WO2016010116A1 - 波長変換シート用保護フィルム、波長変換シート及びバックライトユニット - Google Patents
波長変換シート用保護フィルム、波長変換シート及びバックライトユニット Download PDFInfo
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- WO2016010116A1 WO2016010116A1 PCT/JP2015/070421 JP2015070421W WO2016010116A1 WO 2016010116 A1 WO2016010116 A1 WO 2016010116A1 JP 2015070421 W JP2015070421 W JP 2015070421W WO 2016010116 A1 WO2016010116 A1 WO 2016010116A1
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- layer
- wavelength conversion
- conversion sheet
- barrier
- protective film
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0025—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0033—Means for improving the coupling-out of light from the light guide
- G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
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- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B32B2255/20—Inorganic coating
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/02—Synthetic macromolecular particles
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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
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0013—Means for improving the coupling-in of light from the light source into the light guide
- G02B6/0023—Means for improving the coupling-in of light from the light source into the light guide provided by one optical element, or plurality thereof, placed between the light guide and the light source, or around the light source
Definitions
- the present invention relates to a protective film for a wavelength conversion sheet, and a wavelength conversion sheet and a backlight unit using the same.
- a liquid crystal display is a display device that displays an image or the like by controlling the alignment state of liquid crystal by applying a voltage and transmitting or blocking light in each region.
- a light source of the liquid crystal display a backlight provided on the back surface of the liquid crystal display is used.
- a cold cathode tube is used for the backlight, but recently, an LED (light emitting diode) is being used instead of the cold cathode tube for reasons such as long life and good color development.
- the white LED technology is very important.
- white LED technology a cerium-doped YAG: Ce (yttrium, aluminum, garnet: cerium) down-conversion phosphor is generally excited with a blue (450 nm) LED chip.
- white light is obtained by mixing the blue light of the LED with yellow light having a wide wavelength range generated from the YAG: Ce phosphor.
- this white light is often somewhat bluish and often gives the impression of “cold” or “cool” white.
- Quantum dots are light-emitting semiconductor nanoparticles with a diameter range of about 1 to 20 nm. Since quantum dots show a wide excitation spectrum and high quantum efficiency, they can be used as phosphors for LED wavelength conversion. Furthermore, there is an advantage that the wavelength of light emission can be completely adjusted over the entire visible range only by changing the dot size or the type of semiconductor material. As such, quantum dots have the potential to create virtually any color, especially the warm white that is highly desired in the lighting industry. In addition, it is possible to obtain white light having different color rendering index by combining three types of dots corresponding to red, green, and blue emission wavelengths. In this way, with a liquid crystal display using a quantum dot backlight, the color tone is improved and many colors that can be identified by humans can be expressed without increasing the thickness, power consumption, cost, and manufacturing process. become.
- a backlight using a white LED as described above diffuses a phosphor having a predetermined emission spectrum (quantum dots and YAG: Ce, etc.) into the film, and seals the surface with a barrier film.
- a phosphor having a predetermined emission spectrum quantum dots and YAG: Ce, etc.
- the barrier film forms a thin film by vapor deposition or the like on the surface of a base material such as a plastic film to prevent moisture and gas from permeating.
- this barrier film is required to prevent appearance defects such as splash, scratches and wrinkles.
- splash is a phenomenon in which the vapor deposition material is scattered as high-temperature fine particles, and the vapor deposition material directly adheres to the base material and becomes a foreign object, or a hole is made in the base material. The phenomenon that ends up.
- many of the conventional barrier films have been used as packaging materials such as foods and medical products and packaging materials such as electronic devices, so that satisfactory performance cannot be obtained. There was a problem.
- Patent Document 1 proposes a backlight having a structure in which a phosphor is sandwiched between barrier films in order to suppress degradation of the phosphor.
- the present invention has been made in view of such circumstances, and as a protective film for protecting the phosphor in the wavelength conversion sheet, it can exhibit excellent barrier properties over a long period of time, and splash, scratches, It aims at providing the protective film for wavelength conversion sheets which can suppress generation
- the present invention provides a protective film for a wavelength conversion sheet for protecting a phosphor in a wavelength conversion sheet, which is provided on a base material and at least one surface of the base material.
- a protective film for wavelength conversion sheet by having a structure in which two or more of the barrier films are laminated, an excellent barrier property can be exhibited over a long period of time, and the influence of splash, scratches, wrinkles, etc. Occurrence of poor appearance due to the above can be suppressed.
- two or more barrier films having a laminated structure of a substrate and a barrier layer are laminated, and this structure is adopted.
- the protective film for wavelength conversion sheets of the present invention can also exhibit the effect of reducing the occurrence of interference fringes.
- the wavelength conversion sheet protective film of the present invention preferably further includes a coating layer having an optical function, and the coating layer is preferably disposed on at least one surface of the wavelength conversion sheet protective film.
- the optical function is preferably an interference fringe prevention function.
- the said coating layer contains binder resin and the microparticles
- the substrate is preferably a polyethylene terephthalate film or a polyethylene naphthalate film. Thereby, more excellent transparency and barrier properties can be obtained.
- the barrier layer includes an inorganic thin film layer laminated on one surface of the base material, and a gas barrier coating layer laminated on the inorganic thin film layer. Is preferred. Thereby, the more superior barrier property with respect to a water
- the barrier layer may have a structure in which two or more layers of the inorganic thin film layer and the gas barrier coating layer are alternately laminated. In this case, further excellent barrier properties can be obtained over a longer period.
- the inorganic thin film layer is preferably a layer containing at least one of silicon oxide and aluminum oxide. Thereby, more excellent barrier properties can be obtained.
- the gas barrier coating layer may be a layer containing at least one of a hydroxyl group-containing polymer compound, a metal alkoxide, a metal alkoxide hydrolyzate, and a metal alkoxide polymer. preferable. Thereby, more excellent barrier properties can be obtained.
- the two or more barrier films are preferably laminated using an adhesive layer containing any one of acrylic resin, urethane resin, and ester resin. Thereby, more excellent transparency and adhesiveness can be obtained.
- the two or more barrier films are laminated using an adhesive layer, and the barrier layer of one of the two adjacent barrier films and the other barrier You may have the structure arrange
- the wavelength conversion sheet protective film is disposed with the barrier layer of the other barrier film facing the phosphor, so that the barrier layer can be provided at a location close to the phosphor.
