WO2021070525A1 - Plaque de polarisation avec couche à différence de phase et couche adhésive et dispositif d'affichage électroluminescent organique l'utilisant - Google Patents

Plaque de polarisation avec couche à différence de phase et couche adhésive et dispositif d'affichage électroluminescent organique l'utilisant Download PDF

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Publication number
WO2021070525A1
WO2021070525A1 PCT/JP2020/033266 JP2020033266W WO2021070525A1 WO 2021070525 A1 WO2021070525 A1 WO 2021070525A1 JP 2020033266 W JP2020033266 W JP 2020033266W WO 2021070525 A1 WO2021070525 A1 WO 2021070525A1
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Prior art keywords
layer
adhesive layer
pressure
sensitive adhesive
polarizing plate
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PCT/JP2020/033266
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English (en)
Japanese (ja)
Inventor
潤枝 長田
雄祐 外山
寛 友久
後藤　周作
一生 田中
裕太 高瀬
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日東電工株式会社
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Priority claimed from JP2020060296A external-priority patent/JP2021063972A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202080070942.0A priority Critical patent/CN114502999A/zh
Priority to KR1020227011230A priority patent/KR20220075221A/ko
Publication of WO2021070525A1 publication Critical patent/WO2021070525A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • G02B5/3083—Birefringent or phase retarding elements
    • 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
    • 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
    • G09F9/33—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 being semiconductor devices, e.g. diodes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to a polarizing plate with a retardation layer and an adhesive layer, and an organic electroluminescence (EL) display device using the same.
  • EL organic electroluminescence
  • the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to have excellent durability in a high temperature and high humidity environment, and to remarkably suppress decolorization when applied to an organic EL display device. It is an object of the present invention to provide a polarizing plate with a retardation layer and an adhesive layer.
  • the polarizing plate with a retardation layer and a pressure-sensitive adhesive layer of the present invention includes a polarizing plate, a polarizing plate containing a protective layer at least on the viewing side of the polarizing element, and a first pressure-sensitive adhesive on the side opposite to the viewing side of the polarizing plate. It has a retardation layer bonded via a layer and a second pressure-sensitive adhesive layer arranged as an outermost layer on the opposite side of the retardation layer to the polarizing plate.
  • the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer contains an ultraviolet absorber, and the content of the ultraviolet absorber in the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer is 1% by weight to 12% by weight. By weight%.
  • the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer has a transmittance of 5% or less at a wavelength of 380 nm.
  • the polarizer and the retardation layer are bonded to each other via the first pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer contains an ultraviolet absorber.
  • the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer contains acrylic acid as a monomer component of the base polymer. In one embodiment, the acrylic acid content in the monomer component is 0.1% by weight to 7% by weight.
  • the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer further comprises a radical generator.
  • the solubility of the first pressure-sensitive adhesive layer in ethyl acetate at 25 ° C. is 2 g / 100 g to 70 g / 100 g.
  • the first pressure-sensitive adhesive layer has a molar extinction coefficient of 400 L / (mol ⁇ cm) or more at a wavelength of 380 nm.
  • the moisture permeability of the protective layer of the viewing side is a 200g / m 2 ⁇ 24h or more, greater than the moisture permeability of the retardation layer.
  • an organic electroluminescent display device is provided. This organic electroluminescence display device includes the above-mentioned retardation layer and a polarizing plate with an adhesive layer.
  • the pressure-sensitive adhesive layer or the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer in which the polarizing plate and the retardation layer are laminated is used as an image display cell.
  • a predetermined amount of ultraviolet absorber into the adhesive layer for bonding, it has excellent durability in a high temperature and high humidity environment, and decolorization is remarkably suppressed when applied to an organic EL display device.
  • a polarizing plate with a retardation layer and an adhesive layer can be realized.
  • Refractive index (nx, ny, nz) "Nx" is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), and "ny” is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advance 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. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer and an adhesive layer according to one embodiment of the present invention.
  • the polarizing plate 100 with the retardation layer and the pressure-sensitive adhesive layer in the illustrated example includes the polarizing plate 10, the retardation layer 30 bonded to the polarizing plate 10 via the first pressure-sensitive adhesive layer 20, and the retardation layer 30. It has a second pressure-sensitive adhesive layer 40 provided as an outermost layer on the side opposite to the polarizing plate 10.
  • the second pressure-sensitive adhesive layer 40 makes it possible to attach the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer to the image display cell.
  • the polarizing plate 10 includes a polarizing element 11 and a protective layer (visible side protective layer) 12 at least on the viewing side of the polarizing element 11.
  • the protective layer (inner protective layer) 13 is provided on the side opposite to the visible side of the polarizer 11, but the protective layer 13 may be preferably omitted. That is, the polarizer 11 and the retardation layer 20 can be bonded to each other via the first pressure-sensitive adhesive layer 20.
  • the inner protective layer 13 is omitted, the effect of the embodiment of the present invention is remarkable. Practically, it is preferable that a release film is temporarily attached to the surface of the second pressure-sensitive adhesive layer 40 until the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer are used. By temporarily adhering the release film, it is possible to protect the second pressure-sensitive adhesive layer and form a roll of the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer 20 or the second pressure-sensitive adhesive layer 40 contains an ultraviolet absorber.
