WO2023132148A1 - 偏光板および有機エレクトロルミネセンス表示装置 - Google Patents

偏光板および有機エレクトロルミネセンス表示装置 Download PDF

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WO2023132148A1
WO2023132148A1 PCT/JP2022/043398 JP2022043398W WO2023132148A1 WO 2023132148 A1 WO2023132148 A1 WO 2023132148A1 JP 2022043398 W JP2022043398 W JP 2022043398W WO 2023132148 A1 WO2023132148 A1 WO 2023132148A1
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layer
polarizing plate
polarizer
less
laminated film
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PCT/JP2022/043398
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English (en)
French (fr)
Japanese (ja)
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寛 友久
遼太 藤野
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日東電工株式会社
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • 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
    • H10K59/10—OLED displays

Definitions

  • the present invention relates to a polarizing plate and an organic electroluminescence (EL) display device.
  • the present invention has been made to solve the above problems, and its main purpose is to provide a polarizing plate with extremely excellent durability.
  • a polarizing plate includes a polarizer having a first principal surface and a second principal surface facing each other, and a substrate and a hard coat layer disposed on the first principal surface side of the polarizer. It has a laminated film including in this order from the polarizer side and a retardation layer arranged on the second main surface side of the polarizer, and the laminated film has a moisture permeability of 600 g / m 2 ⁇ 24 h or less. The rate of change in moisture permeability of the laminated film when the laminated film is placed in an environment of 65 ° C.
  • the retardation layer has a moisture permeability of 200 g / m 2.24 hours or less.
  • the rate of change is 1.1 or more.
  • the hard coat layer has a thickness of 1 ⁇ m or more.
  • the hard coat layer has a thickness of 7 ⁇ m or less.
  • the laminated film includes an intermediate layer containing a component derived from the base material and a component derived from the hard coat layer, between the base material and the hard coat layer.
  • the retardation layer is arranged adjacent to the polarizer. In one embodiment, Re(450)/Re(550) of the retardation layer is 0.8 or more and less than 1.
  • the single transmittance of the polarizer is 43.0% or more. In one embodiment, the thickness of the polarizer is 10 ⁇ m or less.
  • an organic electroluminescent display device is provided. This organic electroluminescence display device has the above polarizing plate.
  • FIG. 1 is a schematic cross-sectional view showing a schematic configuration of a polarizing plate according to one embodiment of the present invention
  • FIG. 2 is a cross-sectional view showing an example of a schematic configuration of a laminated film of the polarizing plate shown in FIG. 1
  • 1 is a schematic cross-sectional view showing an outline of a state in which a polarizing plate is arranged on an organic EL panel in an organic EL display device according to one embodiment of the present invention
  • refractive index (nx, ny, nz) is the refractive index in the direction in which the in-plane refractive index is maximum (i.e., slow axis direction), and "ny” is the in-plane direction orthogonal to the slow axis (i.e., fast axis direction) and "nz” is the refractive index in the thickness direction.
  • In-plane retardation (Re) “Re( ⁇ )” is an in-plane retardation measured at 23° C. with light having a wavelength of ⁇ nm.
  • Re(550) is the in-plane retardation measured with light having a wavelength of 550 nm at 23°C.
  • Thickness direction retardation (Rth) is the retardation in the thickness direction measured at 23° C. with light having a wavelength of ⁇ nm.
  • Rth(550) is the retardation in the thickness direction measured at 23° C. with light having a wavelength of 550 nm.
  • FIG. 1 is a schematic cross-sectional view showing the schematic configuration of a polarizing plate according to one embodiment of the present invention
  • FIG. 2 is a cross-sectional view showing an example of the schematic configuration of the laminated film of the polarizing plate shown in FIG. It is a diagram.
  • a polarizing plate (polarizing plate with a retardation layer) 100 includes a polarizer 10 having a first main surface 10a and a second main surface 10b facing each other, and a laminated film arranged on the first main surface 10a side of the polarizer 10. 20 , and a retardation layer 30 and an adhesive layer 40 which are arranged on the second main surface 10 b side of the polarizer 10 .