- the barrier performance against the phosphor can be more effectively exhibited.
- the barrier films are laminated using an adhesive layer, and the barrier layers of two adjacent barrier films are interposed via the adhesive layer. And may be arranged so as to face each other.
- the base material can be disposed between the barrier layer and the phosphor, so that even if irregularities or foreign matter exist on the phosphor, the base material reduces the impact.
- damage to the barrier layer can be suppressed. Therefore, adverse effects on the barrier layer due to splash, scratches, wrinkles and the like can be minimized, and more excellent barrier properties can be obtained.
- the protective film for wavelength conversion sheet of the present invention further includes a coating layer having an optical function disposed on at least one surface, the barrier layer includes a silica vapor deposition layer as an inorganic thin film layer, and the silica vapor deposition
- the O / Si ratio of oxygen and silicon contained in the layer is 1.7 to 2.0 in terms of atomic ratio
- the refractive index of the silica deposited layer is 1.5 to 1.7
- wavelength 450 nm wavelength At all wavelengths of 540 nm and 620 nm
- the wavelength conversion sheet protective film may have a reflectance of 10% to 20% and a transmittance of 80% to 95%.
- this protective film for wavelength conversion sheet since the O / Si ratio is 1.7 or more in atomic ratio, the ratio of Si—Si bonds in the silica vapor deposition layer can be kept low, and the number of colored metals can be reduced. The transmittance of the silica vapor deposition layer is improved. Moreover, since the O / Si ratio is 2.0 or less in terms of atomic ratio, the growth of the deposited film becomes dense and the silica deposited layer has excellent barrier properties.
- This protective film for wavelength conversion sheets can reduce intrusion of water vapor and the like.
- the backlight unit when a backlight unit including a wavelength conversion sheet having the protective film for wavelength conversion sheet is produced, the backlight unit maintains a high luminance for a long period of time, and color unevenness during display application and Suppresses the occurrence of black spots and maintains an excellent appearance.
- the refractive index of the silica vapor deposition layer is 1.5 or more and 1.7 or less
- the reflectance of the protective film for wavelength conversion sheet is 10% or more and 20% or less
- the transmittance is 80% or more and 95% or less. It is.
- this protective film for wavelength conversion sheets reduces the optical interference in a film, and improves the brightness
- the present invention also provides a wavelength conversion sheet comprising a phosphor layer containing a phosphor, and the protective film for wavelength conversion sheet of the present invention laminated on at least one surface of the phosphor layer.
- a wavelength conversion sheet comprising a phosphor layer containing a phosphor, and the protective film for wavelength conversion sheet of the present invention laminated on at least one surface of the phosphor layer.
- the present invention is also a wavelength conversion sheet comprising a phosphor layer containing a phosphor, and the wavelength conversion sheet protective film of the present invention laminated on at least one surface of the phosphor layer, Two or more of the barrier films in the protective film for wavelength conversion sheet are laminated using an adhesive layer, and one of the two adjacent barrier films is a barrier layer of one barrier film and a base material of the other barrier film. Are provided so as to face each other with the adhesive layer interposed therebetween, and a wavelength conversion sheet having a structure in which the barrier layer of the other barrier film is arranged toward the phosphor layer side is provided.
- the wavelength conversion sheet protective film of the present invention since the wavelength conversion sheet protective film of the present invention is provided, it is possible to exhibit excellent barrier properties over a long period of time, and a barrier due to the influence of splash, scratches, wrinkles and the like. The occurrence of defects can be suppressed, and the occurrence of interference fringes can be reduced. Further, the barrier layer of the other barrier film in the protective film for wavelength conversion sheet is disposed toward the phosphor layer side, so that a barrier layer is provided at a location close to the phosphor layer, and the phosphor layer The barrier performance with respect to can be exhibited more effectively.
- the wavelength conversion sheet protective film has a coating layer having an optical function on a surface opposite to the side facing the phosphor layer.
- the present invention further provides a backlight unit comprising an LED light source, a light guide plate, and the wavelength conversion sheet of the present invention.
- a backlight unit comprising an LED light source, a light guide plate, and the wavelength conversion sheet of the present invention.
- the wavelength conversion sheet of the present invention by including the wavelength conversion sheet of the present invention, the decrease in luminance is suppressed over a long period of time, the influence of poor appearance is suppressed, and has a vivid color close to nature,
- the protective film for protecting the phosphor in the wavelength conversion sheet can exhibit excellent barrier properties over a long period of time, and the occurrence of barrier failure due to the influence of splash, scratches, wrinkles, etc. It is possible to provide a protective film for a wavelength conversion sheet that can suppress light, and a wavelength conversion sheet and a backlight unit using the same.
- FIG. 1 is a schematic cross-sectional view of a wavelength conversion sheet according to the first embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view of a wavelength conversion sheet according to the second embodiment of the present invention.
- FIG. 3 is a schematic cross-sectional view of a wavelength conversion sheet protective film according to a third embodiment of the present invention.
- FIG. 1 is a schematic cross-sectional view of a wavelength conversion sheet according to the first embodiment of the present invention.
- the wavelength conversion sheet shown in FIG. 1 contains a phosphor such as a quantum dot, and can be used for a backlight unit, for example, for LED wavelength conversion.
- the wavelength conversion sheet 100 of the present embodiment includes a phosphor layer (wavelength conversion layer) 1 containing a phosphor, and one surface 2 a side and the other surface 2 b side of the phosphor layer 1.
- a wavelength conversion sheet protective film hereinafter also simply referred to as “protective film” 2 and 2 is provided.
- the phosphor layer 1 is encapsulated (ie, sealed) between the protective films 2 and 2.
- a backlight unit is generally composed of a light guide plate and an LED light source.
- the LED light source is installed on the side surface of the light guide plate.
- a plurality of LED elements whose emission color is blue are provided inside the LED light source.
- This LED element may be a purple LED or even a lower wavelength LED.
- the LED light source emits light toward the side surface of the light guide plate.
- the irradiated light is, for example, a layer (phosphor layer) 1 in which a resin such as acrylic or epoxy is mixed with a phosphor through a light guide plate. Will be incident on.
