibitory layer using only the copolymer 1 (that is, containing no isocyanate compound) was further formed between the polarizing element and the first liquid crystal oriented solidified layer.
  • Protective layer HC layer / COP film
  • Adhesive layer / Polarizer / Iodine permeation suppression layer
  • Adhesive layer / Phase difference layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer)
  • a polarizing plate with a retardation layer having a structure of / iodine permeation suppression layer / adhesive layer was produced.
  • the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 10 Protective layer (HC layer / COP film) / adhesion in the same manner as in Example 3 except that an iodine permeation suppressing layer similar to that in Example 3 was further formed between the polarizing element and the first liquid crystal oriented solidified layer.
  • Composition of Agent Layer / Polarizer / Adhesive Layer / Iodine Permeation Suppressing Layer / Phase Difference Layer (First Liquid Liquid Orientation Solidification Layer / Adhesive Layer / Second Liquid crystal Orientation Solidification Layer) / Iodine Permeation Suppression Layer / Adhesive Layer A polarizing plate with a retardation layer was produced. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 11 An iodine permeation suppressing layer using only copolymer 1 (that is, containing no isocyanate compound) and iodine permeation similar to Example 3 in order from the polarizing element side between the polarizing element and the first liquid crystal oriented solidifying layer. Similar to Example 3, except that the inhibitory layer was further formed, the protective layer (HC layer / COP film) / adhesive layer / polarizing element / iodine permeation inhibitory layer / adhesive layer / iodine permeation inhibitory layer / phase difference.
  • the protective layer HC layer / COP film
  • a polarizing plate with a retardation layer having a structure of a layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer) / iodine permeation suppressing layer / pressure-sensitive adhesive layer was produced.
  • the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 3 A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that an iodine permeation inhibitory layer was formed using only the resin blend (that is, containing no isocyanate compound). The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • epoxy / acrylic in the column of constituent resins means a blend of epoxy-based resin and acrylic-based resin; the numbers in the column of forming positions mean the symbols in the drawings. Therefore, for example, "11" means a polarizing element.
  • the polarizing plate with a retardation layer according to the embodiment of the present invention can remarkably suppress metal corrosiveness in a high temperature and high humidity environment. Therefore, it can be seen that the polarizing plate with a retardation layer according to the embodiment of the present invention can suppress corrosion of metal members when applied to an image display device. Further, as is clear when comparing Examples 1 to 8 and Examples 9 to 11, the metal corrosiveness can be remarkably suppressed by providing two or more iodine permeation suppressing layers. In addition, the polarizing plate with a retardation layer according to the embodiment of the present invention suppresses peeling between the iodine permeation suppressing layer and the retardation layer.
  • the polarizing plate with a retardation layer of the present invention is suitably used as a circular polarizing plate for a liquid crystal display device, an organic EL display device, and an inorganic EL display device.
  • Polarizing plate 11 Polarizer 12 Protective layer 20 Phase difference layer 30
  • Adhesive layer 40 Iodine permeation suppression layer 100 Polarizing plate with retardation layer 101 Polarizing plate with retardation layer 102 Polarizing plate with retardation layer 103 Polarizing plate with retardation layer 104 Polarizing plate with retardation layer 105 Polarizing plate with retardation layer 106 Polarizing plate with retardation layer 107 Polarizing plate with retardation layer 108 Polarizing plate with retardation layer 109 Polarizing plate with retardation layer 109

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