  • Laminated film 20 includes substrate 21 and hard coat layer 22 in this order from the polarizer 10 side, and substrate 21 can function as a protective layer for polarizer 10 .
  • the polarizing plate 100 is typically arranged so that the laminated film 20 is on the viewer side of the polarizer 10 in the organic EL display device.
  • the retardation layer 30 is a single layer, but unlike the illustrated example, it may have a laminated structure of two or more layers. Specifically, the retardation layer 30 may include two or more layers having different optical properties (for example, refractive index properties, in-plane retardation, Nz coefficient, photoelastic coefficient). In the illustrated example, no protective layer is arranged between the polarizer 10 and the retardation layer 30, and the retardation layer 30 is arranged adjacent to the polarizer 10 as a protective layer for the polarizer 10. Although functional, polarizer 100 may have a protective layer disposed between polarizer 10 and retardation layer 30 . Note that "adjacent" includes not only direct adjacency but also adjacency via an adhesive layer, which will be described later.
  • Each member constituting the polarizing plate can be laminated via any suitable adhesive layer (not shown).
  • the adhesive layer include an adhesive layer and an adhesive layer.
  • the laminated film 20 is attached to the polarizer 10 via an adhesive layer (preferably using an active energy ray-curable adhesive).
  • the retardation layer 30 is applied via an adhesive layer (preferably using an active energy ray-curable adhesive), or via an adhesive layer (e.g., an acrylic adhesive) to the polarizer 10 or It is attached to a protective layer (not shown).
  • the retardation layer 30 has a laminated structure of two or more layers, the respective retardation layers are bonded together via an adhesive layer (preferably using an active energy ray-curable adhesive), for example.
  • the thickness of the adhesive layer is preferably 0.4 ⁇ m or more, more preferably 0.4 ⁇ m to 3.0 ⁇ m, still more preferably 0.6 ⁇ m to 1.5 ⁇ m.
  • the thickness of the adhesive layer is preferably 1 ⁇ m to 10 ⁇ m.
  • the polarizing plate 100 can be attached to the organic EL panel main body by the adhesive layer 40 arranged on the second main surface 10b side of the polarizer 10 .
  • a release liner is practically adhered to the surface of the pressure-sensitive adhesive layer 40 .
  • the release liner can be temporarily attached until the polarizer is ready for use.
  • a release liner for example, it is possible to protect the pressure-sensitive adhesive layer and roll-form the polarizing plate.
  • the polarizing plate may be elongated or sheet-shaped.
  • the term "elongated” refers to an elongated shape whose length is sufficiently longer than its width, for example, an elongated shape whose length is 10 times or more, preferably 20 times or more, its width.
  • a long polarizing plate can be wound into a roll.
  • the polarizer is typically a film containing a dichroic substance (typically iodine).
  • the thickness of the polarizer is, for example, preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less, even more preferably 10 ⁇ m or less, and particularly preferably 8 ⁇ m or less, from the viewpoint of thinning.
  • the thickness of the polarizer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 3 ⁇ m or more.
  • the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the single transmittance of the polarizer is, for example, 40.0% or more, preferably 41.5% or more, more preferably 43.0% or more, still more preferably 44.5% or more. In a polarizer having a high unitary transmittance, the problem of decolorization can become more pronounced.
  • the single transmittance is, for example, 48.0% or less, may be 46.0% or less, or may be 45.0% or less.
  • the degree of polarization of the polarizer is preferably 97.0% or higher, more preferably 99.0% or higher, still more preferably 99.9% or higher.
  • the single transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
  • the degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
  • Degree of polarization (%) ⁇ (Tp-Tc)/(Tp+Tc) ⁇ 1/2 ⁇ 100
  • the polarizer can be produced by any suitable method. Specifically, the polarizer may be produced from a single-layer resin film, or may be produced using a laminate of two or more layers.
  • the method of producing a polarizer from the single-layer resin film typically includes subjecting the resin film to a dyeing treatment with a dichroic substance such as iodine or a dichroic dye and a stretching treatment.