- the phosphor layer 1 since it is necessary to provide the phosphor layer 1 with a barrier property, it is desirable that the phosphor layer 1 is sandwiched between the pair of protective films 2 and 2 for wavelength conversion sheet.
- each layer constituting the wavelength conversion sheet 100 will be described in detail.
- the phosphor layer 1 is a thin film having a thickness of several tens to several hundreds of ⁇ m including the sealing resin 4 and the phosphor 3.
- the sealing resin 4 for example, a photosensitive resin or a thermosetting resin can be used.
- the sealing resin 4 is sealed in a state where one or more phosphors 3 are mixed.
- the sealing resin 4 plays a role of joining the phosphor layer 1 and the pair of protective films 2 and 2 and filling these gaps while laminating them.
- the phosphor layer 1 may be a laminate in which two or more phosphor layers in which only one kind of phosphor 3 is sealed are laminated.
- the two or more kinds of phosphors 3 used in the one or more phosphor layers those having the same excitation wavelength are selected.
- This excitation wavelength is selected based on the wavelength of light emitted by the LED light source.
- the fluorescent colors of two or more types of phosphors 3 are different from each other. When two types of phosphors 3 are used, the fluorescent colors are preferably red and green.
- the wavelength of each fluorescence and the wavelength of light emitted from the LED light source are selected based on the spectral characteristics of the color filter.
- the peak wavelengths of fluorescence are, for example, 610 nm for red and 550 nm for green.
- quantum dots are preferably used.
- the quantum dots include those in which a core as a light emitting portion is coated with a shell as a protective film.
- the core include cadmium selenide (CdSe), and examples of the shell include zinc sulfide (ZnS). Quantum efficiency is improved by covering surface defects of CdSe particles with ZnS having a large band gap.
- the phosphor 3 may be one in which the core is double-coated with the first shell and the second shell.
- CsSe can be used for the core
- zinc selenide (ZnSe) can be used for the first shell
- ZnS can be used for the second shell
- YAG: Ce etc. can also be used as fluorescent substance 3 other than a quantum dot.
- the average particle diameter of the phosphor 3 is preferably 1 to 20 nm.
- the thickness of the phosphor layer 1 is preferably 1 to 500 ⁇ m.
- the content of the phosphor 3 in the phosphor layer 1 is preferably 1 to 20% by mass, and more preferably 3 to 10% by mass based on the total amount of the phosphor layer 1.
- sealing resin 4 for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or the like can be used. These resins can be used singly or in combination of two or more.
- thermoplastic resin examples include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, and vinylidene chloride and copolymers thereof.
- Acetal resins such as polyvinyl formal and polyvinyl butyral; Acrylic resins and copolymers thereof, Acrylic resins such as methacrylic resins and copolymers; Polystyrene resins; Polyamide resins; Linear polyester resins; Fluorine Resin; and polycarbonate resin etc. can be used.
- thermosetting resins examples include phenolic resins, urea melamine resins, polyester resins, and silicone resins.
- the ultraviolet curable resin examples include photopolymerizable prepolymers such as epoxy acrylate, urethane acrylate, and polyester acrylate. Further, these photopolymerizable prepolymers can be the main components, and monofunctional or polyfunctional monomers can be used as diluents.
- the wavelength conversion sheet protective film 2 includes two barrier films 5 each having a base material 8 and a barrier layer 9, an adhesive layer 6, and a coating layer 7.
- the barrier layer 9 provided on the one surface 8 a of the substrate 8 is laminated so as to face the other substrate 8 with the adhesive layer 6 interposed therebetween.
- each protective film 2 and 2 is laminated
- the barrier film 5 has a base material 8 and a barrier layer 9 provided on one surface 8a of the base material 8, as shown in FIG.
- the substrate 8 is not particularly limited, but a substrate having a total light transmittance of 85% or more is desirable.
- a substrate having a total light transmittance of 85% or more is desirable.
- a polyethylene terephthalate film, a polyethylene naphthalate film, or the like can be used as a substrate having high transparency and excellent heat resistance.
- the thickness of the substrate 8 is not particularly limited, but is desirably 50 ⁇ m or less in order to reduce the total thickness of the wavelength conversion sheet 100. Further, the thickness of the substrate 8 is desirably 12 ⁇ m or more in order to obtain excellent barrier properties.
- the barrier layer 9 includes an inorganic thin film layer 10 and a gas barrier coating layer 11. As shown in FIG. 1, the barrier layer 9 has an inorganic thin film layer 10 laminated on one surface (one surface) 8 a of the substrate 8, and a gas barrier coating layer 11 on the inorganic thin film layer 10. Are laminated.
- the inorganic thin film layer (inorganic oxide thin film layer) 10 is not particularly limited.
- aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof can be used. Among these, it is desirable to use aluminum oxide or silicon oxide from the viewpoint of barrier properties and productivity.
- the thickness (film thickness) of the inorganic thin film layer 10 is preferably in the range of 5 to 500 nm, more preferably in the range of 10 to 100 nm.
- the film thickness is 5 nm or more, it is easy to form a uniform film, and the function as a gas barrier material tends to be more sufficiently achieved.
- the film thickness is 500 nm or less, sufficient flexibility can be maintained by the thin film, and it is possible to more reliably prevent the thin film from cracking due to external factors such as bending and pulling after the film formation. There is a tendency to be able to.
- the gas barrier coating layer 11 is provided in order to prevent various secondary damages in a later process and to impart high barrier properties.
- the gas barrier coating layer 11 contains, as a component, at least one selected from the group consisting of a hydroxyl group-containing polymer compound, a metal alkoxide, a metal alkoxide hydrolyzate, and a metal alkoxide polymer from the viewpoint of obtaining excellent barrier properties. It is preferable.
- hydroxyl group-containing polymer compound examples include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and starch, and the barrier property is most excellent particularly when polyvinyl alcohol is used.
- the metal alkoxide is represented by the general formula: M (OR) n (M represents a metal atom such as Si, Ti, Al, Zr, R represents an alkyl group such as —CH 3 , —C 2 H 5 , and n represents M Represents an integer corresponding to the valence of.
- M represents a metal atom such as Si, Ti, Al, Zr
- R represents an alkyl group such as —CH 3 , —C 2 H 5
- n represents M Represents an integer corresponding to the valence of.
