WO2017086338A1 - 光学積層体および該光学積層体を用いた有機エレクトロルミネセンス表示装置 - Google Patents
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Classifications
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02B1/14—Protective coatings, e.g. hard coatings
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- G—PHYSICS
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- G02B5/30—Polarising elements
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- G02B5/3083—Birefringent or phase retarding elements
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- 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
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- G—PHYSICS
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- 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
- G09F9/301—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 flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- 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
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- 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
- H10K50/84—Passivation; Containers; Encapsulations
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- 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
- H10K50/868—Arrangements for polarized light emission
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- 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
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
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- 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
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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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
- B32B2551/00—Optical elements
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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
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- 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
- H10K50/85—Arrangements for extracting light from the devices
Definitions
- the present invention relates to an optical laminate and an organic electroluminescence display device using the optical laminate.
- the present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide an optical laminate that is very thin and can be suitably applied to a bendable or foldable organic EL display device. To provide a body.
- the optical layered body of the present invention is used for an organic electroluminescence display device.
- the optical laminate includes a surface protective layer, a polarizer, and an optical compensation layer in this order, the surface protective layer is flexible, and has a function of replacing the cover glass of the organic electroluminescence display device, And it functions as a protective layer for the polarizer.
- the said surface protection layer is comprised with the single resin film.
- the surface protective layer includes a hard coat layer and a resin film in order from the surface side.
- the surface protective layer has a bendability that can be bent 200,000 times with a radius of curvature of 3 mm or less, and the surface of the surface protective layer has a pencil hardness of 2H or more and a load of 1000 g. Scratch resistance that does not cause scratches even after 300 reciprocating frictions.
- the optical compensation layer is composed of a retardation film; the retardation film has an in-plane retardation Re (550) of 100 nm to 180 nm, and Re (450) ⁇ Re (550). ⁇ Re (650) is satisfied; the angle formed between the slow axis of the retardation film and the absorption axis of the polarizer is 35 ° to 55 °.
- the optical compensation layer has a first liquid crystal alignment solidified layer and a second liquid crystal alignment solidified layer in this order from the polarizer side; in-plane of the first liquid crystal alignment solidified layer
- the phase difference Re (550) is 180 nm to 320 nm
- the in-plane phase difference Re (550) of the second liquid crystal alignment solidified layer is 100 nm to 180 nm
- the angle formed by the absorption axis of the polarizer is 10 ° to 20 °
- the angle formed by the slow axis of the second liquid crystal alignment solidified layer and the absorption axis of the polarizer is 65 ° to 85 °. .
- the optical layered body further includes a conductive layer on the side of the optical compensation layer opposite to the polarizer.
- an organic electroluminescent display device is provided. This organic electroluminescence display device includes the above-described optical laminated body on the viewing side, and the surface protective layer of the laminated body is disposed on the viewing side. In one embodiment, at least a part of the organic electroluminescent display device can be bent with a radius of curvature of 10 mm or less.
- an optical laminate for an organic EL display device a surface protective layer that has a function of replacing a cover glass and functions as a protective layer of a polarizer is very thin.
- an optical laminate that can be suitably applied to a bendable or foldable organic EL display device can be obtained.
- FIG. 1 is a schematic cross-sectional view of an organic EL display device according to an embodiment of the present invention. It is a schematic sectional drawing of the organic EL element used for the organic EL display apparatus by one Embodiment of this invention. It is the schematic of the testing machine used for the bending resistance evaluation in an Example and a comparative example.
- Refractive index (nx, ny, nz) “Nx” is the refractive index in the direction in which the in-plane refractive index is maximum (ie, the slow axis direction), and “ny” is the direction orthogonal to the slow axis in the plane (ie, the fast axis direction). “Nz” is the refractive index in the thickness direction.
- Refractive index (nx, ny, nz) “Nx” is the refractive index in the direction in which the in-plane refractive index is maximum (ie, the slow axis direction), and “ny” is the direction orthogonal to the slow axis in the plane (ie, the fast axis direction). “Nz” is the refractive index in the thickness direction.
- In-plane retardation (Re) “Re ( ⁇ )” is the in-plane retardation of the film measured with light having a wavelength of ⁇ nm at 23 ° C.
- Re (450) is the in-plane retardation of the film measured with light having a wavelength of 450 nm at 23 ° C.
- Thickness direction retardation (Rth) is a retardation in the thickness direction of the film measured with light having a wavelength of 550 nm at 23 ° C.
- Rth (450) is the retardation in the thickness direction of the film measured with light having a wavelength of 450 nm at 23 ° C.
- the “alignment solidified layer” is a concept including an alignment cured layer obtained by curing a liquid crystal monomer. (6) Angle When referring to an angle in this specification, unless otherwise specified, the angle includes angles in both clockwise and counterclockwise directions.
- An optical laminate according to an embodiment of the present invention is an image display device (for example, a liquid crystal display device or an organic EL display device), preferably a bendable image display device, more preferably bendable.
- the organic EL display device is more preferably used for a foldable organic EL display device.
- the optical laminate can be applied to a liquid crystal display device as well. It is.
- FIG. 1 is a schematic cross-sectional view of an optical layered body according to one embodiment of the present invention.
- the optical layered body 100 of the present embodiment includes the surface protective layer 10, the polarizer 20, and the optical compensation layer 30 in this order.
- the surface protective layer 10 is flexible. Further, the surface protective layer 10 has a function of replacing the cover glass of the organic EL display device and functions as a protective layer of the polarizer 20. In addition, as will be described in detail later, the surface protective layer is much thinner than the conventional cover glass. Therefore, in the embodiment of the present invention, since the surface protective layer itself is thin and the outer protective film of the polarizer can be omitted, it is possible to contribute to remarkable thinning of the organic EL display device.
- the thinning of the organic EL display device has a great commercial value because it widens the range of design choices. Furthermore, it is possible to realize an organic EL display device that is preferably bendable (more preferably foldable) by a synergistic effect of thinning of the organic EL display device and flexibility of the surface protective layer. it can.
- the surface protective layer 10 includes a hard coat layer 11 and a resin film 12 in order from the surface side. Depending on the configuration of the resin film, the hard coat layer may be omitted, or hard coat layers may be formed on both sides of the resin film.
- the surface protective layer 10 preferably has a flexibility that can be bent 200,000 times with a radius of curvature of 3 mm.
- the surface protective layer has such flexibility, an organic EL display device that can be bent or folded when the optical laminate is applied to the organic EL display device can be realized.
- the surface on the visual recognition side (the surface of the hard coat layer or the surface of the resin film) of the surface protective layer 10 preferably has a pencil hardness of 2H or higher and scratch resistance that does not cause scratches even after 300 reciprocating frictions with a load of 1000 g. Have.
- the surface protective layer has such surface characteristics, the surface protective layer can function well as an alternative to the cover glass of the organic EL display device.
- the optical compensation layer 30 is composed of a retardation film.
- the retardation film can also function as a protective layer (inner protective layer) for the polarizer. As a result, it can contribute to further thinning of the optical laminate (as a result, an organic EL display device).
- an inner side protective layer (inner side protective film) may be arrange
- the in-plane retardation Re (550) of the retardation film is preferably 100 nm to 180 nm, and satisfies the relationship of Re (450) ⁇ Re (550) ⁇ Re (650).
- the angle formed between the slow axis of the retardation film and the absorption axis of the polarizer is preferably 35 ° to 55 °.
- FIG. 2 is a schematic cross-sectional view of an optical laminate according to another embodiment of the present invention.
- the optical compensation layer 30 has a laminated structure of an alignment solidified layer of a liquid crystal compound (hereinafter simply referred to as a liquid crystal alignment solidified layer).
- a liquid crystal alignment solidified layer By using the liquid crystal compound, the difference between nx and ny of the obtained optical compensation layer can be significantly increased as compared with the non-liquid crystal material, and thus the thickness of the optical compensation layer for obtaining a desired in-plane retardation. Can be significantly reduced. As a result, it is possible to further reduce the thickness of the optical layered body (as a result, the organic EL display device).
- the optical compensation layer 30 includes a first liquid crystal alignment solidified layer 31 and a second liquid crystal alignment solidified layer 32 in order from the polarizer 20 side.
- the in-plane retardation Re (550) of the first liquid crystal alignment solidified layer 31 is preferably 180 nm to 320 nm
- the in-plane retardation Re (550) of the second liquid crystal alignment solidified layer 32 is preferably 100 nm to 180 nm.
- the angle formed between the slow axis of the first liquid crystal alignment solidified layer and the absorption axis of the polarizer is preferably 10 ° to 20 °
- the slow phase of the second liquid crystal alignment solidified layer is The angle between the axis and the absorption axis of the polarizer is preferably 65 ° to 85 °.
- the angle formed between the slow axis of the first liquid crystal alignment fixed layer and the absorption axis of the polarizer is preferably 65 ° to 85 °
- the slow phase of the second liquid crystal alignment fixed layer is The angle formed between the axis and the absorption axis of the polarizer is preferably 10 ° to 20 °.
- an inner protective layer may be disposed between the polarizer and the first liquid crystal alignment solidified layer as necessary.
- a conductive layer may be provided on the side of the optical compensation layer 30 opposite to the polarizer 20.
- the optical laminate can be applied to a so-called inner touch panel type input display device in which a touch sensor is incorporated between a display cell (organic EL cell) and a polarizer.
- a printed layer (not shown) is formed on the periphery of the optical laminate (more specifically, a position corresponding to the bezel of the organic EL display device).
- the printing layer may be formed on the polarizer 20 side of the surface protective layer 10 (substantially, the polarizer 20 side of the resin film 12), or formed on the opposite side of the optical compensation layer 30 from the polarizer 20. Also good.
- the printed layer is formed on the side of the optical compensation layer 30 opposite to the polarizer 20 and both the conductive layer and the printed layer are formed, typically, the printed layer is interposed between the optical compensation layer and the conductive layer.
- a printed layer can be formed.
- the optical layered body of the present invention is elongated.
- the long optical laminate can be stored and / or transported, for example, wound in a roll.
- the total thickness of the optical layered body of the present invention is typically 30 ⁇ m to 300 ⁇ m, preferably 40 ⁇ m to 250 ⁇ m. This is much thinner than the total thickness (typically 800 ⁇ m) of the cover glass and the circularly polarizing plate in the conventional configuration using the cover glass and the circularly polarizing plate. Therefore, the optical layered body of the present invention can contribute to a remarkable reduction in thickness of the organic EL display device, and can further realize a bendable or foldable organic EL display device.
- the surface protective layer 10 has a function of replacing the cover glass of the organic EL display device, and functions as a protective layer for the polarizer 20.
- the “surface protective layer” in the description of the characteristics of the surface protective layer means a resin film in the case of a resin film alone, and a laminate of these in the case of including a hard coat layer and a resin film.
- the surface protective layer has a curvature radius of 3 mm or less (for example, 3 mm, 2 mm, 1 mm), preferably 200,000 times, more preferably 300,000 times, still more preferably 500,000 times, and more preferably 500,000 times.
- the surface protective layer has such flexibility, an organic EL display device that can be bent or folded when the optical laminate is applied to the organic EL display device can be realized.
- the surface protective layer has a hard coat layer on one side of the resin film, the flexibility test is performed by bending the hard coat layer inside. Flexibility can be measured with a folding tester in which a chuck on one side repeats 180 ° bending with a mandrill in between.
- the surface protective layer preferably has resilience after bending.
- the restoring property after bending means returning to the original state without leaving a fold mark after bending. Restorability after bending can be evaluated by, for example, the number of repetitions until a crease is formed after the surface protective layer (resin film or laminate) is bent 180 ° with a curvature radius of 1 mm.
- the surface protective layer preferably has a restoring property of 10,000 times or more under the conditions.
- the visible side surface (hard coat layer surface or resin film surface) of the surface protective layer preferably has a pencil hardness of 2H or higher, more preferably 3H or higher, still more preferably 4H or higher, and particularly preferably 5H or higher.
- the surface on the viewing side has scratch resistance that does not cause scratches even when reciprocating at a load of 1000 g, preferably 300 times, more preferably 500 times, and even more preferably 1000 times. If the pencil hardness and scratch resistance are in such ranges, the surface protective layer can function well as an alternative to the cover glass.