  • the UV absorber content in the first pressure-sensitive adhesive layer 20 or the second pressure-sensitive adhesive layer 40 is 1% by weight to 12% by weight, preferably 2% by weight to 10% by weight, and more preferably 3% by weight. ⁇ 7% by weight. If the content of the ultraviolet absorber is too large, the durability of the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer in a high-temperature and high-humidity environment may be insufficient.
  • the first pressure-sensitive adhesive layer 20 contains an ultraviolet absorber.
  • the ultraviolet absorber is contained only in the second pressure-sensitive adhesive layer, bleed-out, peeling, etc. may occur in addition to the deterioration of the retardation layer.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer have a transmittance of 5% or less, preferably 4% or less, and more preferably 3.5% or less at a wavelength of 380 nm. It is more preferably 2.5% or less.
  • the transmittance at a wavelength of 380 nm is preferably 0.4% or more. If the transmittance at a wavelength of 380 nm is too low, it is necessary to add a large amount of an ultraviolet absorber, so that the durability of the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer in a high-temperature and high-humidity environment may be insufficient. If the transmittance at a wavelength of 380 nm is too high, the organic EL panel may deteriorate.
  • the protective layer 13 can be preferably omitted.
  • the moisture permeability of the protective layer 12 is larger than the moisture permeability of the retardation layer 20.
  • the protective layer 13 is present, the moisture permeability of the protective layer 12 is larger than the moisture permeability of the protective layer 13 and the moisture permeability of the retardation layer 20, whichever is smaller; the protective layer 13 is present and
  • the retardation layer 20 is an orientation-solidified layer of a liquid crystal compound, the moisture permeability of the protective layer 12 is larger than that of the protective layer 13.
  • the present inventors face a new problem that the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer are decolorized when the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer is applied to an organic EL display device.
  • the cause of the decolorization was ammonia (substantially ammonium ions) generated from the organic EL panel.
  • the decolorization is remarkable by blocking the ammonium ions that have invaded the polarizer as much as possible and discharging the ammonium ions that have invaded as much as possible. I found that it can be suppressed.
  • the protective layer of the polarizer is designed to reduce the moisture permeability of the outer (visual side) protective layer because the main purpose is to protect the polarizer from moisture (water vapor).
  • the embodiment of the present invention is based on such a technical idea completely opposite to the common general technical knowledge in the art.
  • the difference between the moisture permeability of the moisture permeability and the phase difference layer 20 of the protective layer 12 is preferably 200g / m 2 ⁇ 24h or more, more preferably 220g / m 2 ⁇ 24h or more , and still more preferably at 250g / m 2 ⁇ 24h or more, and particularly preferably 300g / m 2 ⁇ 24h or more.
  • the upper limit of the difference may be, for example, 600g / m 2 ⁇ 24h. When the difference is within such a range, decolorization of the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer can be suppressed more satisfactorily.
  • Moisture permeability of the protective layer 12 is 200g / m 2 ⁇ 24h or more, preferably 300g / m 2 ⁇ 24h or more, more preferably 330g / m 2 ⁇ 24h or more, more preferably 360 g / m 2 ⁇ 24h or more, particularly preferably 400 g / m 2 ⁇ 24h or more.
  • the upper limit of the moisture permeability of the protective layer 12 may be, for example, 650g / m 2 ⁇ 24h.
  • Moisture permeability of the retardation layer 20 is preferably not more than 150g / m 2 ⁇ 24h, more preferably not more than 100g / m 2 ⁇ 24h, even more preferably not more than 70g / m 2 ⁇ 24h, particularly preferably is less than or equal to 50g / m 2 ⁇ 24h.
  • Moisture permeability preferably as low retardation layer 20, the lower limit can be, for example, 5g / m 2 ⁇ 24h. If the moisture permeability of the protective layer 12 and the retardation layer 20 is within such a range, it is easy to set the above difference in moisture permeability to a desired range.
  • the moisture permeability can be measured according to JIS Z 0208.
  • the total thickness of the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer is preferably 120 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • the lower limit of the total thickness can be, for example, 45 ⁇ m.
  • a polarizing plate with a retardation layer and an adhesive layer having such a total thickness can have extremely excellent flexibility and bending durability.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer can be particularly preferably applied to a curved organic EL display device and / or a bendable or bendable organic EL display device.
  • the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer may further have another retardation layer (not shown) between the retardation layer 30 and the second pressure-sensitive adhesive layer 40.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may further include other optical functional layers.
  • the types, characteristics, numbers, combinations, arrangement positions, and the like of the optical functional layers that can be provided on the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer can be appropriately set according to the purpose.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may further have a conductive layer or an isotropic base material with a conductive layer (neither is shown).
  • the conductive layer or the isotropic base material with the conductive layer is typically provided on the outside of the retardation layer 20 (opposite to the polarizing plate 10).
  • the retardation layer and the polarizing plate with an adhesive layer are so-called inner touch panel type input display devices in which a touch sensor is incorporated between the organic EL cell and the polarizing plate.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive 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 other retardation layers can be appropriately set according to the purpose.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer may be single-wafered or elongated.