- Specific examples include tetraethoxysilane [Si (OC 2 H 5 ) 4 ], triisopropoxyaluminum [Al (O-iso-C 3 H 7 ) 3 ] and the like. Tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.
- hydrolyzate and polymer of metal alkoxide include, for example, silicic acid (Si (OH) 4 ) as a hydrolyzate or polymer of tetraethoxysilane, and a hydrolyzate or polymer of tripropoxyaluminum.
- silicic acid Si (OH) 4
- examples of the hydrolyzate and polymer of metal alkoxide include, for example, silicic acid (Si (OH) 4 ) as a hydrolyzate or polymer of tetraethoxysilane, and a hydrolyzate or polymer of tripropoxyaluminum.
- Al (OH) 3 aluminum hydroxide
- the thickness (film thickness) of the gas barrier coating layer 11 is preferably in the range of 50 to 1000 nm, and more preferably in the range of 100 to 500 nm.
- the film thickness is 50 nm or more, a sufficient gas barrier property tends to be obtained, and when it is 1000 nm or less, a sufficient flexibility tends to be maintained by the thin film.
- the two barrier films 5 are formed so that the barrier layer 9 of the other substrate 8 is interposed via the barrier layer 9 and the adhesive layer 6 provided on one surface 8 a of the substrate 8. It is provided so as to face the surface 8b side that is not provided.
- the first barrier film 5 is used.
- the first base material 8 and the second base material 8 of the second barrier film 5 are laminated via the adhesive layer 6 so as to sandwich the barrier layer 9 of the first barrier film. .
- the first substrate 8 of the first barrier film 5 and the second substrate 8 of the second barrier film 5 are further used. Since the barrier layers 9 are sandwiched between them, and each barrier layer 9 is disposed closer to the phosphor layer 1, defects such as minute pinholes are generated in the barrier layer 9. Even in this case, the barrier performance can be more effectively exhibited.
- the thickness of the two base materials 8 may be the same or different. From the viewpoint of making the thickness of the wavelength conversion sheet 100 thinner, the thickness of the second substrate 8 of the second barrier film 5 disposed on the side closer to the phosphor layer 1 is set to the side far from the phosphor layer 1. You may make it thinner than the 1st base material 8 of the 1st barrier film 5 arrange
- the adhesive layer 6 is provided between the two barrier films 5 in order to bond and laminate the two barrier films 5 together.
- Adhesives and adhesives such as an acryl-type material, a urethane type material, and a polyester-type material, can be used. More specifically, an acrylic pressure-sensitive adhesive, an acrylic adhesive, a urethane adhesive, or an ester adhesive can be used.
- the thickness of the adhesive layer 6 is not particularly limited, but is desirably 10 ⁇ m or less in order to reduce the total thickness of the wavelength conversion sheet protective film 2 and the wavelength conversion sheet 100. On the other hand, from the viewpoint of obtaining better adhesiveness, the thickness of the adhesive layer 6 is desirably 3 ⁇ m or more.
- the coating layer 7 is provided on each surface of the two wavelength conversion sheet protective films 2, 2, that is, both surfaces of the wavelength conversion sheet 100, in order to exhibit one or more optical functions and antistatic functions.
- the optical function is not particularly limited, and examples thereof include an interference fringe (moire) prevention function, an antireflection function, and a diffusion function.
- the coating layer 7 preferably has at least an interference fringe preventing function as an optical function. In the present embodiment, a case where the coating layer 7 has at least an interference fringe preventing function will be described.
- the coating layer 7 may include a binder resin and fine particles. Then, fine irregularities may be formed on the surface of the coating layer 7 by embedding the fine particles in the binder resin so that a part of the fine particles is exposed from the surface of the coating layer 7.
- the binder resin is not particularly limited, but a resin excellent in optical transparency can be used. More specifically, for example, polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, urethane resins, epoxy resins, polycarbonate resins, polyamide resins, polyimide resins.
- Thermoplastic resins such as melamine resins and phenol resins, thermosetting resins, ionizing radiation curable resins, and the like can be used. Among these, it is desirable to use an acrylic resin excellent in light resistance and optical characteristics. These can be used in combination of not only one type but also a plurality of types.
- the fine particles are not particularly limited.
- inorganic fine particles such as silica, clay, talc, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, and alumina
- styrene resin urethane resin
- silicone resin organic fine particles such as acrylic resin can be used. These can be used in combination of not only one type but also a plurality of types.
- the average particle diameter of the fine particles is preferably from 0.1 to 30 ⁇ m, and more preferably from 0.5 to 10 ⁇ m.
- the average particle size of the fine particles is 0.1 ⁇ m or more, an excellent interference fringe prevention function tends to be obtained, and when it is 30 ⁇ m or less, the transparency tends to be further improved.
- the content of fine particles in the coating layer 7 is preferably 0.5 to 30% by mass, more preferably 3 to 10% by mass based on the total amount of the coating layer 7.
- the content of the fine particles is 0.5% by mass or more, the light diffusion function and the effect of preventing the generation of interference fringes tend to be further improved, and when the content is 30% by mass or less, the luminance is not reduced. .
- the wavelength conversion sheet protective film 2 having the above-described configuration is only between the first substrate 8 of the first barrier film 5 and the second substrate 8 of the second barrier film 5. It is a laminate film in which two barrier films 5 are laminated so that the barrier layer 9 is sandwiched between them, and since the influence of the barrier layer 9 due to splash or the like can be suppressed, it has excellent barrier properties. Further, by sandwiching the barrier layer 9 with a base material 8 such as a PET film having excellent thermal stability, more excellent barrier properties can be exhibited. Furthermore, since the coating layer 7 is provided on the surface of the protective film 2 for wavelength conversion sheet, it is possible to suppress the occurrence of interference fringes and to suppress variations in light from the light source.
- this protective film 2 for wavelength conversion sheets as a protective film for protecting the fluorescent substance of the wavelength conversion sheet 100, the performance of the wavelength conversion sheet 100 using fluorescent substances, such as a quantum dot, is exhibited to the maximum. It becomes possible to do.
- the barrier layer 9 toward the phosphor side, it is possible to prevent intrusion of moisture and gas from the end face, and to further prevent deterioration of the phosphor layer 1.