- the pencil hardness can be measured according to JIS K 5400-5-4. Further, the scratch resistance can be evaluated in the state of scratches when the surface is reciprocated a predetermined number of times with a predetermined load (for example, 500 g / cm 2 , 1000 g / cm 2 ) using steel wool # 0000.
- the light transmittance of the surface protective layer is preferably 91% or more, more preferably 93% or more, and further preferably 95% or more.
- the haze of the surface protective layer is preferably 0.5% or less, more preferably 0.4% or less, and further preferably 0.3% or less.
- the hard coat layer 11 may be formed on one side (typically, the surface side) of the resin film or on both sides of the resin film depending on the configuration of the resin film 12. Or may be omitted.
- the hard coat layer may be composed of any appropriate material that can satisfy the characteristics described in the above section B-1.
- the constituent material include thermosetting resins, thermoplastic resins, active energy ray curable resins (for example, ultraviolet curable resins and electron beam curable resins), two-component mixed resins, and the like.
- An ultraviolet curable resin is preferred. This is because the hard coat layer can be efficiently formed by a simple processing operation.
- the ultraviolet curable resin include various resins such as polyester, acrylic, urethane, amide, silicone, and epoxy. These include ultraviolet curable monomers, oligomers, polymers and the like. An acrylic resin is preferable.
- the ultraviolet curable acrylic resin preferably contains a monomer component and an oligomer component having two or more, more preferably 3 to 6, ultraviolet polymerization functional groups.
- a photopolymerization initiator is blended in the ultraviolet curable resin.
- the curing method may be a radical polymerization method or a cationic polymerization method.
- the constituent material and the forming method of the hard coat layer are described in, for example, Japanese Patent Application Laid-Open No. 2011-237789. The description of the publication is incorporated herein by reference.
- the hard coat layer may be formed by blending a slide ring material with the above constituent materials. By blending the slide ring material, good flexibility can be imparted.
- a representative example of the slide ring material is polyrotaxane.
- a polyrotaxane typically has a structure in which a cyclodextrin (CD) cyclic molecule slides on a linear polyethylene glycol (PEG) main chain. Both ends of the PEG main chain are modified with adamantaneamine to prevent the CD cyclic molecule from dropping off.
- the CD cyclic molecule is chemically modified to give an active energy ray polymerizable group.
- a radical polymerizable monomer having a radical polymerizable group is preferably used as the hard coat layer constituent material.
- the radical polymerizable group include a (meth) acryloyl group and a (meth) acryloyloxy group. This is because the compatibility with the polyrotaxane is excellent and various materials can be selected.
- the polyrotaxane substantially the polymerizable group of the CD cyclic molecule
- the active energy ray-curable component of the hard coat layer constituting material react and cure, a hard coat layer whose crosslinking point is movable even after curing is obtained. can get.
- the hard coat layer may be formed by blending nanofibers and / or nanocrystals with the above constituent materials.
- Representative examples of nanofibers include cellulose nanofibers, chitin nanofibers, and chitosan nanofibers. By blending these, a hard coat layer excellent in flexibility, pencil hardness, scratch resistance and abrasion resistance can be obtained while maintaining excellent transparency.
- Nanofibers and / or nanocrystals (the total when used in combination) can be blended in a proportion of preferably 0.1 wt% to 40 wt% with respect to the entire hard coat layer.
- the nanofiber has an average fiber diameter of, for example, 1 nm to 100 nm, and an average fiber length of, for example, 10 nm to 1000 nm.
- the hard coat layer containing nanofibers is described in, for example, JP2012-131201A and JP2012-171171A. The description of the publication is incorporated herein by reference.
- the thickness of the hard coat layer is preferably 1 ⁇ m to 20 ⁇ m, more preferably 2 ⁇ m to 15 ⁇ m. If the thickness is too small, the hardness may be insufficient, or the effect of suppressing dimensional changes due to bending or the like may be insufficient. If the thickness is too large, the flexibility and / or foldability may be adversely affected.
- the resin film may be composed of any appropriate material that can satisfy the characteristics described in the above section B-1.
- the constituent materials include polyethylene terephthalate resin, polyethylene naphthalate resin, acetate resin, polyethersulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, polyolefin resin, Examples include (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like. These resins may be used alone or in combination of two or more. Polyamide resins, polyimide resins, polyamideimide resins, polyethylene naphthalate resins, and polycarbonate resins are preferable. It is because it is excellent in durability.
- the resin film may contain fine particles in the above-mentioned constituent materials. More specifically, the resin film may be a so-called nanocomposite film in which nanometer-order fine particles are dispersed in the matrix of the constituent material. With such a configuration, very excellent hardness and scratch resistance are imparted, so that the hard coat layer can be omitted.
- the average particle diameter of the fine particles is, for example, about 1 nm to 100 nm.
- the fine particles are typically composed of an inorganic oxide.
- the surface of the fine particles is modified with a predetermined functional group.
- Examples of the inorganic oxide constituting the fine particles include zirconium oxide, yttria-added zirconium oxide, lead zirconate, strontium titanate, tin titanate, tin oxide, bismuth oxide, niobium oxide, tantalum oxide, potassium tantalate, and tungsten oxide. Cerium oxide, lanthanum oxide, gallium oxide, silica, alumina, titanium oxide, zirconium oxide, and barium titanate.
- the thickness of the resin film is preferably 10 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 80 ⁇ m. If it is such thickness, it is excellent in the balance of thickness reduction, handling property, and mechanical strength.
- Polarizer 20 Any appropriate polarizer may be adopted as the polarizer 20.
- the resin film forming the polarizer may be a single-layer resin film or a laminate of two or more layers.
- polarizers composed of a single-layer resin film include hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and ethylene / vinyl acetate copolymer partially saponified films.
- PVA polyvinyl alcohol
- polyene-based oriented films such as those subjected to dyeing treatment and stretching treatment with dichroic substances such as iodine and dichroic dyes, PVA dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer obtained by dyeing a PVA film with iodine and uniaxially stretching is used because of excellent optical properties.
- the dyeing with iodine is performed, for example, by immersing a PVA film in an aqueous iodine solution.
- the stretching ratio of the uniaxial stretching is preferably 3 to 7 times.
- the stretching may be performed after the dyeing treatment or may be performed while dyeing. Moreover, you may dye
- the PVA film is subjected to swelling treatment, crosslinking treatment, washing treatment, drying treatment and the like. For example, by immersing the PVA film in water and washing it before dyeing, not only can the surface of the PVA film be cleaned of dirt and anti-blocking agents, but the PVA film can be swollen to cause uneven staining. Can be prevented.
- a polarizer obtained by using a laminate a laminate of a resin substrate and a PVA resin layer (PVA resin film) laminated on the resin substrate, or a resin substrate and the resin
- a polarizer obtained by using a laminate with a PVA resin layer applied and formed on a substrate examples thereof include a polarizer obtained by using a laminate with a PVA resin layer applied and formed on a substrate.
- a polarizer obtained by using a laminate of a resin base material and a PVA resin layer applied and formed on the resin base material may be obtained by, for example, applying a PVA resin solution to a resin base material and drying it.
- a PVA-based resin layer is formed thereon to obtain a laminate of a resin base material and a PVA-based resin layer; the laminate is stretched and dyed to make the PVA-based resin layer a polarizer; obtain.
- stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching.
- the stretching may further include, if necessary, stretching the laminate in the air at a high temperature (for example, 95 ° C. or higher) before stretching in the aqueous boric acid solution.
- the obtained resin base material / polarizer laminate may be used as it is (that is, the resin base material may be used as a protective layer of the polarizer), and the resin base material is peeled from the resin base material / polarizer laminate.
- Any appropriate protective layer according to the purpose may be laminated on the release surface. Details of a method for manufacturing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. This publication is incorporated herein by reference in its entirety.
- the thickness of the polarizer is preferably 15 ⁇ m or less, more preferably 1 ⁇ m to 12 ⁇ m, still more preferably 3 ⁇ m to 10 ⁇ m, and particularly preferably 3 ⁇ m to 8 ⁇ m.
- the thickness of the polarizer is in such a range, curling during heating can be satisfactorily suppressed, and good appearance durability during heating can be obtained.
- the thickness of the polarizer is in such a range, it can contribute to the thinning of the optical laminate (as a result, the organic EL display device).
- the polarizer preferably exhibits absorption dichroism at any wavelength between 380 nm and 780 nm.
- the single transmittance of the polarizer is preferably 43.0% to 46.0%, more preferably 44.5% to 46.0%.
- the polarization degree of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more.
- Optical compensation layer D-1 Optical Compensation Layer Comprising Retardation Film
- the retardation film can function as a so-called ⁇ / 4 plate.
- the in-plane retardation Re (550) of the retardation film is preferably 100 nm to 180 nm, more preferably 135 nm to 155 nm.
- the retardation film satisfies the relationship of Re (450) ⁇ Re (550) ⁇ Re (650) as described above. That is, the retardation film exhibits the wavelength dependence of reverse dispersion in which the retardation value increases according to the wavelength of the measurement light.
- Re (450) / Re (550) of the retardation film is preferably 0.8 or more and less than 1.0, and more preferably 0.8 to 0.95.
- Re (550) / Re (650) is preferably 0.8 or more and less than 1.0, and more preferably 0.8 to 0.97.
- the retardation film typically has a relationship of refractive index nx> ny and has a slow axis.
- the angle formed between the slow axis of the retardation film 30 and the absorption axis of the polarizer 20 is 35 ° to 55 ° as described above, more preferably 38 ° to 52 °, and still more preferably 42 ° to 48. °, particularly preferably about 45 °. If the angle is in such a range, an optical laminate having very excellent circular polarization characteristics (and very excellent antireflection characteristics) can be obtained by using a retardation film as a ⁇ / 4 plate. Can be.
- the retardation film shows any appropriate refractive index ellipsoid as long as it has a relationship of nx> ny.
- the refractive index ellipsoid of the retardation film exhibits a relationship of nx> ny ⁇ nz.
- the Nz coefficient of the retardation film is preferably 0.9 to 2, more preferably 0.9 to 1.5, and still more preferably 0.9 to 1.3.
- the absolute value of the photoelastic coefficient of the retardation film is preferably 2 ⁇ 10 ⁇ 12 (m 2 / N) or more, more preferably 10 ⁇ 10 ⁇ 12 (m 2 / N) to 100 ⁇ 10 ⁇ . 12 (m 2 / N), more preferably 20 ⁇ 10 ⁇ 12 (m 2 / N) to 40 ⁇ 10 ⁇ 12 (m 2 / N). If the absolute value of the photoelastic coefficient is in such a range, the flexibility of the organic EL display device can be maintained while securing a sufficient phase difference even with a small thickness, and further, the phase difference change due to the stress at the time of bending. (As a result, the color change of the organic EL display device) can be further suppressed.
- the thickness of the retardation film is preferably 1 ⁇ m to 70 ⁇ m, more preferably 1 ⁇ m to 20 ⁇ m, and further preferably 1 ⁇ m to 10 ⁇ m. Since the optical laminated body of the present invention can use a film having a thickness smaller than that of the conventional ⁇ / 4 plate while maintaining desired optical characteristics, the optical laminated body (as a result, an organic EL display device) can be thinned. Can contribute.
- the retardation film is formed of any appropriate resin that can satisfy the above characteristics.
- the resin forming the retardation film include polycarbonate resins, polyvinyl acetal resins, cycloolefin resins, acrylic resins, and cellulose ester resins. Polycarbonate resin is preferable.
- the polycarbonate resin any appropriate polycarbonate resin can be used as long as the effects of the present invention can be obtained.
- the polycarbonate 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.
- the polycarbonate resin is derived from 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 a di-, tri- or polyethylene glycol. More preferably, a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from di, tri, or polyethylene glycol.
- the polycarbonate resin may contain structural units derived from other dihydroxy compounds as necessary. Details of the polycarbonate resin that can be suitably used in the present invention are described in, for example, Japanese Patent Application Laid-Open Nos. 2014-10291 and 2014-26266, and the description is incorporated herein by reference. The
- the glass transition temperature of the polycarbonate resin is preferably 110 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 230 ° C. or lower. If the glass transition temperature is excessively low, the heat resistance tends to deteriorate, there is a possibility of causing a dimensional change after film formation, and the image quality of the obtained organic EL display device may be lowered. If the glass transition temperature is excessively high, the molding stability at the time of film molding may deteriorate, and the transparency of the film may be impaired.