  • 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. Including.
  • the elongated retardation layer and the polarizing plate with the adhesive layer can be wound in a roll shape.
  • Polarizing plate B-1 Polarizer
  • any suitable polarizer can be adopted.
  • the resin film forming the polarizer may be a single-layer resin film or a laminated body having two or more layers.
  • the polarizer composed of a single-layer resin film include a hydrophilic polymer film such as a polyvinyl alcohol (PVA) -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer system partially saponified film.
  • a hydrophilic polymer film such as a polyvinyl alcohol (PVA) -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer system partially saponified film.
  • PVA polyvinyl alcohol
  • a partially formalized PVA-based film ethylene / vinyl acetate copolymer system partially saponified film
  • examples thereof include those which have been dyed and stretched with a bicolor substance such as iodine or a bicolor dye, and polyene-based oriented films such as a dehydrated product of PVA and a dehydrogenated product of polyvinyl chloride.
  • the above-mentioned dyeing with iodine is performed, for example, by immersing a PVA-based film in an aqueous iodine solution.
  • the draw ratio of the uniaxial stretching is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment or while dyeing. Alternatively, it may be stretched and then dyed. If necessary, the PVA-based film is subjected to a swelling treatment, a cross-linking treatment, a washing treatment, a drying treatment and the like.
  • the polarizer obtained by using the laminate include a laminate of a resin base material and a PVA-based resin layer (PVA-based resin film) laminated on the resin base material, or a resin base material and the resin.
  • Examples thereof include a polarizer obtained by using a laminate with a PVA-based resin layer coated and formed on a base material.
  • the polarizer 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 the resin base material.
  • stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching. Further, stretching may further include, 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.
  • a high temperature eg, 95 ° C. or higher
  • the obtained resin substrate / polarizer laminate may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizer), and the resin substrate is peeled off from the resin substrate / polarizer laminate. Then, an arbitrary appropriate protective layer according to the purpose may be laminated on the peeled surface. Details of the method for producing such a polarizer 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.
  • the thickness of the polarizer is preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less, further preferably 10 ⁇ m or less, and particularly preferably 8 ⁇ m or less.
  • the thickness of the polarizer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 3 ⁇ m or more.
  • the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the simple substance transmittance of the polarizer is, for example, 41.5% to 46.0%, preferably 43.0% to 46.0%, and preferably 44.5% to 46.0%.
  • the degree of polarization of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more.
  • the visible side protective layer 12 and the inner protective layer 13 are each composed of any suitable film that can be used as a protective layer for the polarizer.
  • Typical materials constituting the inner protective layer 13 include cycloolefin resins such as polycarbonate, (meth) acrylic resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polyester resins such as polyethylene terephthalate (PEN). Examples thereof include polyolefin resins such as polyethylene and polycarbonate resins.
  • a typical example of the (meth) acrylic resin is a (meth) acrylic resin having a lactone ring structure.
  • the inner protective layer 13 is preferably composed of a cycloolefin-based resin.
  • Typical examples of the material constituting the visible side protective layer 12 include a cellulosic resin such as triacetyl cellulose (TAC) and a resin capable of forming a microporous film (for example, a polyurethane resin).
  • the protective layer may contain an ultraviolet absorber.
  • the UV absorber in the protective layer, the deterioration of the organic EL panel is further improved by the synergistic effect with the effect of the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer containing the UV absorber. Can be prevented.
  • the content of the ultraviolet absorber in the protective layer is preferably 0.01% by weight to 10% by weight, more preferably 0.05% by weight to 7% by weight.
  • the retardation layer and the polarizing plate with the adhesive layer are typically arranged on the visible side of the organic EL display device as described later, and the protective layer 12 is arranged on the visible side thereof. Therefore, the protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, anti-sticking treatment, and anti-glare 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) circularly polarized light function is provided, and an ultra-high phase difference is provided. May be given). By performing such a process, excellent visibility can be realized even when the display screen is visually recognized through a polarized lens such as polarized sunglasses. Therefore, the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer can be suitably applied to an organic EL display device that can be used outdoors.
  • polarized sunglasses typically, a (elliptical) circularly polarized light function is provided,
  • the thickness of the protective layer 12 is preferably 10 ⁇ m to 80 ⁇ m, more preferably 15 ⁇ m to 70 ⁇ m, and even more preferably 20 ⁇ m to 50 ⁇ m.
  • the thickness of the protective layer 12 is a thickness including the thickness of the surface treatment layer.
  • the protective layer 13 is preferably optically isotropic in one embodiment.
  • optically isotropic means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is -10 nm to +10 nm.
  • the thickness of the protective layer 13 can also be appropriately set according to the desired moisture permeability.
  • the thickness of the protective layer 13 is preferably 10 ⁇ m to 80 ⁇ m, more preferably 20 ⁇ m to 70 ⁇ m, and even more preferably 30 ⁇ m to 50 ⁇ m. As mentioned above, the protective layer 13 may be preferably omitted.