  • a dichroic substance such as iodine or a dichroic dye
  • a stretching treatment for example, hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and partially saponified ethylene/vinyl acetate copolymer films are used.
  • the method may further include an insolubilization treatment, a swelling treatment, a cross-linking treatment, and the like. Since such a manufacturing method is well known and commonly used in the industry, detailed description thereof will be omitted.
  • a polarizer obtained using the laminate can be produced, for example, using a laminate of a resin substrate and a resin film or resin layer (typically, a PVA-based resin layer).
  • a PVA-based resin solution is applied to a resin base material, dried to form a PVA-based resin layer on the resin base material, and a laminate of the resin base material and the PVA-based resin layer is obtained; stretching and dyeing the laminate to make the PVA-based resin layer a polarizer;
  • a PVA-based resin layer containing a halide and a PVA-based resin is formed on one side of the resin substrate. Stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching.
  • stretching may further include stretching the laminate in air at a high temperature (eg, 95° C. or higher) before stretching in an aqueous boric acid solution, if necessary.
  • the laminate is preferably subjected to drying shrinkage treatment for shrinking the laminate by 2% or more in the width direction by heating while conveying in the longitudinal direction.
  • the manufacturing method of the present embodiment includes subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order.
  • a polarizing plate can be obtained by laminating a protective layer on the peeled surface of the obtained resin substrate/polarizer laminate, or on the surface opposite to the peeled surface. Details of the method for manufacturing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. These publications are incorporated herein by reference in their entireties.
  • the laminated film 20 has a base material (protective layer) 21 and a hard coat layer 22, and further includes the base material 21 and the hard coat layer 22.
  • An intermediate layer 23 may be formed between.
  • the polarizing plate according to the embodiment of the present invention is typically arranged on the viewing side of the organic EL display device, and the hard coat layer 22 is arranged on the viewing side of the substrate 21 .
  • the hard coat layer 22 may function as other functional layers such as an antireflection layer, an antisticking layer, an antiglare layer, and the like.
  • the thickness of the laminated film is, for example, 15 ⁇ m or more and 70 ⁇ m or less, preferably 20 ⁇ m or more and 50 ⁇ m or less.
  • the moisture permeability of the laminated film at 40° C. and 92% RH is 600 g/m 2 ⁇ 24 h or less, preferably 550 g/m 2 ⁇ 24 h or less, more preferably 500 g/m 2 ⁇ 24 h or less, and further It is preferably 450 g/m 2 ⁇ 24 h or less.
  • the moisture permeability of the laminated film at 40° C. and 92% RH is preferably 300 g/m 2 ⁇ 24 h or more, preferably 320 g/m 2 ⁇ 24 h or more, more preferably 340 g/m 2 ⁇ 24 h or more. is.
  • the moisture permeability of the laminated film subjected to humidification treatment at 40°C and 92% RH is preferably 800g/ m2 ⁇ 24h or less, more preferably 700g/ m2 ⁇ 24h or less, and still more preferably 600g/m2. 2.24 hours or less.
  • the rate of change in moisture permeability due to humidification is 1.5 or less, preferably 1.4 or less.
  • the moisture permeability of the laminated film subjected to humidification treatment at 40°C and 92% RH is preferably 400 g/ m2 ⁇ 24h or more, more preferably 450g/ m2 ⁇ 24h or more, and still more preferably 500g/m2. 2.24 hours or more.
  • the rate of change in moisture permeability due to humidification is preferably 1.1 or more, more preferably 1.2 or more. Decolorization can be suppressed by using such a laminated film.
  • the present inventors have found that the main cause of the problem that the polarizing plate tends to decolor when the polarizing plate is used in an organic EL display device is derived from the members constituting the organic EL panel and occurs in a high-humidity environment. It is ammonia (substantially, ammonium ions) that makes it easier to decolorize, and it was found that decolorization can be suppressed by discharging ammonium ions that have entered the polarizing plate (polarizer). Discoloration can be suppressed by arranging a member having high moisture permeability on one side (typically, the viewing side) of the polarizer. Specifically, decomposition of a dichroic substance (typically an iodine complex) contained in the polarizer can be suppressed.