- the glass transition temperature is determined according to JIS K 7121 (1987).
- the molecular weight of the polycarbonate resin can be represented by a reduced viscosity.
- the reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ⁇ 0.1 ° C., using methylene chloride as a solvent, precisely adjusting the polycarbonate concentration to 0.6 g / dL.
- the lower limit of the reduced viscosity is usually preferably 0.30 dL / g, more preferably 0.35 dL / g or more.
- the upper limit of the reduced viscosity is usually preferably 1.20 dL / g, more preferably 1.00 dL / g, still more preferably 0.80 dL / g.
- the reduced viscosity is less than the lower limit, there may be a problem that the mechanical strength of the molded product is reduced.
- the reduced viscosity is larger than the upper limit, the fluidity at the time of molding is lowered, and there may be a problem that productivity and moldability are lowered.
- the retardation film is obtained, for example, by stretching a film formed from the polycarbonate resin.
- Any appropriate molding method can be adopted as a method of forming a film from a polycarbonate-based resin. Specific examples include compression molding methods, transfer molding methods, injection molding methods, extrusion molding methods, blow molding methods, powder molding methods, FRP molding methods, cast coating methods (for example, casting methods), calendar molding methods, and hot presses. Law. Extrusion molding or cast coating is preferred. This is because the smoothness of the resulting film can be improved and good optical uniformity can be obtained.
- the molding conditions can be appropriately set according to the composition and type of the resin used, the properties desired for the retardation film, and the like.
- the thickness of the resin film can be set to any appropriate value depending on the desired thickness of the obtained retardation film, the desired optical properties, the stretching conditions described later, and the like.
- the thickness is preferably 50 ⁇ m to 300 ⁇ m.
- Any appropriate stretching method and stretching conditions may be employed for the stretching.
- various stretching methods such as free end stretching, fixed end stretching, free end contraction, and fixed end contraction can be used singly or simultaneously or sequentially.
- the stretching direction can also be performed in various directions and dimensions such as a length direction, a width direction, a thickness direction, and an oblique direction.
- a retardation film having the desired optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient) can be obtained by appropriately selecting the stretching method and stretching conditions.
- the retardation film is produced by uniaxially stretching a resin film or uniaxially stretching a fixed end.
- the fixed end uniaxial stretching there is a method of stretching in the width direction (lateral direction) while running the resin film in the longitudinal direction.
- the draw ratio is preferably 1.1 to 3.5 times.
- the retardation film can be produced by continuously stretching a long resin film obliquely in a direction at a predetermined angle with respect to the longitudinal direction.
- a long stretched film having an orientation angle of a predetermined angle with respect to the longitudinal direction of the film (slow axis in the direction of the predetermined angle) is obtained.
- the predetermined angle may be an angle formed between the absorption axis of the polarizer and the slow axis of the retardation layer in the optical layered body.
- the angle is preferably 35 ° to 55 °, more preferably 38 ° to 52 °, still more preferably 42 ° to 48 °, and particularly preferably about 45 °.
- Examples of the stretching machine used for the oblique stretching include a tenter type stretching machine capable of adding feed forces, pulling forces, or pulling forces at different speeds in the lateral and / or longitudinal directions.
- the tenter type stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, and the like, but any suitable stretching machine can be used as long as a long resin film can be continuously stretched obliquely.
- a retardation film having a desired in-plane retardation and having a slow axis in the desired direction (substantially long film) Shaped retardation film) can be obtained.
- Examples of the oblique stretching method include, for example, JP-A-50-83482, JP-A-2-113920, JP-A-3-182701, JP-A-2000-9912, JP-A-2002-86554, Examples thereof include the method described in JP-A-2002-22944.
- the stretching temperature of the film can vary depending on the in-plane retardation value and thickness desired for the retardation film, the type of resin used, the thickness of the film used, the stretching ratio, and the like. Specifically, the stretching temperature is preferably Tg-30 ° C to Tg + 30 ° C, more preferably Tg-15 ° C to Tg + 15 ° C, and most preferably Tg-10 ° C to Tg + 10 ° C. By stretching at such a temperature, a retardation film having appropriate characteristics in the present invention can be obtained. Tg is the glass transition temperature of the constituent material of the film.
- a commercially available film may be used as the polycarbonate resin film.
- Specific examples of commercially available products include “Pure Ace WR-S”, “Pure Ace WR-W”, “Pure Ace WR-M” manufactured by Teijin Limited, and “NRF” manufactured by Nitto Denko Corporation. It is done.
- a commercially available film may be used as it is, and a commercially available film may be used after secondary processing (for example, stretching treatment, surface treatment) depending on the purpose.
- Optical compensation layer D-2-1 composed of a laminate of liquid crystal alignment solidified layers.
- First liquid crystal alignment solidified layer The first liquid crystal alignment solidified layer 31 can function as a so-called ⁇ / 2 plate.
- the first liquid crystal alignment solidified layer is a so-called ⁇ / 2 plate
- the second liquid crystal alignment solidified layer to be described later is a so-called ⁇ / 4 plate
- their slow axis is set in a predetermined direction with respect to the absorption axis of the polarizer.
- the in-plane retardation Re (550) of the first liquid crystal alignment solidified layer is preferably 180 nm to 320 nm, more preferably 200 nm to 290 nm, and further preferably 230 nm to 280 nm.
- the angle formed by the slow axis of the first liquid crystal alignment solidified layer 31 and the absorption axis of the polarizer 20 is preferably 10 ° to 20 °, more preferably 13 ° to 17 °, as described above. Preferably it is about 15 °. If the angle formed by the slow axis of the first liquid crystal alignment solidified layer and the absorption axis of the polarizer is within such a range, the in-plane retardation of the first liquid crystal alignment solidified layer and the second liquid crystal alignment solidified layer will be described.
- the thickness of the first liquid crystal alignment solidified layer is preferably 1 ⁇ m to 7 ⁇ m, more preferably 1.5 ⁇ m to 2.5 ⁇ m.
- the difference between nx and ny of the obtained optical compensation layer can be remarkably increased as compared with a non-liquid crystal material, and thus a layer for obtaining a desired in-plane retardation.
- the thickness can be remarkably reduced. Therefore, an in-plane retardation equivalent to that of the resin film can be realized with a thickness much thinner than that of the resin film.
- the first liquid crystal alignment solidified layer is typically aligned with rod-shaped liquid crystal compounds aligned in a predetermined direction (homogeneous alignment).
- a slow axis can be developed in the alignment direction of the liquid crystal compound.
- the liquid crystal compound include a liquid crystal compound (nematic liquid crystal) whose liquid crystal phase is a nematic phase.
- a liquid crystal compound for example, a liquid crystal polymer or a liquid crystal monomer can be used.
- the liquid crystal compound may exhibit liquid crystallinity either lyotropic or thermotropic.
- the liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
- the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the alignment state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (that is, curing) the liquid crystal monomer. After aligning the liquid crystal monomers, for example, if the liquid crystal monomers are polymerized or cross-linked, the alignment state can be fixed thereby.
- a polymer is formed by polymerization and a three-dimensional network structure is formed by crosslinking, but these are non-liquid crystalline.
- the first liquid crystal alignment solidified layer for example, transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change specific to the liquid crystal compound does not occur.
- the first liquid crystal alignment solidified layer is an extremely stable layer that is not affected by temperature changes.
- the temperature range in which the liquid crystal monomer exhibits liquid crystal properties varies depending on its type. Specifically, the temperature range is preferably 40 ° C. to 120 ° C., more preferably 50 ° C. to 100 ° C., and most preferably 60 ° C. to 90 ° C.
- liquid crystal monomer any appropriate liquid crystal monomer can be adopted as the liquid crystal monomer.
- the polymerizable mesogenic compounds described in JP-T-2002-533742 WO00 / 37585
- EP358208 US521118)
- EP66137 US4388453
- WO93 / 22397 EP0266172
- DE195504224 DE44081171
- GB2280445 Specific examples of such a polymerizable mesogenic compound include, for example, trade name LC242 of BASF, trade name E7 of Merck, and trade name LC-Silicon-CC3767 of Wacker-Chem.
- the liquid crystal monomer for example, a nematic liquid crystal monomer is preferable.
- the first liquid crystal alignment solidified layer is subjected to an alignment treatment on the surface of a predetermined substrate, and a coating liquid containing a liquid crystal compound is applied to the surface to align the liquid crystal compound in a direction corresponding to the alignment treatment. It can be formed by fixing the orientation state.
- the liquid crystal compound can be aligned in a predetermined direction with respect to the long direction of the long substrate, and as a result, in the predetermined direction of the liquid crystal alignment solidified layer to be formed.
- a slow axis can be developed. For example, a liquid crystal alignment solidified layer having a slow axis in the direction of 15 ° with respect to the long direction can be formed on the long base material.
- Such a liquid crystal alignment solidified layer can be laminated using a roll-to-roll even when it is desired to have a slow axis in an oblique direction, so that the productivity of the optical laminate is remarkably increased. It can improve.
- the substrate is any suitable resin film, and the alignment solidified layer formed on the substrate can be transferred to the surface of the polarizer.
- the substrate can be an inner protective layer (inner protective film). In this case, the transfer step is omitted, and lamination can be performed by roll-to-roll continuously from the formation of the alignment solidified layer.
- any appropriate alignment treatment can be adopted as the alignment treatment.
- a mechanical alignment process, a physical alignment process, and a chemical alignment process are mentioned.
- Specific examples of the mechanical alignment treatment include rubbing treatment and stretching treatment.
- Specific examples of the physical alignment process include a magnetic field alignment process and an electric field alignment process.
- Specific examples of the chemical alignment treatment include oblique vapor deposition and photo-alignment treatment.
- Arbitrary appropriate conditions may be employ
- the alignment of the liquid crystal compound is performed by processing at a temperature showing a liquid crystal phase according to the type of the liquid crystal compound.
- the liquid crystal compound takes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the substrate surface.
- the alignment state is fixed by cooling the liquid crystal compound aligned as described above.
- the alignment state is fixed by subjecting the liquid crystal compound aligned as described above to a polymerization treatment or a crosslinking treatment.
- liquid crystal compound and details of the method of forming the alignment solidified layer are described in JP-A No. 2006-163343. The description in this publication is incorporated herein by reference.
- the second liquid crystal alignment solidified layer 32 can function as a so-called ⁇ / 4 plate.
- the second liquid crystal alignment solidified layer is a so-called ⁇ / 4 plate
- the first liquid crystal alignment solidified layer is a so-called ⁇ / 2 plate as described above
- the slow axis of these is predetermined with respect to the absorption axis of the polarizer.
- the in-plane retardation Re (550) of the second liquid crystal alignment solidified layer is preferably 100 nm to 180 nm, more preferably 110 nm to 170 nm, and still more preferably 120 nm to 160 nm as described above.
- the angle formed between the slow axis of the second liquid crystal alignment solidified layer 32 and the absorption axis of the polarizer 20 is preferably 65 ° to 85 °, more preferably 72 ° to 78 °, as described above. Preferably it is about 75 °. If the angle formed between the slow axis of the second liquid crystal alignment solidified layer and the absorption axis of the polarizer is within such a range, the in-plane retardation of the first liquid crystal alignment solidified layer and the second liquid crystal alignment solidified layer will be described.
- the thickness of the second liquid crystal alignment solidified layer is preferably 0.5 ⁇ m to 2 ⁇ m, more preferably 1 ⁇ m to 1.5 ⁇ m.
- the constituent material, characteristics, manufacturing method, and the like of the second liquid crystal alignment solidified layer are as described in the section D-2-1 for the first liquid crystal alignment solidified layer.
- the angle formed by the slow axis of the first liquid crystal alignment solidified layer 31 and the absorption axis of the polarizer 20 is about 15 °, and the slow axis of the second liquid crystal alignment solidified layer 32 and the absorption axis of the polarizer 20 are However, as described in the above section A, the relationship between the shaft angles may be reversed. Specifically, the angle formed by the slow axis of the first liquid crystal alignment solidified layer 31 and the absorption axis of the polarizer 20 is preferably 65 ° to 85 °, more preferably 72 ° to 78 °, and still more preferably.
- the angle formed by the slow axis of the second liquid crystal alignment solidified layer 32 and the absorption axis of the polarizer 20 is preferably 10 ° to 20 °, more preferably 13 °. It can be ⁇ 17 °, more preferably about 15 °.