  • phase difference layer 20 may be a single layer or may have a laminated structure (substantially a two-layer structure).
  • the retardation layer 20 can typically function as a ⁇ / 4 plate.
  • the retardation layer is typically provided to impart antireflection characteristics to an organic EL display device.
  • 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 120 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, an organic EL display device having a very excellent reflected hue can be obtained.
  • the retardation layer When the retardation layer is a single layer, the retardation layer preferably exhibits a reverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light.
  • the 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 and the absorption axis of the polarizer is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably about 45 °.
  • an organic EL display device having very excellent antireflection characteristics can be obtained by using the retardation layer as a ⁇ / 4 plate as described above.
  • the retardation layer can be made of any suitable material as long as the above characteristics can be satisfied.
  • the retardation layer may be a stretched film of a resin film, or may be an orientation-solidifying layer of a liquid crystal compound (hereinafter, a liquid crystal alignment solidification layer).
  • the resin constituting the resin film include a polycarbonate-based resin or a polyester carbonate-based resin (hereinafter, may be simply referred to as a polycarbonate-based resin).
  • a polycarbonate-based resin any suitable polycarbonate-based resin can be used as long as the desired moisture permeability can be obtained.
  • the polycarbonate-based resin contains a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, an alicyclic diol, an alicyclic dimethanol, di, tri or polyethylene glycol, and an alkylene.
  • the polycarbonate-based resin is a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, a structural unit derived from an alicyclic dimethanol, and / or di, tri or polyethylene glycol.
  • the polycarbonate-based resin may contain structural units derived from other dihydroxy compounds, if necessary.
  • the retardation layer can be formed by stretching a film made of the above-mentioned polycarbonate resin under arbitrary suitable stretching conditions.
  • a film made of the above-mentioned polycarbonate resin under arbitrary suitable stretching conditions.
  • the retardation layer is a liquid crystal oriented solidified layer
  • the difference between nx and ny of the obtained retardation layer can be remarkably increased as compared with the non-liquid crystal material by using the liquid crystal compound, so that the desired surface can be obtained.
  • the thickness of the retardation layer for obtaining the inner retardation can be remarkably reduced.
  • the term "aligned 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.
  • 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).
  • specific examples of the liquid crystal compound and details of the method for forming the liquid crystal oriented solidified layer are described in, for example, JP-A-2006-163343 and JP-A-2006-178389. The descriptions in these publications are incorporated herein by reference.
  • the thickness of the retardation layer can be typically set to a thickness that can properly function as a ⁇ / 4 plate.
  • the thickness of the retardation layer can be, for example, 10 ⁇ m to 60 ⁇ m.
  • the thickness of the retardation layer can be, for example, 1 ⁇ m to 5 ⁇ m.
  • the retardation layer When the retardation layer has a laminated structure, the retardation layer typically has a two-layer structure of a first liquid crystal oriented solidified layer and a second liquid crystal oriented solidified layer.
  • either one of the first liquid crystal oriented solidified layer or the second liquid crystal oriented solidified layer can function as a ⁇ / 2 plate, and the other can function as a ⁇ / 4 plate.
  • the case where the first liquid crystal oriented solidified layer can function as a ⁇ / 2 plate and the second liquid crystal oriented solidified layer can function as a ⁇ / 4 plate will be described, but these may be reversed. ..
  • the thickness of the first liquid crystal oriented solidified layer can be adjusted so as to obtain a desired in-plane phase difference of the ⁇ / 2 plate, and can be, for example, 2.0 ⁇ m to 4.0 ⁇ m.
  • the thickness of the second liquid crystal oriented solidified layer can be adjusted so as to obtain the desired in-plane phase difference of the ⁇ / 4 plate, and can be, for example, 1.0 ⁇ m to 2.5 ⁇ 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 preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and further preferably 120 nm to 160 nm.
  • the angle formed by the slow axis of the first liquid crystal oriented solidified layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and even more 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 polarizer is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and even more preferably about 75 °. Is. With such a configuration, it is possible to obtain characteristics close to the ideal reverse wavelength dispersion characteristic, and as a result, it is possible to realize extremely excellent antireflection characteristics.
  • first adhesive layer and the second adhesive layer may be composed of the same adhesive, or may be composed of different adhesives. You may. Composition of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (for example, type of base polymer (polarity, Tg, softness), molecular weight), cross-linking structure (for example, type of cross-linking agent, distance between cross-linking points (molecular weight between cross-linking points), By adjusting the crosslink density) and the like, the effect of the embodiment of the present invention (for example, durability in a high temperature and high humidity environment) can be made more remarkable.
  • type of base polymer polarity, Tg, softness
  • molecular weight for example, type of cross-linking agent, distance between cross-linking points (molecular weight between cross-linking points)
  • the thickness of the first pressure-sensitive adhesive layer is preferably 2 ⁇ m to 15 ⁇ m, more preferably 3 ⁇ m to 12 ⁇ m, and even more preferably 5 ⁇ m to 10 ⁇ m.
  • the thickness of the second pressure-sensitive adhesive layer is preferably 10 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 30 ⁇ m, and even more preferably 10 ⁇ m to 20 ⁇ m.