- the coating layer 7 having an optical function on the surface opposite to the side facing the phosphor layer 1 the occurrence of interference fringes such as Newton rings can be prevented, and as a result, high efficiency and A high-definition and long-life display can be obtained.
- the obtained display can display an image having a vivid color closer to nature and an excellent color tone.
- the manufacturing method of the wavelength conversion sheet 100 of this embodiment is demonstrated.
- the fluorescent substance layer 1 can be laminated
- the coating layer 7 is formed on one surface 8 b of the first substrate 8. Specifically, the coating layer 7 is formed by applying a coating liquid in which a binder resin, fine particles, and a solvent as necessary are mixed on the surface 8b of the first base member 8 and drying it. Next, the inorganic thin film layer 10 is laminated
- a coating agent mainly comprising an aqueous solution or a water / alcohol mixed solution containing at least one component selected from the group consisting of a hydroxyl group-containing polymer compound, a metal alkoxide, a metal alkoxide hydrolyzate, and a metal alkoxide polymer.
- the gas barrier coating layer 11 is formed by applying on the surface of the inorganic thin film layer 10 and drying.
- the coating layer 7 is provided on one surface of the first base material 8 and the barrier layer 9 including the inorganic thin film layer 10 and the gas barrier coating layer 11 is provided on the other surface.
- a first barrier film 5 is obtained.
- the second barrier film 5 provided with the barrier layer 9 is obtained by performing the same operation as above except that the coating layer 7 is not formed on the one surface 8a of the second base material 8.
- the first barrier film 5 on which the coating layer 7 is formed and the second barrier film 5 on which the coating layer 7 is not formed are bonded together using the adhesive layer 6 and laminated.
- the barrier layer 9 of the first barrier film 5 provided with the coating layer 7 is opposed to the surface of the second barrier film 5 not provided with the coating layer 7 where the barrier layer 9 is not provided.
- Lamination is performed using the adhesive layer 6.
- the adhesive layer 6 any of an acrylic pressure-sensitive adhesive, an acrylic adhesive, a urethane adhesive, and an ester adhesive can be used.
- the example in which the coating layer 7 is formed first has been described.
- the timing at which the coating layer 7 is formed is not particularly limited, and for example, the first barrier film 5 before the coating layer 7 is formed. And the second barrier film 5 may be bonded together, and the coating layer 7 may be formed on the surface of the first barrier film 5.
- the sealing resin 4 is a photosensitive resin
- the wavelength conversion sheet 100 of the present embodiment can be obtained by curing the photosensitive resin by UV irradiation (UV curing).
- the photosensitive resin may be further thermally cured after UV curing.
- a thermosetting resin, a chemical curable resin, or the like may be used as the sealing resin 4.
- the UV curing can be performed, for example, at 100 to 1000 mJ / cm 2 .
- the thermosetting can be performed at 60 to 120 ° C. for 0.1 to 3 minutes, for example.
- the phosphor layer 1 is formed on the surface of the wavelength conversion sheet protective film 2 on which the coating layer 7 is not provided, and then the other wavelength conversion is performed on the surface of the phosphor layer 1.
- stacks the protective film 2 for sheets was demonstrated, it is not limited to this.
- FIG. 2 is a schematic cross-sectional view of a wavelength conversion sheet according to the second embodiment of the present invention.
- the wavelength conversion sheet 200 of the second embodiment differs from the wavelength conversion sheet 100 of the first embodiment only in the configuration of the wavelength conversion sheet protective film 20. Therefore, about the wavelength conversion sheet 200 of 2nd Embodiment, the same code
- the wavelength conversion sheet 200 of the present embodiment includes a phosphor layer (wavelength conversion layer) 1 containing a phosphor, and one surface 2 a side and the other surface 2 b side of the phosphor layer 1.
- the wavelength conversion sheet protective films 20 and 20 provided are roughly configured.
- the phosphor layer 1 is enclosed (sealed) between the wavelength conversion sheet protective films 20 and 20.
- the protective film 20 for wavelength conversion sheet of this embodiment has two barrier films 5 having a base material 8 and a barrier layer 9, an adhesive layer 6, and a coating layer 7.
- the barrier layer 9 provided on the one surface 8a of the first substrate 8 of the first barrier film 5 and the one surface 8a of the second substrate 8 of the second barrier film 5 are provided.
- the barrier layer 9 is laminated so as to oppose the adhesive layer 6.
- the protective film 20 for wavelength conversion sheet is formed between the barrier films 5 such that the respective barrier layers 9 of the two barrier films 5 are sandwiched between the first substrate 8 and the second substrate 8.
- the protective film 20 for wavelength conversion sheet since the base material 8 is disposed between the barrier layer 9 and the phosphor layer 1 to be protected, there are irregularities and foreign matters on the phosphor layer 1. However, the impact can be alleviated by the base material 8, and the barrier layer 9 can be prevented from being damaged.
- each protective film 20 for wavelength conversion sheets 20 and 20 is the 2nd base material 8 of the 2nd barrier film 5.
- Lamination is performed with the side surface facing the phosphor layer 1 side.
- the wavelength conversion sheet protective films 20 and 20 are provided with the barrier layer 9 of the second base material 8 of the second barrier film 5 having no coating layer 7.
- the surfaces 8 b opposite to the formed surfaces are stacked so as to be sandwiched between the phosphor layers 1. That is, also in this embodiment, the coating layer 7 is provided on each surface of the wavelength conversion sheet protective films 20 and 20 and is provided on both surfaces of the wavelength conversion sheet 200.
- the thickness of the two base materials 8 of the protective film 20 for wavelength conversion sheet may be the same or different. From the viewpoint of making the thickness of the wavelength conversion sheet 200 thinner, the thickness of the second substrate 8 of the second barrier film 5 disposed on the side close to the phosphor layer 1 is set to the side far from the phosphor layer 1. You may make it thinner than the 1st base material 8 of the 1st barrier film 5 arrange
- the permeation of moisture and oxygen occurs not only from the surface of the barrier film 5 but also from the end face, so that the thinner the second substrate 8 can suppress the intrusion of moisture and oxygen from the end face. For this reason, it is desirable that the thickness of the second base material 8 adjacent to the phosphor layer 1 be 40 ⁇ m or less.
- the same effects as those of the wavelength conversion sheet 100 of the first embodiment described above can be obtained.