- the conductive layer (not shown) is typically transparent (ie, the conductive layer is a transparent conductive layer).
- the optical laminate is a so-called inner touch panel input display in which a touch sensor is incorporated between the display cell (organic EL cell) and the polarizer. It can be applied to the device.
- the conductive layer may be a component layer of the optical laminate alone, or may be laminated on the optical compensation layer as a laminate with the substrate (conductive layer with a substrate). In the case of a single conductive layer, the conductive layer can be transferred from the substrate on which the conductive layer is formed to the optical compensation layer.
- the conductive layer can be patterned as needed. By conducting the patterning, a conductive portion and an insulating portion can be formed. As a result, an electrode can be formed.
- the electrode can function as a touch sensor electrode that senses contact with the touch panel.
- the pattern shape is preferably a pattern that works well as a touch panel (for example, a capacitive touch panel). Specific examples include the patterns described in JP2011-511357A, JP2010-164938A, JP2008-310550A, JP2003-511799A, and JP2010-541109A. It is done.
- the total light transmittance of the conductive layer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
- a transparent conductive layer having openings can be formed, and a transparent conductive layer having a high light transmittance can be obtained.
- the density of the conductive layer is preferably 1.0 g / cm 3 to 10.5 g / cm 3 , more preferably 1.3 g / cm 3 to 3.0 g / cm 3 .
- the surface resistance value of the conductive layer is preferably 0.1 ⁇ / ⁇ to 1000 ⁇ / ⁇ , more preferably 0.5 ⁇ / ⁇ to 500 ⁇ / ⁇ , and further preferably 1 ⁇ / ⁇ to 250 ⁇ / ⁇ .
- Typical examples of the conductive layer include a conductive layer containing a metal oxide, a conductive layer containing a conductive nanowire, and a conductive layer containing a metal mesh.
- a conductive layer including conductive nanowires or a conductive layer including a metal mesh is preferable. This is because it is excellent in bending resistance and it is difficult to lose conductivity even when bent, so that a conductive layer that can be bent well can be formed.
- a conductive layer containing a metal oxide is formed on any appropriate base material by any appropriate film formation method (for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.). It can be formed by forming an oxide film.
- the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Of these, indium-tin composite oxide (ITO) is preferable.
- the conductive layer containing conductive nanowires is formed by applying a dispersion liquid (conductive nanowire dispersion liquid) in which conductive nanowires are dispersed in a solvent onto any appropriate substrate, and then drying the coating layer.
- a dispersion liquid conductive nanowire dispersion liquid
- Any appropriate conductive nanowire can be used as the conductive nanowire as long as the effects of the present invention can be obtained.
- the conductive nanowire refers to a conductive substance having a needle shape or a thread shape and a diameter of nanometer size.
- the conductive nanowire may be linear or curved. As described above, the conductive layer including the conductive nanowire has excellent bending resistance.
- a conductive layer containing conductive nanowires can form a good electrical conduction path even with a small amount of conductive nanowires by forming gaps between conductive nanowires and forming a mesh.
- a conductive layer having a small electric resistance can be obtained.
- openings can be formed in the mesh gaps to obtain a conductive layer having a high light transmittance.
- the conductive nanowire include metal nanowires made of metal, conductive nanowires including carbon nanotubes, and the like.
- the ratio between the thickness d and the length L of the conductive nanowire is preferably 10 to 100,000, more preferably 50 to 100,000, still more preferably 100 to 10,000.
- the conductive nanowires having a large aspect ratio are used in this way, the conductive nanowires can cross well and high conductivity can be expressed by a small amount of conductive nanowires. As a result, a conductive layer having a high light transmittance can be obtained.
- the thickness of the conductive nanowire means the diameter when the cross section of the conductive nanowire is circular, and the short diameter when the cross section of the conductive nanowire is elliptical. If it is square, it means the longest diagonal.
- the thickness and length of the conductive nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.
- the thickness of the conductive nanowire is preferably less than 500 nm, more preferably less than 200 nm, still more preferably 1 nm to 100 nm, and particularly preferably 1 nm to 50 nm. If it is such a range, a conductive layer with high light transmittance can be formed.
- the length of the conductive nanowire is preferably 2.5 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, and further preferably 20 ⁇ m to 100 ⁇ m. Within such a range, a conductive layer having high conductivity can be obtained.
- the metal constituting the conductive nanowire any appropriate metal can be used as long as it is a highly conductive metal.
- the metal nanowire is preferably composed of one or more metals selected from the group consisting of gold, platinum, silver, and copper. Among these, silver, copper, or gold is preferable from the viewpoint of conductivity, and silver is more preferable.
- a material obtained by performing a plating process for example, a gold plating process
- any appropriate carbon nanotube can be used as the carbon nanotube.
- so-called multi-walled carbon nanotubes, double-walled carbon nanotubes, single-walled carbon nanotubes and the like are used.
- single-walled carbon nanotubes are preferably used because of their high conductivity.
- any appropriate metal mesh can be used as long as the effects of the present invention can be obtained.
- the thickness of the conductive layer is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.05 ⁇ m to 3 ⁇ m, and still more preferably 0.1 ⁇ m to 1 ⁇ m. If it is such a range, the conductive layer excellent in electroconductivity and light transmittance can be obtained. When the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 0.01 ⁇ m to 0.05 ⁇ m.
- the print layer is formed at the peripheral edge of the optical laminate, more specifically, at a position corresponding to the bezel of the organic EL display device in plan view.
- the printing layer may be formed on the polarizer 20 side of the surface protective layer 10 (substantially, the polarizer 20 side of the resin film 12). It may be formed on the opposite side.
- the printed layer may be a design layer having a predetermined design or a solid colored layer.
- the printed layer is preferably a solid colored layer, more preferably a black colored layer. By forming the black colored layer at a position corresponding to the bezel, the non-display area can be concealed.
- an organic EL display device that does not use a bezel is realized. Can do. As a result, it is possible to provide an organic EL display device having a very excellent appearance with no step on the outermost surface. Further, when the printing layer is formed on the optical compensation layer, the following advantages can be obtained: That is, with such a configuration, the printing layer is necessarily on the lower side of the polarizer (the organic EL display device side). As a result, the reflected light at the interface of the printing layer is reduced by the polarizer. Therefore, an organic EL display device having an even better appearance can be realized.
- the printing layer can be formed by any appropriate printing method using any appropriate ink or paint. Specific examples of the printing method include gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.
- the ink or paint used typically includes a binder, a colorant, a solvent, and any suitable additive that may be used as needed.
- the binder include chlorinated polyolefin (for example, chlorinated polyethylene, chlorinated polypropylene), polyester resin, urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, and cellulose resin.
- Binder resin may be used independently and may use 2 or more types together.
- the binder resin is a thermopolymerizable resin. Since the amount of the heat-polymerizable resin used is smaller than that of the photopolymerizable resin, the amount of the colorant used (the colorant content in the colored layer) can be increased.
- the binder resin is an acrylic resin, preferably an acrylic resin containing a polyfunctional monomer (eg, pentaerythritol triacrylate) as a copolymerization component.
- a polyfunctional monomer eg, pentaerythritol triacrylate
- a colored layer having an appropriate elastic modulus can be formed, so that blocking can be satisfactorily prevented when the retardation film is rolled.
- a step due to the thickness of the printed layer is also formed, and the step can effectively function to prevent blocking.
- any appropriate colorant can be used depending on the purpose.
- the coloring agent include titanium white, zinc white, carbon black, iron black, dial, chrome vermillion, ultramarine, cobalt blue, yellow lead, titanium yellow and other inorganic pigments; phthalocyanine blue, indanthrene blue, iso Organic pigments or dyes such as indolinone yellow, benzidine yellow, quinacridone red, polyazo red, perylene red, aniline black; metal pigments composed of scaly foils such as aluminum and brass; scales such as titanium dioxide-coated mica and basic lead carbonate Pearl luster pigments (pearl pigments) composed of foil-like foil pieces.
- the colorant is preferably used in combination. This is because visible light is absorbed in a wide range and evenly, and a colored layer having no color (that is, black) can be formed.
- azo compounds and / or quinone compounds can be used.
- the colorant includes carbon black as a main component and another colorant (for example, an azo compound and / or a quinone compound). According to such a configuration, it is possible to form a colored layer that is not colored and has excellent temporal stability.
- the colorant may be used in a proportion of preferably 50 parts by weight to 200 parts by weight with respect to 100 parts by weight of the binder resin.
- the content ratio of carbon black in the colorant is preferably 80% to 100%.
- the thickness of the printing layer is preferably 3 ⁇ m to 5 ⁇ m. Further, the total light transmittance at a thickness of 3 ⁇ m to 5 ⁇ m is preferably 0.01% or less, and more preferably 0.008% or less. If the total light transmittance is in such a range, the non-display area of the organic EL display device can be well concealed without using a bezel.
- Inner protective layer (inner protective film)
- the inner protective film is preferably optically isotropic.
- “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 inner protective film is preferably 20 ⁇ m to 200 ⁇ m, more preferably 30 ⁇ m to 100 ⁇ m, and still more preferably 35 ⁇ m to 95 ⁇ m.
- the inner protective film is formed of any appropriate film as long as the desired characteristics are obtained.
- the material as the main component of the film include cellulose resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based materials.
- transparent resins such as polystyrene, polynorbornene, polyolefin, (meth) acryl, and acetate.
- thermosetting resins such as (meth) acrylic, urethane-based, (meth) acrylurethane-based, epoxy-based, and silicone-based or ultraviolet curable resins are also included.
- a glassy polymer such as a siloxane polymer is also included.
- a polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used.
- a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and nitrile group in the side chain for example, a resin composition having an alternating copolymer of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer can be mentioned.
- the polymer film can be, for example, an extruded product of the resin composition.
- Adhesive layer or adhesive layer Arbitrary appropriate adhesive layers or adhesive layers are used for lamination
- a pressure-sensitive adhesive layer can be typically used for a layer other than these layers.
- the pressure-sensitive adhesive layer used for the lamination of the surface protective layer and the polarizer is simply referred to as a pressure-sensitive adhesive layer
- the pressure-sensitive adhesive layer used for the other lamination is referred to as another pressure-sensitive adhesive layer.
- Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a polyamide-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, A fluorine-type adhesive, an epoxy-type adhesive, and a polyether-type adhesive are mentioned.
- An adhesive may be used independently and may be used in combination of 2 or more type.
- An acrylic pressure-sensitive adhesive is preferably used in terms of transparency, workability, durability, and the like.
- the thickness of the pressure-sensitive adhesive layer is typically 10 ⁇ m to 250 ⁇ m, preferably 10 ⁇ m to 150 ⁇ m.
- the pressure-sensitive adhesive layer may be a single layer or may have a laminated structure.
- the storage elastic modulus (G ′) of the pressure-sensitive adhesive layer is preferably 0.01 (MPa) to 1.00 (MPa) at 25 ° C., more preferably 0.05 (MPa) to 0.50 (MPa). ).
- the storage elastic modulus of the pressure-sensitive adhesive layer is in such a range, an optical laminate having very excellent flexibility can be obtained. As a result, a bendable or foldable organic EL display device can be realized.
- any appropriate form of adhesive can be adopted as the adhesive constituting the adhesive layer.
- Specific examples include aqueous adhesives, solvent adhesives, emulsion adhesives, solventless adhesives, active energy ray curable adhesives, and thermosetting adhesives.
- the active energy ray curable adhesive include an electron beam curable adhesive, an ultraviolet curable adhesive, and a visible light curable adhesive.
- An aqueous adhesive and an active energy ray curable adhesive can be suitably used.
- Specific examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
- the active energy ray-curable adhesive include (meth) acrylate adhesives.
- (Meth) acrylate means acrylate and / or methacrylate.
- the curable component in the (meth) acrylate adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group.
- a compound having an epoxy group or an oxetanyl group can also be used as the cationic polymerization curable adhesive.
- the compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used.
- a compound having at least two epoxy groups and at least one aromatic ring in the molecule aromatic epoxy compound
- examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
- the storage elastic modulus of the adhesive layer is preferably 1.0 ⁇ 10 6 Pa or more, more preferably 1.0 ⁇ 10 7 Pa or more in the region of 70 ° C. or less.