  • the solubility of the first pressure-sensitive adhesive layer (substantially the pressure-sensitive adhesive constituting the first pressure-sensitive adhesive layer) in ethyl acetate at 25 ° C. is preferably 2 g / 100 g to 70 g / 100 g, more preferably 10 g. / 100 g to 60 g / 100 g, more preferably 15 g / 100 g to 60 g / 100 g.
  • the ultraviolet absorber can be appropriately incorporated into the first pressure-sensitive adhesive layer.
  • the molar extinction coefficient of the first pressure-sensitive adhesive layer at a wavelength of 380 nm is preferably 400 L / (mol ⁇ cm) or more, more preferably 500 L / (mol ⁇ cm) or more, and even more preferably 600 L / (mol ⁇ cm) or more. cm) or more.
  • the molar extinction coefficient is preferably 1500 mol / (L ⁇ cm) or less.
  • the molar extinction coefficient is a value obtained by the following formula.
  • Molar extinction coefficient A / (c ⁇ l) (In the formula, A represents the absorbance, c represents the molar concentration (mol / L), and l represents the cell thickness (cm).)
  • the gel fraction of the first pressure-sensitive adhesive layer is preferably 60% or more, more preferably 60% to 90%, and further preferably 80% to 90%.
  • the gel fraction is determined by (dry weight after immersion / dry weight before immersion) ⁇ 100 when the crosslinked pressure-sensitive adhesive is immersed in a predetermined solvent (for example, ethyl acetate) for 6 days and then dried.
  • the constituent material adheresive composition
  • a pressure-sensitive adhesive layer by combining the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer.
  • the base polymer pressure-sensitive adhesive layer is typically formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer, a urethane-based polymer, a silicone-based polymer, or a rubber-based polymer as the base polymer.
  • a (meth) acrylic polymer is used as the base polymer
  • the pressure-sensitive adhesive layer is formed from, for example, a pressure-sensitive adhesive composition containing the (meth) acrylic polymer (A).
  • the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component.
  • the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component.
  • the alkyl (meth) acrylate is preferably 50% by weight or more in all the monomer components forming the (meth) acrylic polymer (A) from the viewpoint of improving the adhesiveness of the pressure-sensitive adhesive layer, and the alkyl (meth) acrylate is said. ) It can be arbitrarily set as the remainder of the monomer other than acrylate.
  • (meth) acrylate means acrylate and / or methacrylate.
  • Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group and a decyl group.
  • Alkyl (meth) acrylates can be used alone or in combination.
  • the average carbon number of the alkyl group is preferably 3 to 10, and more preferably 3 to 6.
  • the (meth) acrylic polymer (A) may contain a copolymerization monomer such as a carboxyl group-containing monomer (a1) and a hydroxyl group-containing monomer (a2) as a monomer component in addition to the alkyl (meth) acrylate. Good.
  • the copolymerizable monomers can be used alone or in combination.
  • the carboxyl group-containing monomer (a1) is a compound containing a carboxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acrylic acid is preferable from the viewpoint of improving copolymerizability, price, and adhesive properties of the pressure-sensitive adhesive layer.
  • the content of the carboxyl group-containing monomer (a1) is usually 0.01% by weight in all the monomer components forming the (meth) acrylic polymer (A). It is 10% by weight or less.
  • the hydroxyl group-containing monomer (a2) is a compound containing a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as 10-hydroxydecyl (meth) acrylate and 12-hydroxylauryl (meth) acrylate; (4-hydroxymethylcyclohexyl) -methylacrylate and the like.
  • 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of improving the durability of the pressure-sensitive adhesive layer.
  • the content of the hydroxyl group-containing monomer (a2) is usually 0.01% by weight in all the monomer components forming the (meth) acrylic polymer (A). It is 10% by weight or less, and more preferably 0.05% by weight to 3% by weight.
  • copolymerization monomer (a3) may be further used as the monomer component.
  • the other copolymerizable monomer (a3) has a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • the other copolymerization monomer (a3) can be used alone or in combination.
  • the amino group-containing monomer is, for example, N, N-dimethylaminoethyl (meth) acrylate or N, N-dimethylaminopropyl (meth) acrylate.
  • the amide group-containing monomer includes, for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-methyl (meth) acrylamide, and N-butyl ( Meta) acrylamide, N-hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) ) Acrylamides such as acrylamide and mercaptoethyl (meth) acrylamide; N-acrylloyl heterocyclic monomers such as N- (meth) acryloylmorpholin, N- (meth) acryloylpiperidin and N- (meth) acryloylpyrrolidin. It is an
  • copolymerization monomers (a3) include, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and (meth).
  • (Meta) acrylic acid alkoxyalkyl esters such as 3-methoxypropyl acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate; 2-( Cyclic polymerizable monomer such as methyl allyloxymethyl) acrylate; epoxy group-containing monomer such as (meth) glycidyl acrylate, methyl glycidyl (meth) acrylate; sulfonic acid group-containing monomer such as sodium vinyl sulfonate; phosphoric acid Group-containing monomer; (meth) acrylate having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; phenyl (meth) acrylate, (meth).