  • a dichroic substance typically an iodine complex
  • the base material can be composed of any suitable film that can be used as a protective layer for a polarizer.
  • Materials constituting such a substrate (film) include, for example, cellulose-based resins such as triacetylcellulose (TAC), cycloolefin-based resins such as polynorbornene, polycarbonate-based resins, (meth)acrylic-based resins, and polyethylene.
  • cellulose-based resins such as triacetylcellulose (TAC)
  • cycloolefin-based resins such as polynorbornene
  • polycarbonate-based resins polycarbonate-based resins
  • (meth)acrylic-based resins and polyethylene.
  • polyester resins such as terephthalate (PET) and polyethylene naphthalate (PEN)
  • polyolefin resins such as polyethylene.
  • a cellulose-based resin such as triacetyl cellulose (TAC) is used as the material constituting the base material.
  • the thickness of the base material is, for example, 10 ⁇ m or more and 65 ⁇ m or less, preferably 15 ⁇ m or more and 45 ⁇ m or less.
  • the hard coat layer is typically formed by applying a hard coat layer-forming material to the substrate and curing the applied layer.
  • a hard coat layer-forming material typically contains a curable compound as a layer-forming component. Curing mechanisms of the curable compound include, for example, thermosetting and photocuring. Curable compounds include, for example, monomers, oligomers, and prepolymers. Preferably, polyfunctional monomers or oligomers are used as curable compounds.
  • Polyfunctional monomers or oligomers include, for example, monomers or oligomers having two or more (meth)acryloyl groups, urethane (meth)acrylates or urethane (meth)acrylate oligomers, epoxy-based monomers or oligomers, silicone-based monomers or oligomers. is mentioned.
  • the hard coat layer-forming material may contain any appropriate additive.
  • Additives include, for example, polymerization initiators, leveling agents, antiblocking agents, dispersion stabilizers, thixotropic agents, antioxidants, UV absorbers, antifoaming agents, thickeners, dispersants, surfactants, and catalysts. , fillers, lubricants, antistatic agents, and the like.
  • the type, combination, content, etc. of additives can be appropriately set according to the purpose and desired properties.
  • the heating temperature is, for example, 60°C to 140°C, preferably 60°C to 100°C.
  • the curing treatment is typically carried out by UV irradiation.
  • the integrated amount of UV irradiation is, for example, 100 mJ/cm 2 to 300 mJ/cm 2 . UV irradiation and heating may be combined.
  • the thickness of the hard coat layer is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, and still more preferably 2 ⁇ m or more. With such a thickness, it is possible to prevent the moisture permeability of the laminated film from becoming too high. Moreover, the abrasion resistance of the obtained polarizing plate can be ensured.
  • the thickness of the hard coat layer is preferably 7 ⁇ m or less, more preferably 6 ⁇ m or less, and even more preferably 5 ⁇ m or less. With such a thickness, the moisture permeability can be satisfactorily satisfied and, for example, decolorization can be suppressed.
  • the scratch resistance is evaluated, for example, by rubbing the surface of the hard coat layer with a cylinder having steel wool #0000 attached to the bottom surface at a load of 1.0 kg at a speed of about 100 mm per second for 1000 reciprocations. It can be evaluated by visually confirming the degree of scratches on the layer surface.
  • the intermediate layer may contain a component derived from the base material and a component derived from the hard coat layer.
  • the component that forms the base material and the component that forms the hard coat layer may be compatible (mixed) together.
  • the substrate comprises TAC
  • components derived from the substrate include TAC, acetic acid and cellulose.
  • the interface between the intermediate layer and the substrate and the interface between the intermediate layer and the hard coat layer can be confirmed by observation with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the thickness of the intermediate layer is, for example, 1 ⁇ m or more and 30 ⁇ m or less, preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • the ratio of the thickness of the hard coat layer to the thickness of the intermediate layer is preferably 0.5 or more, more preferably 0.6 or more. According to such a thickness ratio, for example, change in moisture permeability of the laminated film due to humidification can be suppressed.