- the upper limit of the storage elastic modulus of the adhesive layer is, for example, 1.0 ⁇ 10 10 Pa.
- the storage elastic modulus of the adhesive layer affects the polarizer cracks when the optical laminate is subjected to a heat cycle ( ⁇ 40 ° C. to 80 ° C., etc.). If the storage elastic modulus is low, defects of the polarizer cracks occur. Cheap.
- the temperature region having a high storage elastic modulus is more preferably 80 ° C. or lower, and further preferably 90 ° C. or lower.
- the thickness of the adhesive layer is typically 0.01 ⁇ m to 7 ⁇ m, preferably 0.01 ⁇ m to 5 ⁇ m.
- An acrylic pressure-sensitive adhesive is an example of the pressure-sensitive adhesive constituting the other pressure-sensitive adhesive layer. It is preferable that a separator is bonded to the surface of another pressure-sensitive adhesive layer provided outside the optical compensation layer (a conductive layer if present) until the optical laminate is used.
- FIG. 3 is a schematic cross-sectional view of an organic EL display device according to an embodiment of the present invention.
- the organic EL display device 300 includes an organic EL element (organic EL display cell) 200 and the optical laminate 100 or 101 on the viewing side of the organic EL element 200.
- the optical laminated body is the optical laminated body of the present invention described in the above items A to H.
- the optical laminated body is laminated so that the optical compensation layer is on the organic EL element side (so that the surface protective layer is on the viewing side).
- the optical layered body is not limited to the optical layered body 100 or 101 described above, and may be an optical layered body according to still another embodiment of the present invention (not shown).
- the organic EL display device is preferably bendable.
- a bendable organic EL display device can be realized by combining the above-described optical laminate of the present invention and a bendable organic EL element described later. More specifically, at least a part of the organic EL display device can be bent with a radius of curvature of preferably 10 mm or less, more preferably 8 mm or less.
- the organic EL display device can be bent at any appropriate portion.
- the organic EL display device may be bendable at the center as in a foldable display device, or may be bendable at the end from the viewpoint of ensuring the maximum design and display screen. Good.
- the organic EL display device may be bendable along its longitudinal direction or may be bendable along its short direction. It goes without saying that a specific portion of the organic EL display device can be bent depending on the application (for example, part or all of the four corners can be bent in an oblique direction).
- the slow axis direction of the retardation film 30 is preferably 20 ° to the bending direction of the organic EL display device.
- the optical layered body 100 can be arranged so as to be in the vicinity of 70 °, more preferably 30 ° to 60 °, still more preferably 40 ° to 50 °, and particularly preferably 45 °.
- the optical laminated body 101 is used (when the optical compensation layer has a laminated structure of the first liquid crystal alignment solidified layer 31 and the second liquid crystal alignment solidified layer 32), the first liquid crystal alignment solidified layer 31 is delayed.
- the phase axis direction is preferably 10 ° to 20 °, more preferably 11 ° to 19 °, still more preferably 12 ° to 18 °, and particularly preferably about 15 ° with respect to the bending direction of the organic EL display device.
- the optical laminate 101 can be disposed.
- the slow axis direction of the second liquid crystal alignment solidified layer 32 is preferably 70 ° to 80 °, more preferably 71 ° to 79 °, and still more preferably 72 ° with respect to the bending direction of the organic EL display device. It is ⁇ 78 °, particularly preferably around 75 °.
- the adjustment of the axis angle may not be as strict as in the case of the retardation film.
- the bending direction of the organic EL display device 300 (or the organic EL element 200) is a longitudinal direction or a direction (short direction) perpendicular to the longitudinal direction.
- the optical compensation layer is stacked when the organic EL element is stacked.
- the absorption axis of the polarizer 20 of the optical layered body is set to be orthogonal or parallel to the longitudinal direction (or short direction)
- the optical compensation layer is stacked when the organic EL element is stacked.
- FIG. 4 is a schematic cross-sectional view illustrating one embodiment of the organic EL element used in the present invention.
- the organic EL element 200 typically includes a substrate 210, a first electrode 220, an organic EL layer 230, a second electrode 240, and a sealing layer 250 that covers them.
- the organic EL element 200 may further include any appropriate layer as necessary. For example, a planarization layer (not shown) may be provided on the substrate, and an insulating layer (not shown) for preventing a short circuit may be provided between the first electrode and the second electrode.
- the substrate 210 can be made of any appropriate material as long as it can be bent with the predetermined radius of curvature.
- the substrate 210 is typically made of a flexible material. If a flexible substrate is used, in addition to the effects of the present invention described above, when a long optical laminate is used, the organic EL display device can be manufactured by a so-called roll-to-roll process. And mass production can be realized.
- the substrate 210 is preferably made of a material having a barrier property. Such a substrate can protect the organic EL layer 230 from oxygen and moisture.
- Specific examples of the material having barrier properties and flexibility include thin glass imparted with flexibility, thermoplastic resin or thermosetting resin film imparted with barrier properties, alloys, and metals.
- thermoplastic resin or thermosetting resin examples include polyester resins, polyimide resins, epoxy resins, polyurethane resins, polystyrene resins, polyolefin resins, polyamide resins, polycarbonate resins, silicone resins, fluorine And acrylonitrile-butadiene-styrene copolymer resin.
- the alloy examples include stainless steel, 36 alloy, and 42 alloy.
- the metal examples include copper, nickel, iron, aluminum, and titanium.
- the thickness of the substrate is preferably 5 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, and still more preferably 10 ⁇ m to 200 ⁇ m. With such a thickness, the organic EL display device can be bent with the predetermined radius of curvature, and the balance between flexibility, handleability and mechanical strength is excellent. Moreover, an organic EL element can be used suitably for a roll to roll process.
- the first electrode 220 can typically function as an anode.
- the material constituting the first electrode is preferably a material having a large work function from the viewpoint of facilitating hole injection.
- specific examples of such materials include indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide added with silicon oxide (ITSO), indium oxide containing tungsten oxide (IWO), Transparent conductive materials such as indium zinc oxide containing tungsten oxide (IWZO), indium oxide containing titanium oxide (ITO), indium tin oxide containing titanium oxide (ITTiO), indium tin oxide containing molybdenum (ITMO) And metals such as gold, silver, platinum, and alloys thereof.
- ITO indium tin oxide
- IZO indium zinc oxide
- ITSO indium tin oxide added with silicon oxide
- IWO indium oxide containing tungsten oxide
- Transparent conductive materials such as indium zinc oxide containing tungsten oxide (IWZO), indium oxide
- the organic EL layer 230 is a laminate including various organic thin films.
- the organic EL layer 230 is made of a hole-injecting organic material (for example, a triphenylamine derivative), and a hole-injecting layer 230a provided to improve the hole-injecting efficiency from the anode, for example, copper
- a hole transport layer 230b made of phthalocyanine, and a light-emitting organic material (eg, anthracene, bis [N- (1-naphthyl) -N-phenyl] benzidine, N, N′-diphenyl-NN—bis (1- Naphthyl) -1,1 ′-(biphenyl) -4,4′-diamine (NPB))
- an electron transport layer 230d made of, for example, 8-quinolinol aluminum complex
- an electron injecting material for example, And an electron injection layer 230e provided to improve electron injection efficiency from the cathode.
- the organic EL layer 230 is not limited to the illustrated example, and any appropriate combination capable of causing light emission by recombination of electrons and holes in the light emitting layer 230c can be adopted.
- the thickness of the organic EL layer 230 is preferably as thin as possible. This is because it is preferable to transmit the emitted light as much as possible.
- the organic EL layer 230 can be composed of a very thin laminate of, for example, about 5 nm to 200 nm, preferably about 10 nm.
- the second electrode 240 can typically function as a cathode.
- the material constituting the second electrode is preferably a material having a low work function from the viewpoint of facilitating electron injection and increasing luminous efficiency. Specific examples of such materials include aluminum, magnesium, and alloys thereof.
- the sealing layer 250 is made of any appropriate material.
- the sealing layer 25 is preferably made of a material having excellent barrier properties and transparency.
- Representative examples of the material constituting the sealing layer include epoxy resin and polyurea.
- the sealing layer 250 may be formed by applying an epoxy resin (typically an epoxy resin adhesive) and attaching a barrier sheet thereon.
- the organic EL element 200 can be preferably manufactured continuously by a roll-to-roll process.
- the organic EL element 200 can be manufactured by a procedure according to the procedure described in, for example, 2012-169236. The description of the publication is incorporated herein by reference.
- the organic EL element 200 can be continuously laminated with the long optical laminate 100 by a roll-to-roll process, and the organic EL display device 300 can be continuously produced.
- bendable organic EL display device The details of the bendable organic EL display device are described in, for example, Japanese Patent No. 4601463 or Japanese Patent No. 4707996. These descriptions are incorporated herein by reference.
- Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Subsequently, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Thereafter, polymerization was allowed to proceed until a predetermined stirring power was obtained. When a predetermined power is reached, nitrogen is introduced into the reactor, the pressure is restored, the reaction solution is withdrawn in the form of strands, pelletized with a rotary cutter, and BHEPF / ISB / DEG 43.8 / 53.7 / A polycarbonate resin having a copolymer composition of 2.5 [mol%] was obtained.
- This polycarbonate resin had a reduced viscosity of 0.430 dL / g and a glass transition temperature of 145 ° C.
- the obtained polycarbonate resin was vacuum-dried at 80 ° C. for 5 hours, and then a single screw extruder (manufactured by Isuzu Chemical Industries, screw diameter 25 mm, cylinder set temperature: 240 ° C.), T die (width 900 mm, set temperature: 240 ° C.). ), A film forming apparatus equipped with a chill roll (set temperature: 120 to 130 ° C.) and a winder, to produce a polycarbonate resin film having a thickness of 125 ⁇ m.
- a sample having a width of 250 mm and a length of 250 mm was cut out from the polycarbonate resin film obtained as described above. Then, this sample was stretched uniaxially at a fixed end at a stretching temperature of 145.6 ° C. and a stretching ratio of 2.4 times using a batch type biaxial stretching apparatus (trade name “KARO-IV” manufactured by Bruckner Co., Ltd.), and a thickness of 58 ⁇ m.
- a retardation film 1 was prepared.
- Polarizer Production of Polarizer A1
- An amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a water absorption of 0.75% and a Tg of 75 ° C. is subjected to corona treatment on one side, and polyvinyl alcohol is applied to the corona-treated surface.
- the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment). Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance.
- 0.2 parts by weight of iodine was blended with 100 parts by weight of water, and immersed in an aqueous iodine solution obtained by blending 1.0 part by weight of potassium iodide (dyeing treatment). .
- a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C.
- a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water (Crosslinking treatment).
- the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C.
- Circularly polarizing plate production of protective film B1
- One side of the protective film ((meth) acrylic resin film having a lactone ring structure: thickness 40 ⁇ m) (surface to be bonded to the polarizer) was subjected to corona treatment.
- the composition for forming a hard coat layer was prepared by diluting with methyl isobutyl ketone. On the protective film B1, the obtained composition for forming a hard coat layer was applied to form a coating layer, and the coating layer was heated at 90 ° C. for 1 minute. The heated coating layer was irradiated with ultraviolet rays having an integrated light quantity of 300 mJ / cm 2 with a high-pressure mercury lamp to form a hard coat layer having a thickness of 5 ⁇ m.
- An ultraviolet curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO), and 3 parts by weight of a photoinitiator “IRGACURE 819” (manufactured by BASF).
- HEAA N-hydroxyethylacrylamide
- ACMO acryloylmorpholine
- UVGACURE 819 3 parts by weight of a photoinitiator “IRGACURE 819” (manufactured by BASF).
- HEAA N-hydroxyethylacrylamide
- ACMO acryloylmorpholine
- UVGACURE 819 photoinitiator
- Adhesive The adhesive layer used in this example was produced by the following method. (Preparation of (meth) acrylic polymer) A monomer mixture containing 99 parts by weight of butyl acrylate (BA) and 1 part by weight of 4-hydroxybutyl acrylate (HBA) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. . Further, 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator is charged with ethyl acetate with respect to 100 parts by weight of the monomer mixture (solid content), and nitrogen gas is added while gently stirring.