  • aromatic hydrocarbon groups such as phenoxyethyl acrylate and benzyl (meth) acrylate
  • vinyl esters such as vinyl acetate and vinyl propionate
  • aromatic vinyl compounds such as styrene and vinyl toluene Olefins or dienes such as ethylene, propylene, butadiene, isoprene, isobutylene
  • vinyl ethers such as vinylalkyl ethers
  • vinyl chloride can be used.
  • the content of the other copolymerization monomer (a3) in the (meth) acrylic polymer is preferably 20% by weight or less.
  • the (meth) acrylic polymer is, for example, a copolymer of butyl acrylate, acrylic acid, hydroxybutyl acrylate, hydroxyethyl acrylate and acryloyl morpholine, a copolymer of butyl acrylate, acrylic acid and hydroxyethyl acrylate, and butyl acrylate. It can be a copolymer of hydroxybutyl acrylate, or a polymer of butyl acrylate, acrylic acid, hydroxybutyl acrylate, N-vinylpyrrolidone, and phenoxyethyl acrylate.
  • the (meth) acrylic polymer (A) may contain acrylic acid in the monomer component, preferably 0.1% by weight to 7% by weight, more preferably 2% by weight to 6% by weight. ..
  • the weight average molecular weight Mw of the (meth) acrylic polymer (A) is, for example, 200,000 to 3 million, preferably 1 million to 2.5 million, and more preferably 1.2 million to 2.5 million.
  • a pressure-sensitive adhesive layer having excellent durability (particularly heat resistance) can be obtained. If the weight average molecular weight Mw exceeds 3 million, an increase in viscosity and / or gelation during polymer polymerization may occur.
  • the pressure-sensitive adhesive composition can contain a reactive functional group-containing silane coupling agent.
  • the reactive functional group is typically a functional group other than the acid anhydride group.
  • the functional group other than the acid anhydride group include an epoxy group, a mercapto group, an amino group, an isocyanate group, an isocyanurate group, a vinyl group, a styryl group, an acetoacetyl group, a ureido group, a thiourea group and a (meth) acrylic.
  • Examples include groups, heterocyclic groups, and combinations thereof.
  • Reactive functional group-containing silane coupling agents can be used alone or in combination.
  • the blending amount of the reactive functional group-containing silane coupling agent is usually 100 parts by weight of the (meth) acrylic polymer (A). 0.001 part by weight or more and 5 parts by weight or less.
  • the pressure-sensitive adhesive composition can contain a cross-linking agent.
  • a cross-linking agent an organic cross-linking agent, a polyfunctional metal chelate, or the like can be used.
  • the organic cross-linking agent include isocyanate-based cross-linking agents, peroxide-based cross-linking agents, epoxy-based cross-linking agents, and imine-based cross-linking agents.
  • a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinated to an organic compound.
  • a polyfunctional monomer can be used as a cross-linking agent.
  • Crosslinkers can be used alone or in combination.
  • the blending amount of the cross-linking agent is usually 0.01 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A).
  • the blending amount of the isocyanate-based cross-linking agent is usually 0.01 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the pressure-sensitive adhesive layer (substantially, the pressure-sensitive adhesive composition) contains an ultraviolet absorber as described above.
  • the ultraviolet absorber may be contained in the first pressure-sensitive adhesive layer or may be contained in the second pressure-sensitive adhesive layer.
  • the UV absorber is preferably contained in the first pressure-sensitive adhesive layer.
  • the content of the ultraviolet absorber in the pressure-sensitive adhesive layer is as described in the above item A.
  • any suitable ultraviolet absorber may be adopted. Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber.
  • the ultraviolet absorber may be used alone or in combination of two or more. Further, the UV absorber may be used in combination with an antioxidant.
  • the radical generator pressure-sensitive adhesive layer may contain a radical generator.
  • the radical generator include those that generate radicals by irradiation with visible light or ultraviolet rays having a wavelength shorter than 450 nm. Specific examples include hydroxyketones, benzyldimethylketals, aminoketones, acylphosphine oxides, benzophenones, and trichloromethyl group-containing triazine derivatives.
  • the radical generator may be used alone or in combination of two or more.
  • the radical generator can be a peroxide-based cross-linking agent.
  • the radical generator is preferably 0.01 parts by weight to 2 parts by weight, more preferably 0.01 parts by weight to 1 part by weight, based on 100 parts by weight of the base polymer ((meth) acrylic polymer (A)). Can be used in proportions. Within such a range, it is easy to adjust workability, cross-linking stability, and the like.
  • the pressure-sensitive adhesive composition may contain (meth) acrylic oligomers and / or ionic compounds. Moreover, the pressure-sensitive adhesive composition may contain an additive. Specific examples of additives include powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antiaging agents, light stabilizers, and polymerizations. Prohibition agents, inorganic or organic fillers, metal powders, particulates, foils and the like. Further, a redox system to which a reducing agent is added may be adopted within a controllable range. The type, number, combination, content, etc. of additives can be appropriately set according to the purpose. The content of the additive is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A). is there.
  • an embodiment of the present invention includes an organic EL display device using such a retardation layer and a polarizing plate with an adhesive layer.