  • the ratio of the thickness of the hard coat layer to the thickness of the intermediate layer is preferably 1.0 or less, more preferably 0.9 or less. According to such a thickness ratio, the moisture permeability can be satisfactorily satisfied, and, for example, decolorization can be suppressed.
  • the intermediate layer can be formed, for example, by adding a good solvent capable of dissolving the substrate into the solvent that may be contained in the hard coat layer-forming material. Specifically, some of the components contained in the hard coat layer-forming material (typically, a solvent) are mixed with the base material and/or permeate into the base material to form the base material and the hard coat. The components that form the layer are compatible (mixed), and an intermediate layer can be formed.
  • a good solvent capable of dissolving the substrate into the solvent that may be contained in the hard coat layer-forming material.
  • some of the components contained in the hard coat layer-forming material typically, a solvent
  • the components that form the layer are compatible (mixed), and an intermediate layer can be formed.
  • Examples of the solvent that may be contained in the hard coat layer-forming material include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, TBA (tertiary butyl alcohol), and 2-methoxyethanol; acetone and MEK (methyl ethyl ketone).
  • alcohols such as methanol, ethanol, isopropyl alcohol, butanol, TBA (tertiary butyl alcohol), and 2-methoxyethanol
  • acetone and MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • ketones such as cyclopentanone
  • esters such as methyl acetate, ethyl acetate, butyl acetate, PMA (propylene glycol monomethyl ether acetate); ethers such as diisopropyl ether, propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane and octane; and aromatic hydrocarbons such as benzene, toluene and xylene.
  • the content of the solvent is set so that the solid concentration of the hard coat layer-forming material is, for example, 20% by weight or more and 50% by weight or less, preferably 30% by weight or more and 45% by weight or less.
  • good solvent capable of dissolving the base material for example, a solvent that dissolves 30 parts by weight or more of the base material (solute) with respect to 100 parts by weight of the solvent is used.
  • good solvents capable of dissolving the substrate include, for example, cyclopentanone (for example, the amount of TAC dissolved in 100 parts by weight of cyclopentanone is 40 parts by weight), MEK ( For example, the amount of TAC dissolved in 100 parts by weight of MEK is 60 parts by weight), cyclohexanone, methyl acetate, and ethyl acetate are preferably used.
  • the hard coat layer-forming material contains a good solvent that can dissolve the substrate and a poor solvent that does not substantially dissolve the substrate.
  • a poor solvent that does not substantially dissolve the base material for example, a solvent that dissolves less than 30 parts by weight of the base material (solute) with respect to 100 parts by weight of the solvent is used. ) is dissolved in an amount of 10 parts by weight or less.
  • the substrate contains TAC, for example, ethanol, isopropyl alcohol, and hexane are preferably used as poor solvents that do not substantially dissolve the substrate.
  • Ratio of the content of a good solvent capable of dissolving a substrate to the content of a poor solvent that does not substantially dissolve the substrate in the hard coat layer-forming material is, for example, 1.5 or less, preferably 0.3 or more and 1.2 or less, more preferably 0.4 or more and 1.1 or less.
  • the retardation layer may be a single layer as illustrated, or may have a laminated structure of two or more layers. When the retardation layer is a single layer, the retardation layer can typically function as a ⁇ /4 plate.
  • a retardation layer is typically provided to impart antireflection properties 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, still more preferably 120 nm to 160 nm.
  • the Nz coefficient of the retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3. By satisfying such a relationship, it is possible to obtain an organic EL display device having a very excellent reflective hue.
  • the retardation layer When the retardation layer is a single layer, the retardation layer preferably exhibits reverse dispersion wavelength characteristics in which the retardation value increases according to the wavelength of the measurement light.
  • Re(450)/Re(550) of the retardation layer is preferably 0.8 or more and less than 1, more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection properties can be achieved.
  • 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°, still more preferably about 45°. If the angle is within such a range, an organic EL display device having extremely excellent antireflection properties can be obtained by using a ⁇ /4 plate as the retardation layer as described above.