- BA butyl acrylate
- HBA 4-hydroxybutyl acrylate
- 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator is charged with ethyl acetate with respect to 100 parts by weight of the monomer mixture (solid content),
- acrylic pressure-sensitive adhesive composition 0.2 parts by weight of an isocyanate crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) with respect to 100 parts by weight of the solid content of the obtained (meth) acrylic polymer solution Then, 0.08 part by weight of a silane coupling agent (trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended to prepare an acrylic pressure-sensitive adhesive composition.
- an isocyanate crosslinking agent trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.
- silane coupling agent trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.
- Optical Laminate 1 The acrylic pressure-sensitive adhesive composition was uniformly applied to the surface of a 38 ⁇ m-thick polyethylene terephthalate (PET) film (separator) treated with a silicone release agent with a fountain coater, It dried for 2 minutes in the 155 degreeC air circulation type thermostat oven, and formed the 25-micrometer-thick adhesive layer on the separator surface. Next, a separator is bonded to the retardation film side of the circularly polarizing plate obtained above via the pressure-sensitive adhesive layer, and after peeling the separator, a PET film (thickness 38 ⁇ m: assuming a flexible organic EL panel) is bonded. In addition, an optical laminate 1 was produced.
- PET polyethylene terephthalate
- Transparent conductive film 1 (Formation of cured resin layer) Acrylic spherical particles (trade name, manufactured by Soken Chemical Co., Ltd.) having 100 parts by weight of an ultraviolet curable resin composition (trade name “UNIDIC (registered trademark) RS29-120” manufactured by DIC) and a mode particle diameter of 1.9 ⁇ m.
- an ultraviolet curable resin composition (trade name “UNIDIC (registered trademark) RS29-120” manufactured by DIC) and a mode particle diameter of 1.9 ⁇ m.
- a long substrate polycycloolefin film, trade name “ZEONOR (registered trademark)” manufactured by Nippon Zeon Co., Ltd.
- ZEONOR registered trademark
- a coating layer was formed.
- the coating layer was irradiated with ultraviolet rays from the side on which the coating layer was formed, and a second cured resin layer was formed so as to have a thickness of 1.0 ⁇ m.
- a first cured resin layer was formed on the other surface of the substrate by the same method as described above except that spherical particles were not included, so that the thickness became 1.0 ⁇ m.
- an organic-inorganic hybrid resin (trade name: OPSTAR Z7412 (registered trademark) manufactured by JSR Corporation, solid content) composed of a binder of zirconium oxide particles having an average particle diameter of 30 nm and an acrylic resin is used. : 20%, solvent: 80%) was applied to form an optical adjustment layer to obtain a substrate laminate.
- This base laminate was subjected to a heating roll-up process to produce a roll of base laminate wound in a roll shape.
- the base material laminate fed out from the roll is put into a take-up type sputtering apparatus, and an amorphous indium tin oxide (ITO) layer having a thickness of 27 nm is formed on the surface of the first cured resin layer. Formed.
- the substrate laminate on which the amorphous ITO layer (transparent conductive layer) is formed is put into an air circulation oven by a roll-to-roll method, and subjected to a heat treatment at 130 ° C. for 90 minutes.
- the film was converted from amorphous to crystalline to form a transparent conductive film having a transparent conductive layer having a surface resistance value of 100 ⁇ / ⁇ , and a transparent conductive film 1 wound into a roll was produced.
- Transparent conductive film 2 It was produced in the same manner as the transparent conductive film 1 except that the substrate was changed from a polycycloolefin film to a polyethylene terephthalate (PET) film (thickness: 23 ⁇ m).
- 3-2. Production of Optical Laminate 3 A protective film B1 (without a hard coat layer) was bonded to one side of the polarizer A1 via the ultraviolet curable adhesive. Subsequently, the said transparent conductive film 2 was bonded together through the said adhesive to the protective film B1 side of the laminated body of polarizer A1 / protective film B1. Furthermore, the protective film B1 hard-coated on the ITO side was bonded through the adhesive.
- the retardation film was bonded to the other side of the polarizer A1 via the ultraviolet curable adhesive.
- the retardation film was laminated so that the slow axis of the retardation film was 45 ° counterclockwise with respect to the absorption axis of the polarizer.
- the optical laminated body 3 was produced.
- Example 4 The same as Example 1 except that the first liquid crystal alignment solidified layer ( ⁇ / 2 plate) and the second liquid crystal alignment solidified layer ( ⁇ / 4 plate) were used in order from the polarizer side instead of the retardation film 1. Thus, an optical laminate 4 was produced.
- the liquid crystal alignment solidified layer was produced as follows.
- As the liquid crystal material a polymerizable liquid crystal material exhibiting a nematic liquid crystal phase (manufactured by BASF: trade name Paliocolor LC242) was used.
- a photopolymerization initiator manufactured by BASF: trade name Irgacure 907 for the polymerizable liquid crystal material was dissolved in toluene.
- a liquid crystal coating solution was prepared by adding about 0.1 to 0.5% in accordance with the thickness of the liquid crystal layer from which a DIC mega-fac series can be obtained.
- the liquid crystal coating solution was applied onto an alignment substrate with a bar coater, then heated and dried at 90 ° C. for 2 minutes, and then fixed in alignment by ultraviolet curing in a nitrogen atmosphere.
- a second liquid crystal alignment solidified layer ( ⁇ / 4 plate) and a first liquid crystal alignment solidified layer ( ⁇ / 2 plate) were formed on the alignment substrate, respectively.
- the thickness of the first liquid crystal alignment solidified layer ( ⁇ / 2 plate) was 2 ⁇ m
- the thickness of the second liquid crystal alignment solidified layer ( ⁇ / 4 plate) was 1 ⁇ m.
- the alignment substrate for example, a material such as PET that can transfer the liquid crystal alignment solidified layer later is used, and the first liquid crystal alignment solidified layer ( ⁇ / 2 plate) is adjacent to the polarizer A1.
- the alignment solidified layer ( ⁇ / 2 plate) and the second liquid crystal alignment solidified layer ( ⁇ / 4 plate) were sequentially transferred.
- Example 18 An optical laminate having the same layer configuration as that of the optical laminate 1 was produced in the same manner as in Example 1 except that the hard coat layer forming material was changed.
- the material for forming the hard coat layer is as follows. 6 parts of UV curable polyrotaxane (trade name: Celm Superpolymer SA2403P, manufactured by Advanced Soft Materials) and nano silica particles (manufactured by Nissan Chemical Industries, Ltd.) with respect to 100 parts of the hard coat layer forming composition described in Example 1. What added 20 parts of organo silica sol MIBK-ST (average particle diameter 10-15nm)) was mixed, and it was set as the composition for hard-coat layer formation.
- UV curable polyrotaxane trade name: Celm Superpolymer SA2403P, manufactured by Advanced Soft Materials
- nano silica particles manufactured by Nissan Chemical Industries, Ltd.
- the optical laminated body 6 was produced like Example 1 except having used protective film B7 (triacetyl cellulose (TAC): thickness 40 micrometers) instead of protective film B1.