- a backlight unit for a liquid crystal display can be provided using the wavelength conversion sheet 100 or 200 described above.
- the backlight unit according to the present embodiment includes an LED (light emitting diode) light source, a light guide plate, and a wavelength conversion sheet 100 or 200.
- the LED light source is installed on the side surface of the light guide plate, and the wavelength conversion sheet 100 or 200 is disposed on the light guide plate (light traveling direction).
- the light guide plate efficiently guides light emitted from the LED light source, and a known material is used.
- a known material for example, acrylic, polycarbonate, and cycloolefin film are used.
- the light guide plate can be formed by, for example, a silk printing method, a molding method such as injection molding or extrusion molding, or an ink jet method.
- the thickness of the light guide plate is, for example, 100 to 1000 ⁇ m.
- the configuration of the wavelength conversion sheets 100 and 200 and the configuration of the protective films 2 and 20 for the wavelength conversion sheet of the first and second embodiments described above are examples, and the present invention is not limited thereto.
- the phosphor layer 1 is sandwiched between the same wavelength conversion sheet protective films 2 and 2 (or 20, 20). Or may be sandwiched between protective films for wavelength conversion sheets having different configurations.
- the wavelength conversion sheet of the present invention may have a configuration in which any one of the wavelength conversion sheet protective films covering the phosphor layer 1 has the coating layer 7,
- the structure which has the coating layer 7 may be sufficient as both the protective films for wavelength conversion sheets.
- the wavelength conversion sheet of the present invention in order to improve the adhesion between the protective film for wavelength conversion sheet and the phosphor layer 1 on the surface in contact with the phosphor layer 1 of the protective film for wavelength conversion sheet, A modification treatment may be performed, or an easy adhesion layer made of urethane resin or the like may be provided.
- the barrier layer 9 has the inorganic thin film layer 10 and the gas barrier coating layer 11 one by one. Two or more layers of the thin film layer 10 and the gas barrier coating layer 11 may be provided. In this case, the inorganic thin film layers 10 and the gas barrier coating layers 11 are preferably laminated alternately.
- both end faces of the phosphor layer 1 are sealed. It may be sealed with a resin, and the entire phosphor layer 1 may be covered with a sealing resin.
- the wavelength conversion sheet protective film 300 having the configuration shown in FIG. 3 may be used as the wavelength conversion sheet protective film.
- the protective film 300 for wavelength conversion sheets is demonstrated.
- FIG. 3 is a schematic cross-sectional view of a protective film for a wavelength conversion sheet according to a third embodiment of the present invention.
- the wavelength conversion sheet protective film 300 includes a first barrier film 50, a second barrier film 60, an adhesive layer 30, and a coating layer 31.
- the adhesive layer 30 is located between the first barrier film 50 and the second barrier film 60 and bonds the first barrier film 50 and the second barrier film 60 together.
- the coating layer 31 is provided on the surface of the second barrier film 60 opposite to the surface where the second barrier film 60 is in contact with the adhesive layer 30.
- the coating layer 31 is a layer having one or more optical functions, and can have the same configuration as the coating layer 7 in the wavelength conversion sheets 100 and 200 described above.
- the coating layer 31 preferably has a light diffusion function as an optical function.
- a preferred embodiment of the coating layer 31 (diffusion layer 31) having a light diffusion function will be described in detail below.
- the coating layer 31 has, for example, a concavo-convex shape on the surface thereof to impart light diffusibility. Further, an interference fringe (moire) prevention function and an antireflection function are also provided.
- the uneven shape is formed by, for example, a method of coating an organic layer in which particles or the like are dispersed and a method of further embossing the organic layer after coating.
- fine particles are embedded so that a part of the fine particles is exposed from the surface of the organic layer. Thereby, fine irregularities are generated on the surface of the coating layer 31, and Newton's rings are prevented from occurring in the coating layer 31.
- the organic layer is, for example, a layer containing a polymer resin such as a polyester resin, an acrylic resin, an acrylic urethane resin, a polyester acrylate resin, a polyurethane acrylate resin, an epoxy acrylate resin, and a urethane resin. it can.
- a polymer resin such as a polyester resin, an acrylic resin, an acrylic urethane resin, a polyester acrylate resin, a polyurethane acrylate resin, an epoxy acrylate resin, and a urethane resin. it can.
- the organic layer can be a layer containing a polymer resin such as a thermoplastic resin, a thermosetting resin, or an ultraviolet curable resin.
- a polymer resin such as a thermoplastic resin, a thermosetting resin, or an ultraviolet curable resin.
- thermoplastic resin examples include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like.
- Resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, fluororesins, polycarbonates
- resins examples include resins.
- thermosetting resin examples include phenol resin, urea melamine resin, polyester resin, and silicone resin.
- the ultraviolet curable resin examples include photopolymerizable prepolymers such as epoxy acrylate, urethane acrylate, and polyester acrylate. Further, the ultraviolet curable resin can be constituted by using the above-mentioned photopolymerizable prepolymer as a main component and using a monofunctional or polyfunctional monomer as a diluent.
- the thickness (film thickness) of the organic layer is preferably in the range of 0.1 to 20 ⁇ m, and particularly preferably in the range of 0.3 to 10 ⁇ m.
- the film thickness of the organic layer is less than 0.1 ⁇ m because a uniform film cannot be obtained because the film thickness is too thin or an optical function cannot be sufficiently achieved. Absent.
- the film thickness exceeds 20 ⁇ m, fine particles may not be exposed on the surface of the coating layer 31, and the unevenness imparting effect may not be obtained. This is not preferable because of inconsistency.
- the particles dispersed in the organic layer can be inorganic fine particles such as silica, clay, talc, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, titanium oxide, synthetic zeolite, alumina, smectite, and zirconia.
- the particles dispersed in the organic layer may be, for example, organic fine particles made of styrene resin, urethane resin, benzoguanamine resin, silicone resin, acrylic resin, tetrafluoroethylene resin, polyethylene resin, epoxy resin, or the like. it can. Only one of these may be used, or two or more may be used.
- the average primary particle size of the fine particles is preferably 0.5 to 30 ⁇ m.