  • the organic EL display device according to the embodiment of the present invention includes the retardation layer and the polarizing plate with an adhesive layer according to the above items A to D on the visible side thereof.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer are laminated so that the retardation layer is on the organic EL cell side (the polarizing plate is on the visual recognition side).
  • the organic EL display device has a curved shape (substantially a curved display screen) and / or is bendable or bendable.
  • the present inventors have a phase difference due to ammonia (substantially ammonium ions) generated from the organic EL panel.
  • ammonia substantially ammonium ions
  • Polarization degree P (%) ⁇ (Tp-Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100 (3) Moisture Permeability Measured according to JIS Z 0208. Specifically, the protective layer or the retardation layer (the film constituting the layer) used in Examples and Comparative Examples was cut out in a circle of 10 cm ⁇ and used as a measurement sample. The moisture permeability of this measurement sample was measured using "MOCON" manufactured by Hitachi, Ltd. under the test conditions of 40 ° C. and 92% RH. (4) Transmittance at a Wavelength of 380 nm The retardation layer and the polarizing plate with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples were cut out to a predetermined size and used as a measurement sample.
  • This measurement sample was attached to a measuring jig via a second pressure-sensitive adhesive layer, and measured at a wavelength of 380 nm using a spectrophotometer (product name: LPF-2000, manufactured by Otsuka Electronics Co., Ltd.).
  • a spectrophotometer product name: LPF-2000, manufactured by Otsuka Electronics Co., Ltd.
  • Ammonia decolorization test 10 g of a 10% aqueous ammonia solution was placed in a glass bottle (cylindrical shape having a diameter of 30 mm and a depth of 50 mm). At this time, the distance from the liquid level of the aqueous ammonia solution to the mouth (upper end) of the glass bottle was about 30 mm.
  • the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut out to a size of 15 mm ⁇ 15 mm and used as a measurement sample.
  • the measurement sample was attached to the edge of the mouth of the glass bottle via the second adhesive layer so that the mouth of the glass bottle was completely covered with this measurement sample and steam did not leak through the gap.
  • the glass bottle covered with the measurement sample was heated at 60 ° C. for 2 hours.
  • thermoplastic resin base material As the thermoplastic resin base material, an amorphous isophthalic copolymerized 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 acetoacetyl-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 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).
  • the finally obtained polarizing film was placed in a dyeing bath having a liquid temperature of 30 ° C.
  • HC-TAC film was attached to the surface of the polarizer of the resin base material / polarizer laminate obtained above via an ultraviolet curable adhesive. Specifically, the curable adhesive was coated so as to have a thickness of 1.0 ⁇ m, and bonded using a roll machine. Then, UV light was irradiated from the HC-TAC film side to cure the adhesive.
  • the HC-TAC film is a film in which a hard coat (HC) layer (thickness 7 ⁇ m) is formed on a triacetyl cellulose (TAC) film (thickness 25 ⁇ m), and the TAC film is attached so as to be on the polarizer side. I matched it.
  • a polarizing plate P1 having a visible side protective layer (HC-TAC film) / polarizer was peeled off to obtain a polarizing plate P1 having a visible side protective layer (HC-TAC film) / polarizer.
  • Moisture permeability of the HC-TAC film was 427g / m 2 ⁇ 24h.
  • the HC-COP film is a film in which an HC layer (thickness 2 ⁇ m) is formed on a cycloolefin resin (COP) film (thickness 25 ⁇ m), and the COP film is bonded so as to be on the polarizer side.
  • Moisture permeability of the HC-COP film was 17g / m 2 ⁇ 24h.
  • the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
  • polyester carbonate-based resin pellet
  • T-die width 200 mm, set temperature: 250.
  • a long resin film having a thickness of 135 ⁇ m was prepared by using a film forming apparatus equipped with a chill roll (set temperature: 120 to 130 ° C.) and a winder.
  • the obtained long resin film was stretched in the width direction at a stretching temperature of 133 ° C. and a stretching ratio of 2.8 times to obtain a retardation film having a thickness of 47 ⁇ m.
  • the Re (550) of the obtained retardation film was 141 nm, the Re (450) / Re (550) was 0.82, and the Nz coefficient was 1.12. Further, the moisture permeability of the obtained retardation film was 75g / m 2 ⁇ 24h.
  • the obtained coating film was subjected to a rubbing treatment to form an alignment film.
  • the rubbing treatment was performed using a commercially available rubbing device.
  • the polymerizable composition obtained above was applied to a base material (substantially an alignment film) by a spin coating method, and dried at 100 ° C. for 2 minutes.
  • the obtained coating film was cooled to room temperature and then irradiated with ultraviolet rays at an intensity of 30 mW / cm 2 for 30 seconds using a high-pressure mercury lamp to obtain a liquid crystal oriented solidified layer.
  • the in-plane retardation Re (550) of the liquid crystal oriented solidified layer was 130 nm.
  • the Re (450) / Re (550) of the liquid crystal oriented solidified layer was 0.851, showing the inverse dispersion wavelength characteristic.