  • the moisture permeability of the retardation layer at 40° C. and 92% RH is 200 g/m 2 ⁇ 24h or less, preferably 150 g/m 2 ⁇ 24h or less, more preferably 100 g/m 2 ⁇ 24h or less.
  • Such a retardation layer can function as a blocking layer that blocks penetration of ammonia (ammonium ions) into the polarizer, and can contribute to suppression of decoloration.
  • the moisture permeability of the retardation layer at 40° C. and 92% RH is, for example, 50 g/m 2 ⁇ 24 h or more.
  • the moisture permeability of the retardation layer refers to the moisture permeability of the laminate structure that may include an adhesive layer.
  • the retardation layer can be made of any suitable material as long as it can satisfy the properties described above.
  • the retardation layer may be a resin film (stretched resin film), or may be an alignment and solidification layer of a liquid crystal compound (liquid crystal alignment and solidification layer).
  • the retardation layer is composed of a resin film (stretched resin film).
  • the thickness of the retardation layer is preferably 10 ⁇ m or more and 70 ⁇ m or less, more preferably 20 ⁇ m or more and 60 ⁇ m or less.
  • a representative example of the resin that constitutes the resin film is a polycarbonate-based resin or a polyester carbonate-based resin (hereinafter sometimes simply referred to as a polycarbonate-based resin). Any appropriate polycarbonate-based resin can be used as the polycarbonate-based resin as long as the desired moisture permeability can be obtained.
  • a polycarbonate-based resin includes 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 and a structural unit derived from at least one dihydroxy compound selected from the group consisting of glycols or spiroglycols.
  • 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, 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 as necessary.
  • the retardation layer can be formed by stretching a film composed of a polycarbonate-based resin as described above under any appropriate stretching conditions.
  • the thickness of the adhesive layer 40 is preferably 10 ⁇ m to 20 ⁇ m.
  • the adhesive layer can be composed of any appropriate adhesive. Specific examples include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, urethane adhesives, epoxy adhesives, and polyether adhesives. By adjusting the type, number, combination and compounding ratio of the monomers forming the base resin of the adhesive, as well as the compounding amount of the cross-linking agent, the reaction temperature, the reaction time, etc., a pressure-sensitive adhesive having desired properties according to the purpose. can be prepared.
  • the base resin of the adhesive may be used alone or in combination of two or more.
  • the base resin is preferably an acrylic resin (specifically, the pressure-sensitive adhesive layer is preferably composed of an acrylic pressure-sensitive adhesive).
  • Organic EL Display Device The polarizing plate can be used in an organic EL display device. Therefore, an organic EL display device according to an embodiment of the present invention has the above polarizing plate.
  • FIG. 3 is a schematic cross-sectional view showing an outline of a state in which a polarizing plate is arranged on an organic EL panel in an organic EL display device according to one embodiment of the present invention.
  • the polarizing plate (polarizing plate with a retardation layer) 100 is arranged in the organic EL panel 200 such that the polarizer 10 is closer to the organic EL panel main body 70 than the laminated film 20 is.
  • the polarizing plate 100 is attached to the organic EL panel main body 70 with the adhesive layer 40 .
  • the organic EL panel main body 70 has a substrate 71, a circuit layer including thin film transistors (TFTs), etc., an organic light emitting diode (OLED), an upper structural layer 72 including a sealing film for sealing the OLED, and the like.
  • TFTs thin film transistors
  • OLED organic light emitting diode
  • the upper structural layer 72 includes, for example, a nitrogen-containing layer (eg, a nitride layer such as silicon nitride, silicon oxynitride, etc.), and ammonia (ammonium ions) can be generated from the upper structural layer 72 .
  • a nitrogen-containing layer eg, a nitride layer such as silicon nitride, silicon oxynitride, etc.
  • ammonia ammonium ions
  • Example 1 (Production of polarizer)
  • a thermoplastic resin substrate a long amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a water absorption of 0.75% and a Tg of about 75° C. was used. Corona treatment was applied to one side of the resin substrate.