- protective film B7 triacetyl cellulose (TAC): thickness 40 micrometers
- Pencil Hardness The pencil hardness of JIS K 5600-5-4 for the hard coat treated surface of the protective film (the surface of the protective film when not hard coated) of the optical laminate obtained in each Example and each Comparative Example. The pencil hardness was measured according to the test (however, the load was 500 g). 2.
- FIG. 5 shows a schematic diagram of a 180 ° folding resistance tester (manufactured by Imoto Seisakusho).
- This apparatus has a mechanism in which the chuck on one side repeats 180 ° bending with the mandrel interposed therebetween, and the bending radius (curvature radius) can be changed depending on the diameter of the mandrel.
- the optical laminate (30 mm ⁇ 150 mm) obtained in each Example and Comparative Example was set in an apparatus so that the hard coat side or the surface of the protective film was inwardly bent, the temperature was 25 ° C., the bending angle was 170 °, Bending was repeated under the conditions of a bending radius of 1 mm to 3 mm, a bending speed of 1 second / time, and a weight of 100 g. Bending resistance was evaluated by the number of times until the optical laminate was broken. The fracture was evaluated visually. The evaluation criteria are as follows. A: No break even after 1 million cycles B: Break at 200,000 to 500,000 times C: Break at 1 to less than 100,000 times D: Break at less than 10,000 times
- optical laminates of the examples of the present invention are excellent in the balance of pencil hardness, scratch resistance and flex resistance.
- the optical layered body of the present invention is suitably used for an organic EL display device, and can be particularly suitably used for a bendable or foldable organic EL display device.
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Abstract
Description
1つの実施形態においては、上記表面保護層は単一の樹脂フィルムで構成されている。別の実施形態においては、上記表面保護層は、表面側から順にハードコート層と樹脂フィルムとを含む。
1つの実施形態においては、上記表面保護層は曲率半径3mm以下で20万回折り曲げ可能な屈曲性を有し、かつ、該表面保護層の視認側表面は、2H以上の鉛筆硬度と1000g荷重で300回往復摩擦しても傷を生じない耐擦傷性とを有する。
1つの実施形態においては、上記光学補償層は位相差フィルムで構成され;該位相差フィルムの面内位相差Re(550)が100nm~180nmであり、かつ、Re(450)<Re(550)<Re(650)の関係を満たし;該位相差フィルムの遅相軸と上記偏光子の吸収軸とのなす角度が35°~55°である。別の実施形態においては、上記光学補償層は上記偏光子の側から順に第1の液晶配向固化層と第2の液晶配向固化層とを有し;該第1の液晶配向固化層の面内位相差Re(550)が180nm~320nmであり、該第2の液晶配向固化層の面内位相差Re(550)が100nm~180nmであり;該第1の液晶配向固化層の遅相軸と上記偏光子の吸収軸とのなす角度が10°~20°であり、該第2の液晶配向固化層の遅相軸と該偏光子の吸収軸とのなす角度が65°~85°である。
1つの実施形態においては、上記光学積層体は、上記光学補償層の上記偏光子と反対側に導電層をさらに備える。
本発明の別の局面によれば、有機エレクトロルミネセンス表示装置が提供される。この有機エレクトロルミネセンス表示装置は、上記の光学積層体を視認側に備え、該積層体の表面保護層が視認側に配置されている。
1つの実施形態においては、上記有機エレクトロルミネセンス表示装置は、少なくとも一部が曲率半径10mm以下で屈曲可能である。
本明細書における用語および記号の定義は下記の通りである。
(1)屈折率(nx、ny、nz)
「nx」は面内の屈折率が最大になる方向(すなわち、遅相軸方向)の屈折率であり、「ny」は面内で遅相軸と直交する方向(すなわち、進相軸方向)の屈折率であり、「nz」は厚み方向の屈折率である。
(2)面内位相差(Re)
「Re(λ)」は、23℃における波長λnmの光で測定したフィルムの面内位相差である。例えば、「Re(450)」は、23℃における波長450nmの光で測定したフィルムの面内位相差である。Re(λ)は、フィルムの厚みをd(nm)としたとき、式:Re=(nx-ny)×dによって求められる。
(3)厚み方向の位相差(Rth)
「Rth(λ)」は、23℃における波長550nmの光で測定したフィルムの厚み方向の位相差である。例えば、「Rth(450)」は、23℃における波長450nmの光で測定したフィルムの厚み方向の位相差である。Rth(λ)は、フィルムの厚みをd(nm)としたとき、式:Rth=(nx-nz)×dによって求められる。
(4)Nz係数
Nz係数は、Nz=Rth/Reによって求められる。
(5)液晶化合物の配向固化層
「配向固化層」とは、液晶化合物が層内で所定の方向に配向し、その配向状態が固定されている層をいう。なお、「配向固化層」は、液晶モノマーを硬化させて得られる配向硬化層を包含する概念である。
(6)角度
本明細書において角度に言及するときは、特に明記しない限り、当該角度は時計回りおよび反時計回りの両方の方向の角度を包含する。
本発明の実施形態による光学積層体は、画像表示装置(例えば、液晶表示装置、有機EL表示装置)、好ましくは屈曲可能(ベンダブル)な画像表示装置、より好ましくは屈曲可能な有機EL表示装置、さらに好ましくは折りたたみ可能(フォルダブル)な有機EL表示装置に用いられる。以下、簡単のため、光学積層体が屈曲可能または折りたたみ可能な有機EL表示装置に適用される場合について説明するが、光学積層体が液晶表示装置にも同様に適用され得ることは当業者に自明である。
B-1.表面保護層の特性
上記のとおり、表面保護層10は、有機EL表示装置のカバーガラスを代替する機能を有し、かつ、偏光子20の保護層として機能する。以下、表面保護層の特性についての説明における「表面保護層」は、樹脂フィルム単独の場合には樹脂フィルムを、ハードコート層と樹脂フィルムとを含む場合にはこれらの積層体を意味する。表面保護層は、曲率半径3mm以下(例えば、3mm、2mm、1mm)で好ましくは20万回、より好ましくは30万回、さらに好ましくは50万回折り曲げ可能な屈曲性を有する。表面保護層がこのような屈曲性を有することにより、光学積層体を有機EL表示装置に適用した場合に屈曲可能または折り畳み可能な有機EL表示装置を実現することができる。表面保護層が樹脂フィルムの片側にハードコート層を有する場合、屈曲性の試験は、ハードコート層を内側にして折り曲げて行われる。屈曲性は、マンドリルを挟んで片側のチャックが180°折り曲げを繰り返す耐折試験機にて測定され得る。
ハードコート層11は、上記のとおり、樹脂フィルム12の構成に応じて、樹脂フィルムの片側(代表的には、表面側)に形成されてもよく、樹脂フィルムの両側に形成されてもよく、省略されてもよい。
樹脂フィルムは、上記B-1項に記載の特性を満足し得る任意の適切な材料で構成され得る。構成材料の具体例としては、ポリエチレンテレフタレート系樹脂、ポリエチレンナフタレート系樹脂、アセテート系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリオレフィン系樹脂、(メタ)アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリフェニレンサルファイド系樹脂等が挙げられる。これらの樹脂は、単独で用いてもよく、2種以上を組み合わせて用いてもよい。好ましくは、ポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート系樹脂、ポリカーボネート系樹脂である。耐久性に優れるからである。
偏光子20としては、任意の適切な偏光子が採用され得る。例えば、偏光子を形成する樹脂フィルムは、単層の樹脂フィルムであってもよく、二層以上の積層体であってもよい。
D-1.位相差フィルムで構成される光学補償層
図1に示すように光学補償層が位相差フィルムで構成される場合、当該位相差フィルムは、いわゆるλ/4板として機能し得る。位相差フィルムの面内位相差Re(550)は、好ましくは100nm~180nm、より好ましくは135nm~155nmである。
D-2-1.第1の液晶配向固化層
第1の液晶配向固化層31は、いわゆるλ/2板として機能し得る。第1の液晶配向固化層をいわゆるλ/2板とし、後述の第2の液晶配向固化層をいわゆるλ/4板とし、これらの遅相軸を偏光子の吸収軸に対して所定の方向に設定することにより、広帯域において優れた円偏光特性を有する光学積層体が得られ得る。第1の液晶配向固化層の面内位相差Re(550)は、好ましくは180nm~320nmであり、より好ましくは200nm~290nmであり、さらに好ましくは230nm~280nmである。
第2の液晶配向固化層32は、いわゆるλ/4板として機能し得る。第2の液晶配向固化層をいわゆるλ/4板とし、第1の液晶配向固化層を上記のようにいわゆるλ/2板とし、これらの遅相軸を偏光子の吸収軸に対して所定の方向に設定することにより、広帯域において優れた円偏光特性を有する光学積層体が得られ得る。第2の液晶配向固化層の面内位相差Re(550)は、上記のとおり好ましくは100nm~180nmであり、より好ましくは110nm~170nmであり、さらに好ましくは120nm~160nmである。
導電層(図示せず)は、代表的には透明である(すなわち、導電層は透明導電層である)。光学補償層の偏光子と反対側に導電層を形成することにより、光学積層体は、表示セル(有機ELセル)と偏光子との間にタッチセンサが組み込まれた、いわゆるインナータッチパネル型入力表示装置に適用され得る。
印刷層は、上記のとおり、光学積層体の周縁部、より具体的には平面視で有機EL表示装置のベゼルに対応する位置に形成されている。これも上記のとおり、印刷層は、表面保護層10の偏光子20側(実質的には、樹脂フィルム12の偏光子20側)に形成されてもよく、光学補償層30の偏光子20と反対側に形成されてもよい。印刷層は、所定のデザインが施された意匠層であってもよく、ベタの着色層であってもよい。印刷層は、好ましくはベタの着色層であり、より好ましくは黒色の着色層である。黒色の着色層をベゼルに対応する位置に形成することにより、非表示領域を隠蔽することができるので、本実施形態の光学積層体を用いれば、ベゼルを用いない有機EL表示装置を実現することができる。その結果、最表面に段差のない、きわめて優れた外観を有する有機EL表示装置を提供することができる。さらに、印刷層を光学補償層に形成する場合には以下の利点が得られる:すなわち、このような構成であれば、印刷層は必然的に偏光子の下側(有機EL表示装置側)に配置されることとなり、その結果、印刷層の界面の反射光が偏光子により軽減される。したがって、さらに優れた外観を有する有機EL表示装置を実現することができる。
内側保護層(内側保護フィルム:図示せず)を設ける場合には、当該内側保護フィルムは、光学的に等方性であることが好ましい。本明細書において「光学的に等方性である」とは、面内位相差Re(550)が0nm~10nmであり、厚み方向の位相差Rth(550)が-10nm~+10nmであることをいう。
本発明の光学積層体を構成する各層の積層には、任意の適切な粘着剤層または接着剤層が用いられる。より具体的には、表面保護層と偏光子とは、粘着剤層または接着剤層を介して積層されている。これらの積層以外の積層には、代表的には粘着剤層が用いられ得る。以下、便宜上、表面保護層と偏光子との積層に用いられる粘着剤層を単に粘着剤層と称し、これら以外の積層に用いられる粘着剤層を他の粘着剤層と称する。
本発明の光学積層体が適用され得る画像表示装置の一例として、有機EL表示装置について説明する。なお、本発明の光学積層体は、上記のとおり液晶表示装置にも適用され得る。図3は、本発明の1つの実施形態による有機EL表示装置の概略断面図である。有機EL表示装置300は、有機EL素子(有機EL表示セル)200と、有機EL素子200の視認側に光学積層体100または101を備える。光学積層体は、上記A項~H項に記載した本発明の光学積層体である。光学積層体は、光学補償層が有機EL素子側となるように(表面保護層が視認側となるように)積層されている。なお、光学積層体は、上記の光学積層体100または101に限られず、図示していない本発明のさらに別の実施形態による光学積層体であってもよい。
有機EL素子200としては、本発明の効果が得られる限りにおいて、任意の適切な有機EL素子を採用することができる。図4は、本発明に用いられる有機EL素子の一形態を説明する概略断面図である。有機EL素子200は、代表的には、基板210と、第1電極220と、有機EL層230と、第2電極240と、これらを覆う封止層250とを有する。有機EL素子200は、必要に応じて、任意の適切な層をさらに有し得る。例えば、基板上に平坦化層(図示せず)を設けてもよく、第1電極と第2電極との間に短絡を防止するための絶縁層(図示せず)を設けてもよい。
1-1.位相差フィルム1
撹拌翼および100℃に制御された還流冷却器を具備した縦型反応器2器からなるバッチ重合装置を用いて重合を行った。9,9-[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(BHEPF)、イソソルビド(ISB)、ジエチレングリコール(DEG)、ジフェニルカーボネート(DPC)、および酢酸マグネシウム4水和物を、モル比率でBHEPF/ISB/DEG/DPC/酢酸マグネシウム=0.438/0.537/0.025/1.005/1.00×10-5になるように仕込んだ。反応器内を十分に窒素置換した後(酸素濃度0.0005~0.001vol%)、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を100℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。
第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、50分で内温240℃、圧力0.2kPaにした。その後、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、反応液をストランドの形態で抜出し、回転式カッターでペレット化を行い、BHEPF/ISB/DEG=43.8/53.7/2.5[mol%]の共重合組成のポリカーボネート樹脂を得た。このポリカーボネート樹脂の還元粘度は0.430dL/g、ガラス転移温度は145℃であった。
得られたポリカーボネート樹脂を80℃で5時間真空乾燥した後、単軸押出機(いすず化工機社製、スクリュー径25mm、シリンダー設定温度:240℃)、Tダイ(幅900mm、設定温度:240℃)、チルロール(設定温度:120~130℃)および巻取機を備えたフィルム製膜装置を用いて、厚み125μmのポリカーボネート樹脂フィルムを作製した。