- the average primary particle size can be measured by a laser diffraction method. If the average particle size of the fine particles is less than 0.5 ⁇ m, the effect of imparting irregularities to the surface of the coating layer 31 cannot be obtained, which is not preferable. On the other hand, when the average particle size exceeds 30 ⁇ m, particles considerably larger than the organic layer thickness are used, which is not preferable because there is a problem that the light transmittance is lowered. On the other hand, when the average particle size is within the above range, the surface can be provided with an uneven shape while maintaining a high light transmittance.
- the adhesive layer 30 can have the same configuration as the adhesive layer 6 in the wavelength conversion sheets 100 and 200 described above.
- the first barrier film 50 includes a base material 51, an adhesion layer 52, a first silica vapor deposition layer 53 that is an inorganic thin film layer, a first gas barrier coating layer (first composite coating layer) 54, and a second silica that is an inorganic thin film layer.
- a vapor deposition layer 55 and a second gas barrier coating layer (second composite coating layer) 56 are provided.
- an adhesion layer 52, a first silica vapor deposition layer 53, a first gas barrier coating layer 54, a second silica vapor deposition layer 55, and a second gas barrier coating layer 56 are provided in this order.
- a barrier layer is formed by the first silica deposited layer 53, the first gas barrier coating layer 54, the second silica deposited layer 55, and the second gas barrier coating layer 56.
- the second gas barrier coating layer 56 adheres to the adhesive layer 30.
- the second barrier film 60 includes a substrate 61, an adhesion layer 62, a first silica vapor deposition layer 63, a first gas barrier coating layer 64, a second silica vapor deposition layer 65, and a second gas barrier coating layer 66.
- an adhesion layer 62, a first silica vapor deposition layer 63, a first gas barrier coating layer 64, a second silica vapor deposition layer 65, and a second gas barrier coating layer 66 are provided in this order.
- a barrier layer is formed by the first silica vapor deposition layer 63, the first gas barrier coating layer 64, the second silica vapor deposition layer 65, and the second gas barrier coating layer 66.
- the second gas barrier coating layer 66 adheres to the adhesive layer 30.
- the base materials 51 and 61 can have the same configuration as the base material 8 in the wavelength conversion sheets 100 and 200 described above. Moreover, as the base materials 51 and 61, it is preferable to use a polyester film. Although it does not specifically limit as a polyester film, For example, it consists of a polyester film, such as a polyethylene terephthalate (PET) and a polyethylene naphthalate (PEN), polyethylene, a polypropylene, a cyclic olefin copolymer (COC), a cycloolefin polymer (COP), etc.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- COC cyclic olefin copolymer
- COP cycloolefin polymer
- the substrates 51 and 61 are particularly preferably biaxially stretched polyester films arbitrarily stretched in the biaxial direction.
- a biaxially stretched polyester film is excellent in dimensional stability, heat resistance, and transparency.
- the thickness of the substrates 51 and 61 is not particularly limited, but is preferably in the range of 3 ⁇ m to 200 ⁇ m, and more preferably in the range of 6 ⁇ m to 50 ⁇ m.
- the thicknesses of the base materials 51 and 61 are the adhesion layers 52 and 62, the first silica vapor deposition layers 53 and 63, the first gas barrier coating layers 54 and 64, the second silica vapor deposition layers 55 and 65, and the second gas barrier coating. This is a value considering workability when the layers 56 and 66 are laminated.
- plasma treatment, corona discharge treatment, ozone treatment, glow discharge treatment, and other pretreatments are optionally performed in order to improve the adhesion of each layer.
- the base materials 51 and 61 it is particularly preferable to use a polyethylene terephthalate film having an acid value (mg number of potassium hydroxide necessary for neutralizing 1 g of resin) of 25 mgKOH / g or less.
- an acid value molecular weight of the base materials 51 and 61
- the acid value of the base materials 51 and 61 exceeds 25 mgKOH / g
- the base material stability is deteriorated particularly in a high-temperature and high-humidity environment, and the barrier property is lowered.
- the acid value is 25 mgKOH / g or less, the substrate stability is increased, and the barrier property is not lowered even in a high-temperature and high-humidity environment, which is preferable.
- the cut base materials 51 and 61 are weighed and, for example, heated and dissolved in cresol, cooled, and then titrated with a potassium hydroxide ethanol solution or the like to determine the acid value.
- a potassium hydroxide ethanol solution for example, a phenolphthalein solution can be used as the indicator (see JIS K0070).
- the barrier properties of the base materials 51 and 61 are stably expressed in an accelerated deterioration test of a display function under a severe environment such as 60 ° C./90% RH and 85 ° C./85% RH. Therefore, it is preferable that the hydrolysis resistance is excellent.
- the PET film as the base material 51 or 61 preferably has a weight average molecular weight of 60,000 or more. When the PET film has a weight average molecular weight of less than 60,000, it usually tends to cause hydrolysis, so that the barrier property of the PET film tends to deteriorate.
- the concentration of the terminal carboxy group is reduced to 25 equivalents / 10 6 g or less.
- concentration of the terminal carboxy group in polyester can be measured by the method described in literature (ANALYTICAL CHEMISTRY 26th volume, 1614 pages).
- the weight average molecular weight is measured by a method such as room temperature GPC analysis.
- the PET film is preferably a film excellent in light transmittance and smoothness. For this reason, in order to improve the light transmittance of the PET film, it is desirable to reduce the lubricant used in the PET film. In addition, when the first silica vapor deposition layer is laminated on the PET film, the first silica vapor deposition layer is not cracked, and the first silica vapor deposition layer is a uniform thin film.
- the center line surface roughness (Ra) of the PET film is desirably 30 nm or less. If the center line surface roughness (Ra) is 30 nm or less, it can be said that the PET film has excellent smoothness.
- the surface roughness of the PET film can be measured by a method according to JIS B0601.
- the adhesion layers 52 and 62 are provided on the base materials 51 and 61.
- the adhesion layers 52 and 62 are appropriately provided to obtain adhesion with the first silica vapor deposition layer.
- the adhesion layers 52 and 62 are either one of an in-line method applied when the substrates 51 and 61 are stretched and an offline method applied offline after the substrates 51 and 61 are formed, or It can be formed by both an inline method and an offline method.
- the adhesion layers 52 and 62 are not particularly limited, but the composition for the adhesion layer for forming the adhesion layers 52 and 62 by the in-line method can be, for example, an acrylic material or a urethane material.