  • a PVA system obtained by mixing polyvinyl alcohol (degree of polymerization: 4200, degree of saponification: 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER Z410”) at a weight ratio of 9:1.
  • aqueous PVA solution 100 parts by weight of resin and 13 parts by weight of potassium iodide were dissolved in water to prepare an aqueous PVA solution (coating liquid).
  • the above 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, thereby producing a laminate.
  • the obtained laminate was uniaxially stretched 2.4 times at the free end in the machine direction (longitudinal direction) between rolls with different peripheral speeds in an oven at 130° C. (in-air auxiliary stretching treatment).
  • the laminate was immersed in an insolubilizing bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (insolubilizing treatment).
  • an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water
  • the finally obtained polarizer is added to a dyeing bath (iodine aqueous solution obtained by blending iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. It was immersed for 60 seconds while adjusting the concentration so that the single transmittance (Ts) was 43.0% (dyeing treatment).
  • the laminate was immersed in a washing bath (aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment). After that, while drying in an oven kept at 90° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at 75° C. for about 2 seconds (drying shrinkage treatment). The shrinkage ratio in the width direction of the laminate due to the drying shrinkage treatment was 5.2%. Thus, a polarizer having a thickness of 5 ⁇ m was formed on the resin substrate.
  • the obtained mixture was diluted with a mixed solvent in which isopropyl alcohol (IPA) and cyclopentanone (CPN) were mixed at a weight ratio of 65:35 so that the solid content concentration was 36%, and a hard coat was formed.
  • IPA isopropyl alcohol
  • CPN cyclopentanone
  • the obtained hard coat layer forming material (coating solution) was coated on a 25 ⁇ m-thick TAC film (manufactured by Konica Minolta, trade name “KC2UA”) using a bar coater. After drying the coating layer by heating the TAC film with the coating layer formed thereon at 80° C. for 1 minute, the coating layer was dried by irradiating ultraviolet rays with an integrated light intensity of 300 mJ/cm 2 from a high-pressure mercury lamp. After curing, a laminated film having a thickness of 32 ⁇ m and a moisture permeability at 40° C. and 92% RH of 440 g/m 2 ⁇ 24 h was obtained.
  • polyester carbonate resin pellet
  • a single screw extruder Toshiba Machine Co., Ltd., cylinder setting temperature: 250 ° C.
  • T die width 200 mm, setting temperature: 250 ° C.
  • a chill roll set temperature: 120 to 130° C.
  • a film forming apparatus equipped with a winder to prepare a long resin film having a thickness of 135 ⁇ m.
  • the obtained long resin film was stretched in the width direction at a stretching temperature of 143 ° C. and a stretching ratio of 2.8 times, and the moisture permeability at 40 ° C. and 92% RH was 75 g / m 2 ⁇ 24 h with a thickness of 47 ⁇ m.
  • a stretched film was obtained.
  • the obtained stretched film had Re(550) of 147 nm, Re(450)/Re(550) of 0.86, and Nz coefficient of 1.12.
  • the laminate film obtained above was attached to the surface of the polarizer of the resin substrate/polarizer laminate obtained above via an ultraviolet curable adhesive (thickness after curing: 1.0 ⁇ m). .
  • the resin substrate was peeled off from the polarizer, and the retardation layer (stretched film) obtained above was attached to the peeled surface via a 5 ⁇ m-thick acrylic pressure-sensitive adhesive layer. At this time, they were attached so that the absorption axis of the polarizer and the slow axis of the retardation layer formed an angle of 45°.
  • a 15 ⁇ m-thick pressure-sensitive adhesive layer was formed on the surface of the retardation layer using an acrylic pressure-sensitive adhesive to obtain a polarizing plate.
  • Example 2 A polarizing plate was obtained in the same manner as in Example 1, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 50:50 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • Examples 3 and 4 A polarizing plate was obtained in the same manner as in Examples 1 and 2, except that the film constituting the retardation layer was produced by the method described below.
  • the thickness of the obtained stretched film was 37 ⁇ m
  • the moisture permeability at 40° C. and 92% RH was 105 g/m 2 ⁇ 24 h
  • Re (550) was 144 nm
  • Re (450)/Re (550 ) was 0.86 and the Nz coefficient was 1.09.