  • Example 1 An ultraviolet absorber, a radical generator, a cross-linking agent, and an antioxidant were added to 100 parts of the base polymer A obtained in Production Example 6 at the ratios shown in Table 1 to prepare a pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive layer having a thickness of 5 ⁇ m was formed from this pressure-sensitive adhesive composition to form a first pressure-sensitive adhesive layer.
  • a radical generator, a cross-linking agent, and an antioxidant were blended with 100 parts of the base polymer B obtained in Production Example 7 at the ratio shown in Example 7 of Table 1 to prepare a pressure-sensitive adhesive composition. ..
  • a pressure-sensitive adhesive layer having a thickness of 15 ⁇ m was formed from this pressure-sensitive adhesive composition to form a second pressure-sensitive adhesive layer.
  • the retardation film obtained in Production Example 4 is attached to the surface of the polarizer of the polarizing plate P1 obtained in Production Example 1 via the first pressure-sensitive adhesive layer, and further, the second retardation film is attached to the surface of the retardation film.
  • the pressure-sensitive adhesive layer was provided. In this way, the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer of this example was produced.
  • the obtained retardation layer and the polarizing plate with the pressure-sensitive adhesive layer were subjected to the evaluations (4) to (6) above. The results are shown in Table 1.
  • Examples 2 to 14, Comparative Examples 1 to 6, and Reference Example 1 A pressure-sensitive adhesive composition is prepared according to the formulation shown in Table 1, and a retardation layer and a retardation layer and a combination of a polarizing plate, a retardation film or a liquid crystal oriented solidifying layer, a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer shown in Table 1 are used.
  • a polarizing plate with an adhesive layer was prepared.
  • the obtained retardation layer and the polarizing plate with the pressure-sensitive adhesive layer were subjected to the same evaluation as in Example 1.
  • the results are shown in Table 1.
  • the liquid crystal oriented solidified layer Example 4 was transferred from the base material to the surface of the polarizer via the first pressure-sensitive adhesive layer.
  • the phase difference is excellent in ultraviolet absorption ability and excellent durability in a high temperature and high humidity environment (specifically, bubbles are suppressed).
  • a polarizing plate with a layer and an adhesive layer can be obtained.
  • the retardation layer and the polarizing plate with the pressure-sensitive adhesive layer of the examples have an advantage that the degree of polarization hardly changes (that is, does not decolorize) even when exposed to ammonia.
  • Example 14 in which the ultraviolet absorber was introduced only into the second pressure-sensitive adhesive layer, some deterioration was observed in the retardation layer.
  • the effect of containing the ultraviolet absorber in the pressure-sensitive adhesive layer is an effect obtained in a configuration in which the polarizing plate has a protective layer only on the visual side (however, polarized light). In a configuration in which the plate has protective layers on both sides, it is not denied that the pressure-sensitive adhesive layer contains an ultraviolet absorber).
  • the polarizing plate with the retardation layer and the pressure-sensitive adhesive layer of the present invention is suitably used as an antireflection circular polarizing plate of an organic EL display device.
  • Polarizing plate 11 Polarizing element 12
  • Protective layer 13 Protective layer 20
  • Phase difference layer 100

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Abstract

L'invention concerne une plaque de polarisation avec une couche à différence de phase et une couche adhésive, qui a une excellente durabilité dans des environnements à haute température, à humidité élevée et une décoloration significativement supprimée lorsqu'elle est appliquée à un dispositif d'affichage électroluminescent organique. Cette plaque de polarisation avec une couche à différence de phase et une couche adhésive comprend : une plaque de polarisation comprenant un polariseur et une couche de protection sur au moins le côté visible du polariseur ; une couche à différence de phase collée sur le côté opposé au côté visible de la plaque de polarisation, ayant une première couche adhésive entre celles-ci ; et une seconde couche adhésive disposée en tant que couche la plus à l'extérieur sur le côté opposé de la couche à différence de phase vers la plaque de polarisation. La première couche adhésive ou la seconde couche adhésive comprend un agent absorbant la lumière UV. La teneur en agent absorbant la lumière UV dans la première couche adhésive ou la seconde couche adhésive est de 1 % à 12 % en masse La plaque de polarisation avec une couche à différence de phase et une couche adhésive a une transmittance inférieure ou égale à 5 % à une longueur d'onde de 380 nm.
PCT/JP2020/033266 2019-10-10 2020-09-02 Plaque de polarisation avec couche à différence de phase et couche adhésive et dispositif d'affichage électroluminescent organique l'utilisant WO2021070525A1 (fr)

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WO2022224494A1 (fr) * 2021-04-19 2022-10-27 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard
WO2023042518A1 (fr) * 2021-09-14 2023-03-23 日東電工株式会社 Corps stratifié optique
WO2023100406A1 (fr) * 2021-11-30 2023-06-08 日東電工株式会社 Plaque de polarisation avec couche de retard et dispositif d'affichage d'image ayant ladite plaque de polarisation avec couche de retard
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WO2023100406A1 (fr) * 2021-11-30 2023-06-08 日東電工株式会社 Plaque de polarisation avec couche de retard et dispositif d'affichage d'image ayant ladite plaque de polarisation avec couche de retard

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