上記のようにして得られたポリカーボネート樹脂フィルムから幅250mm、長さ250mmの試料を切り出した。そして、この試料を、バッチ式二軸延伸装置(ブルックナー社製 商品名「KARO-IV」)にて、延伸温度145.6℃、延伸倍率2.4倍で固定端一軸横延伸し、厚み58μmの位相差フィルム1を作製した。
(偏光子A1の作製)
吸水率0.75%、Tg75℃の非晶質のイソフタル酸共重合ポリエチレンテレフタレート(IPA共重合PET)フィルム(厚み:100μm)基材の片面にコロナ処理を施し、このコロナ処理面に、ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%以上、日本合成化学工業社製、商品名「ゴーセファイマーZ200」)を9:1の比で含む水溶液を25℃で塗布および乾燥して、厚み11μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、120℃のオーブン内で周速の異なるロール間で縦方向(長手方向)に2.0倍に自由端一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温30℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴に、偏光板が所定の透過率となるようにヨウ素濃度、浸漬時間を調整しながら浸漬させた。本実施例では、水100重量部に対して、ヨウ素を0.2重量部配合し、ヨウ化カリウムを1.0重量部配合して得られたヨウ素水溶液に60秒間浸漬させた(染色処理)。
次いで、液温30℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を3重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(水100重量部に対して、ホウ酸を4重量部配合し、ヨウ化カリウムを5重量部配合して得られた水溶液)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温30℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
以上により、厚み5μmの偏光子A1を含む光学フィルム積層体を得た。
(保護フィルムB1の作製)
保護フィルム(ラクトン環構造を有する(メタ)アクリル樹脂フィルム:厚み40μm)の片面(偏光子と接着される面)にコロナ処理を施して用いた。
(保護フィルムB1へのハードコート処理)
15官能ウレタンアクリルオリゴマー(新中村化学社製、商品名:NK オリゴ UA-53H、重量平均分子量:2300)40部、ペンタエリスリトールトリアクリレート(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)40部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)16部、エトキシル化グリセリントリアクリレート(新中村化学社製 商品名:A-GLY-9E)4部、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈してハードコート層形成用組成物を調製した。
保護フィルムB1上に、得られたハードコート層形成用組成物を塗布して塗布層を形成し、当該塗布層を90℃で1分間加熱した。加熱後の塗布層に高圧水銀ランプにて積算光量300mJ/cm2の紫外線を照射して厚み5μmのハードコート層を形成した。
(保護フィルムに適用する接着剤の作製)
N-ヒドロキシエチルアクリルアミド(HEAA)40重量部とアクリロイルモルホリン(ACMO)60重量部と光開始剤「IRGACURE 819」(BASF社製)3重量部を混合し、紫外線硬化型接着剤を調製した。
(偏光板の作製)
上記偏光子A1の片側に上記紫外線硬化型接着剤を介してハードコート層を有する保護フィルムB1を貼り合せた。次いで上記偏光子のもう片側に、上記紫外線硬化型接着剤を介して上記位相差フィルムを貼り合せた。ここで、位相差フィルムの遅相軸が偏光子の吸収軸に対して反時計まわりに45°となるように貼り合せ、円偏光板(光学積層体)を作製した。
本実施例で使用する粘着層を以下の方法により作製した。
((メタ)アクリル系ポリマーの調製)
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート(BA)99重量部、4-ヒドロキシブチルアクリレート(HBA)1重量部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物(固形分)100重量部に対して、重合開始剤として2,2´-アゾビスイソブチロニトリルを0.1重量部を酢酸エチルと共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を55℃付近に保って7時間重合反応を行った。その後、得られた反応液に、酢酸エチルを加えて、固形分濃度30%に調整した、重量平均分子量160万の(メタ)アクリル系ポリマーの溶液を調製した。
(アクリル系粘着剤組成物の調製)
得られた(メタ)アクリル系ポリマー溶液の固形分100重量部に対して、イソシアネート系架橋剤(商品名:タケネートD110N、トリメチロールプロパンキシリレンジイソシアネート、三井化学(株)製)0.2重量部と、シランカップリング剤(商品名:KBM403、信越化学工業(株)製)0.08重量部を配合して、アクリル系粘着剤組成物を調製した。
上記アクリル系粘着剤組成物を、シリコーン系剥離剤で処理された厚さ38μmのポリエチレンテレフタレート(PET)フィルム(セパレータ)の表面に、ファウンテンコータで均一にて塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、セパレータ表面に厚さ25μmの粘着剤層を形成した。次いで、上記で得られた円偏光板の位相差フィルム側に上記粘着剤層を介してセパレータを貼り合わせ、当該セパレータを剥離した後PETフィルム(厚み38μm:屈曲性有機ELパネルを想定)を貼り合わせ、光学積層体1を作製した。
2-1.透明導電性フィルム1
(硬化樹脂層の形成)
紫外線硬化性樹脂組成物(DIC社製 商品名「UNIDIC(登録商標)RS29-120」)を100重量部と、最頻粒子径が1.9μmであるアクリル系球状粒子(綜研化学社製 商品名「MX-180TA」)を0.002重量部とを含む、球状粒子入り硬化性樹脂組成物を準備した。準備した球状粒子入り硬化性樹脂組成物を厚みが23μm、幅1550mmの長尺状の基材(ポリシクロオレフィンフィルム、日本ゼオン製 商品名「ZEONOR(登録商標)」)の一方の面に塗布し、塗布層を形成した。次いで、塗布層が形成された側から塗布層に紫外線を照射して、厚みが1.0μmとなるように第2硬化樹脂層を形成した。基材の他方の面に、球状粒子を含まないこと以外は上記と同様の方法で、厚みが1.0μmとなる様に第1硬化樹脂層を形成した。さらに、第1硬化樹脂層上に、平均粒径が30nmの酸化ジルコニウム粒子とアクリル系樹脂のバインダーで構成された有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7412(登録商標)、固形分:20%、溶媒:80%)を塗布して光学調整層を形成し、基材積層体とした。この基材積層体に加熱巻き上げ処理を行い、ロール状に巻かれた基材積層体のロールを作製した。
(透明導電層の形成)
次に、上記ロールから繰り出された基材積層体を、巻き取り式スパッタ装置に投入し、第1硬化樹脂層の表面に、厚みが27nmの非晶質のインジウム・スズ酸化物(ITO)層を形成した。その後、該非晶質ITO層(透明導電層)が形成された基材積層体を、ロールトゥロール方式で空気循環式オーブンに投入し、130℃で90分間の加熱処理を行い、透明導電層を非晶質から結晶質に転化させ、透明導電層の表面抵抗値が100Ω/□の透明導電性フィルムを形成し、ロール状に巻かれた透明導電性フィルム1を作製した。
実施例1で得た円偏光板の位相差フィルム側に上記粘着剤を介して上記で得た透明導電性フィルム1を貼り合せ、次いでそのITO側に上記粘着剤層を介してセパレータを貼り合せ、光学積層体2を作製した。
3-1.透明導電性フィルム2
基材をポリシクロオレフィンフィルムからポリエチレンテレフタレート(PET)フィルム(厚み23μm)に変更したこと以外は透明導電性フィルム1と同様にして作製した。
3-2.光学積層体3の作製
上記偏光子A1の片側に上記紫外線硬化型接着剤を介して保護フィルムB1(ハードコート層なし)を貼り合せた。次いで、偏光子A1/保護フィルムB1の積層体の保護フィルムB1側に上記粘着剤を介して、上記透明導電性フィルム2を貼り合せた。さらに、そのITO側にハードコート処理された保護フィルムB1を上記粘着剤を介して貼り合せた。さらに、偏光子A1のもう片側に、上記紫外線硬化型接着剤を介して上記位相差フィルムを貼り合せた。ここで、位相差フィルムの遅相軸が偏光子の吸収軸に対して反時計まわりに45°となるように貼り合せた。このようにして、光学積層体3を作製した。
位相差フィルム1の代わりに偏光子側から順に第1の液晶配向固化層(λ/2板)および第2の液晶配向固化層(λ/4板)を用いたこと以外は実施例1と同様にして、光学積層体4を作製した。液晶配向固化層は、以下のようにして作製した。
液晶材料として、ネマチック液晶相を示す重合性液晶材料(BASF社製:商品名Paliocolor LC242)を用いた。当該重合性液晶材料に対する光重合開始剤(BASF社製: 商品名イルガキュア907)をトルエンに溶解した。さらに塗工性向上を目的としてDIC製のメガファックシリーズを得られる液晶層厚みに応じて0.1から0.5%程度加え、液晶塗工液を調製した。配向基材上に、当該液晶塗工液をバーコーターにより塗工した後、90℃で2分間加熱乾燥後、窒素雰囲気下で紫外線硬化により配向固定化させた。配向基材上に第2の液晶配向固化層(λ/4板)および第1の液晶配向固化層(λ/2板)をそれぞれ配向基材上に形成した。第1の液晶配向固化層(λ/2板)の厚みは2μmであり、第2の液晶配向固化層(λ/4板)の厚みは1μmであった。配向基材は、例えばPETのように液晶配向固化層を後から転写できるものを使用し、第1の液晶配向固化層(λ/2板)が偏光子A1に隣接するように第1の液晶配向固化層(λ/2板)および第2の液晶配向固化層(λ/4板)を順次転写した。
表1に示す構成としたこと以外は実施例1と同様にして、光学積層体1と同様の層構成を有する光学積層体を作製した。なお、表1中の保護フィルムB2~B6は以下のとおりである。
・保護フィルムB2:ポリアミドフィルム(ユニチカ製 「ユニアミド EX-25」、厚み25μm)
・保護フィルムB3:透明ポリイミドフィルム(I.S.T製 「トーメッド 」、厚み25μm)
・保護フィルムB4:透明ポリイミドフィルム(三菱瓦斯化学製 「ネオプリム L-AJFF-50」、厚み50μm)
・保護フィルムB5:ポリカーボネートフィルム(三菱エンジニアリングプラスチック製 ユーピロン「KH3520 UR」、厚み40μm)
・保護フィルムB6:ポリエチレンテレフタレートフィルム(東洋紡製 「コスモシャイン A4100」、厚み50μm)
ハードコート層の形成材料を変更したこと以外は実施例1と同様にして、光学積層体1と同様の層構成を有する光学積層体を作製した。ハードコート層の形成材料は以下のとおりである。
実施例1記載のハードコート層形成用組成物100部に対してUV硬化型ポリロタキサン(アドバンスト・ソフトマテリアル社製 商品名:セルムスーパーポリマーSA2403P)6部とナノシリカ粒子(日産化学工業社製 商品名:オルガノシリカゾルMIBK-ST(平均粒径 10~15nm))20部添加したものを混合し、ハードコート層形成用組成物とした。
実施例1記載のハードコート処理された保護フィルムB1をそのまま用い、光学積層体5とした。
保護フィルムB1の代わりに保護フィルムB7(トリアセチルセルロース(TAC):厚み40μm)を用いたこと以外は実施例1と同様にして光学積層体6を作製した。
C3-1.偏光子A2(厚さ12μmの偏光子)の作製
平均重合度2400、ケン化度99.9モル%の厚み30μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、総延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子を得た。得られた偏光子の厚みは12μmであった。
C3-2.保護フィルムB7
保護フィルムB7としてトリアセチルセルロース(TAC、厚み40μm)を用いた。
C3-3.光学積層体6の作製
偏光子A1の代わりに偏光子A2を用い、保護フィルムB1の代わりに保護フィルムB7を用いたこと以外は実施例1と同様にして、光学積層体6と同様の層構成を有する光学積層体を作製した。
保護フィルムB7にハードコート処理を行わなかったこと以外は比較例3と同様にして、光学積層体6と同様の層構成を有する光学積層体を作製した。
偏光子A2の代わりに偏光子A3(厚さ18μm)を用いたこと以外は比較例3と同様にして、光学積層体6と同様の層構成を有する光学積層体を作製した。
偏光子A2の代わりに偏光子A4(厚さ23μm)を用いたこと以外は比較例3と同様にして、光学積層体6と同様の層構成を有する光学積層体を作製した。
1.鉛筆硬度
各実施例および各比較例で得られた光学積層体の保護フィルムのハードコート処理面(ハードコート処理されていない場合には保護フィルム表面)について、JIS K 5600-5-4の鉛筆硬度試験に準じて(但し、荷重500g)、鉛筆硬度を測定した。
2.耐擦傷性(スチールウール(SW)評価)
各実施例および各比較例で得られた光学積層体の保護フィルムのハードコート処理面(ハードコート処理されていない場合には保護フィルム表面)について、学振型摩擦堅牢度試験機(テスター産業株式会社製、AB-301)を用いて、500g/cm2の荷重をかけたスチールウール(日本スチールウール社製、ボンスター#0000)で300往復擦り、擦り跡やキズなどによる外観の変化を目視で評価した。評価基準は以下のとおりである。
○:傷は認められなかった
×:傷を確認した
3.耐屈曲性評価
図5に180°耐折性試験機(井元製作所製)の概略図を示す。本装置は、マンドレルを挟んで片側のチャックが180°曲げを繰り返す機構となっており、マンドレルの直径により折り曲げ半径(曲率半径)を変えることができる。試験は、各実施例および比較例で得られた光学積層体(30mm×150mm)をハードコート側または保護フィルム表面が内曲げになるように装置にセットし、温度25℃、曲げ角度170°、折り曲げ半径1mm~3mm、曲げ速度1秒/回、重り100gの条件で曲げの繰り返しを実施した。光学積層体の破断までの回数で耐屈曲性を評価した。破断は目視にて評価した。評価基準は以下のとおりである。
A:100万回以上でも破断しない
B:20万~50万回で破断
C:1~10万回未満で破断
D:1万回未満で破断
20 偏光子
30 光学補償層(位相差フィルム)
31 第1の液晶配向固化層
32 第2の液晶配向固化層
100 光学積層体
101 光学積層体
200 有機EL素子
300 有機EL表示装置
Claims (9)
- 有機エレクトロルミネセンス表示装置に用いられる光学積層体であって、
表面保護層と偏光子と光学補償層とをこの順に備え、
該表面保護層が可撓性であり、有機エレクトロルミネセンス表示装置のカバーガラスを代替する機能を有し、かつ、偏光子の保護層として機能する、
光学積層体。 - 前記表面保護層が単一の樹脂フィルムで構成されている、請求項1に記載の光学積層体。
- 前記表面保護層が、表面側から順にハードコート層と樹脂フィルムとを含む、請求項1に記載の光学積層体。
- 前記表面保護層が曲率半径3mm以下で20万回折り曲げ可能な屈曲性を有し、かつ、該表面保護層の視認側表面が、2H以上の鉛筆硬度と1000g荷重で300回往復摩擦しても傷を生じない耐擦傷性とを有する、請求項1から3のいずれかに記載の光学積層体。
- 前記光学補償層が位相差フィルムで構成され、
該位相差フィルムの面内位相差Re(550)が100nm~180nmであり、かつ、Re(450)<Re(550)<Re(650)の関係を満たし、
該位相差フィルムの遅相軸と前記偏光子の吸収軸とのなす角度が35°~55°である、
請求項1から4のいずれかに記載の光学積層体。 - 前記光学補償層が前記偏光子の側から順に第1の液晶配向固化層と第2の液晶配向固化層とを有し、
該第1の液晶配向固化層の面内位相差Re(550)が180nm~320nmであり、該第2の液晶配向固化層の面内位相差Re(550)が100nm~180nmであり、
該第1の液晶配向固化層の遅相軸と前記偏光子の吸収軸とのなす角度が10°~20°であり、該第2の液晶配向固化層の遅相軸と該偏光子の吸収軸とのなす角度が65°~85°である、
請求項1から4のいずれかに記載の光学積層体。 - 前記光学補償層の前記偏光子と反対側に導電層をさらに備える、請求項1から6のいずれかに記載の光学積層体。
- 請求項1から7のいずれかに記載の光学積層体を視認側に備え、該積層体の表面保護層が視認側に配置されている、有機エレクトロルミネセンス表示装置。
- 少なくとも一部が曲率半径10mm以下で屈曲可能である、請求項8に記載の有機エレクトロルミネセンス表示装置。
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