  • Machine manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250 ° C
  • T-die width 200 mm, set temperature: 250 ° C
  • chill roll set temperature: 120 to 130 ° C
  • a long resin film having a thickness of 105 ⁇ m was produced by using.
  • the resulting long resin film was stretched in the width direction at a stretching temperature of 138° C. at a stretching ratio of 2.8 to obtain a stretched film.
  • Example 1 A polarizing plate was obtained in the same manner as in Example 1, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 30:70 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • Example 2 A polarizing plate was obtained in the same manner as in Example 1, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 20:80 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • Example 3 A polarizing plate was obtained in the same manner as in Example 1, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 10:90 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • Example 4 A polarizing plate was obtained in the same manner as in Example 3, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 30:70 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • Example 5 A polarizing plate was obtained in the same manner as in Example 3, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 20:80 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • Example 6 A polarizing plate was obtained in the same manner as in Example 3, except that a mixed solvent in which IPA and CPN were mixed at a weight ratio of 10:90 was used in the preparation of the hard coat layer forming material.
  • the laminated film obtained had a thickness of 33 ⁇ m and a moisture permeability of 380 g/m 2 ⁇ 24 h at 40° C. and 92% RH.
  • the resulting solution was filtered through a 0.20 ⁇ m membrane filter to obtain a polymerizable composition.
  • a polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100° C. for 10 minutes, and then baked at 200° C. for 60 minutes to obtain a coating film. .
  • the resulting coating film was rubbed 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 substrate (substantially an alignment film) by a spin coating method and dried at 100° C. for 2 minutes.
  • the resulting liquid crystal alignment fixed layer had a thickness of 3 ⁇ m, a moisture permeability at 40° C. and 92% RH of 815 g/m 2 24 h, an in-plane retardation Re (550) of 130 nm, and a Re (450) /Re(550) was 0.851.
  • Transmittance change 1 (ammonia decolorization)
  • the resulting polarizing plate was attached to an alkali-free glass plate having a silicon oxynitride film having a thickness of 500 nm formed on the surface, and then placed in an environment of 65° C. and 95% RH for 48 hours (humidification test ).
  • LPF-2000 ultraviolet-visible spectrophotometer
  • LPF-2000 ultraviolet-visible spectrophotometer
  • Formation of an intermediate layer was confirmed by TEM observation in each example and comparative example. In each example, it was confirmed that the transmittance change ⁇ Ts was within the range of ⁇ 3%.
  • a polarizing plate according to an embodiment of the present invention is preferably used for an organic EL display device, for example.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
PCT/JP2022/043398 2022-01-06 2022-11-24 偏光板および有機エレクトロルミネセンス表示装置 WO2023132148A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009139712A (ja) * 2007-12-07 2009-06-25 Nitto Denko Corp 偏光板、光学フィルムおよび画像表示装置
JP2019148734A (ja) * 2018-02-28 2019-09-05 住友化学株式会社 円偏光板
JP2021117484A (ja) * 2020-01-24 2021-08-10 日東電工株式会社 偏光板および位相差層付偏光板ならびにこれらを用いた画像表示装置
JP2021124616A (ja) * 2020-02-05 2021-08-30 日東電工株式会社 防眩性ハードコートフィルム、防眩性ハードコートフィルムの製造方法、光学部材および画像表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009139712A (ja) * 2007-12-07 2009-06-25 Nitto Denko Corp 偏光板、光学フィルムおよび画像表示装置
JP2019148734A (ja) * 2018-02-28 2019-09-05 住友化学株式会社 円偏光板
JP2021117484A (ja) * 2020-01-24 2021-08-10 日東電工株式会社 偏光板および位相差層付偏光板ならびにこれらを用いた画像表示装置
JP2021124616A (ja) * 2020-02-05 2021-08-30 日東電工株式会社 防眩性ハードコートフィルム、防眩性ハードコートフィルムの製造方法、光学部材および画像表示装置

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