- the composition for the adhesion layer for forming the adhesion layers 52 and 62 by off-line can be, for example, a two-component reaction composite of a compound having a hydroxyl group such as acrylic polyol and an isocyanate compound having an isocyanate group.
- the adhesion layers 52 and 62 may be provided on both sides as well as on one side.
- the first silica vapor-deposited layers 53 and 63 and the second silica vapor-deposited layers 55 and 65 are layers that exhibit barrier properties, and are inorganic in the wavelength conversion sheets 100 and 200 described above. It corresponds to the thin film layer 10.
- Examples of the inorganic compound exhibiting barrier properties as the vapor deposition layer include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, zinc oxide, or a mixture thereof.
- the silica vapor deposition layer containing silicon oxide is used. Selected.
- the silica vapor deposition layer has moisture resistance in an accelerated deterioration test of a display function under a severe environment such as 60 ° C./90% RH and 85 ° C./85% RH.
- a silica vapor deposition layer is produced by methods, such as a vacuum evaporation method, sputtering method, an ion plating method, plasma vapor deposition method (CVD), for example.
- the O / Si ratio of oxygen and silicon constituting the silica vapor deposition layer is preferably 1.7 or more and 2.0 or less in terms of atomic ratio. If the O / Si ratio is less than 1.7 in terms of atomic ratio, the ratio of Si—Si bonds in the silica vapor deposition layer increases and a large amount of colored metal is contained, so that the transmittance of the silica vapor deposition layer may decrease. . On the other hand, when the O / Si ratio exceeds 2.0 in terms of atomic ratio, the barrier property of the silica deposited layer may be deteriorated.
- the O / Si ratio of the silica deposited layer suitable for display applications is more preferably 1.85 to 2.0 in terms of atomic ratio.
- the O / Si ratio of the silica vapor deposition layer is measured by, for example, X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the XPS measuring device can be, for example, an X-ray photoelectron spectrometer (JPS-90MXV manufactured by JEOL Ltd.).
- Non-monochromated MgK ⁇ (1253.6 eV) is used for the X-ray source, and the X-ray output value can be, for example, 100 W (10 kV-10 mA).
- a relative sensitivity factor of 2.28 is used for the 1s orbit of O
- a relative sensitivity factor of 0.9 is used for the 2p orbit of Si.
- the refractive index of the organic layer constituting the wavelength conversion sheet protective film 300 is preferably 1.5 to 1. .7.
- the refractive index of a silica vapor deposition layer is 1.5 or more and 1.7 or less.
- the refractive index of the silica vapor deposition layer is more preferably 1.6 to 1.65 from the viewpoint of transparency for display applications in addition to barrier properties.
- silica vapor deposition films having different refractive indexes are formed on the PET film by physical vapor deposition (PVD).
- the refractive index of the silica vapor deposition layer is calculated from the thickness of the silica vapor deposition layer and the transmittance curve generated by light interference.
- the thickness of the silica vapor deposition layer is preferably in the range of 5 nm to 300 nm.
- the thickness of the silica vapor deposition layer is less than 5 nm, it is difficult to obtain a uniform film and it is difficult to sufficiently perform the function as a gas barrier material.
- the thickness of the silica vapor deposition layer exceeds 300 nm, it is difficult to maintain the flexibility of the silica vapor deposition layer, and after the vapor deposition film is formed, the vapor deposition film is likely to crack due to external factors such as bending and pulling. .
- the thickness of the silica vapor deposition layer is more preferably in the range of 10 to 50 nm in consideration of productivity by in-line film formation.
- any of vacuum vapor deposition, sputtering, ion plating, plasma vapor deposition (CVD), and the like may be used.
- a heating means necessary for the vacuum deposition method any one of an electron beam heating method, a resistance heating method, and an induction heating method can be used.
- a reactive vapor deposition method in which various gases such as oxygen are blown may be used.
- the first gas barrier coating layers 54 and 64 and the second gas barrier coating layers 56 and 66 are coating layers having gas barrier properties, and the wavelength conversion sheet 100 described above. , 200 can be configured in the same manner as the gas barrier coating layer 11.
- the gas barrier coating layer can be formed using a coating agent.
- the coating agent is mainly composed of, for example, an aqueous solution containing at least one selected from the group consisting of water-soluble polymers, metal alkoxides, metal alkoxide hydrolysates, and silane coupling agents, or water / alcohol mixed solutions. .
- the coating agent is produced, for example, by directly mixing a metal alkoxide, a hydrolyzate of metal alkoxide, and a silane coupling agent into an aqueous solution of a water-soluble polymer or a water / alcohol mixed solution.
- the coating agent is prepared, for example, by mixing an aqueous solution of a water-soluble polymer or a water / alcohol mixed solution with a metal alkoxide and a silane coupling agent that have been subjected to a treatment such as hydrolysis in advance.
- the coating agent solution is coated on the adhesion layers 52 and 62 and then dried by heating to form a gas barrier coating layer.
- the coating agent solution forms a gas barrier coating layer by coating and heating and drying on the silica vapor deposition layer.
- water-soluble polymer used in the coating agent examples include a hydroxyl group-containing polymer compound.
- the hydroxyl group-containing polymer compound can be, for example, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, and the like.
- PVA polyvinyl alcohol
- starch methyl cellulose, carboxymethyl cellulose, sodium alginate, and the like.
- methyl cellulose carboxymethyl cellulose
- sodium alginate sodium alginate
- a gas barrier coating layer made of PVA is excellent in gas barrier properties.
- the metal alkoxide is a general formula, M (OR) n (M: metal such as Si, Ti, Al, Zr, etc., alkyl group such as R: CH 3 , C 2 H 5, etc., n: number corresponding to the valence of M. ).
- M metal such as Si, Ti, Al, Zr, etc.
- alkyl group such as R: CH 3 , C 2 H 5, etc.
- n number corresponding to the valence of M.
- Specific examples of the metal alkoxide include tetraethoxysilane [Si (OC 2 H 5 ) 4 ] and triisopropoxy aluminum [Al (O-2′-C 3 H 7 ) 3 ].
- tetraethoxysilane and triisopropoxyaluminum are particularly preferable. Tetraethoxysilane and triisopropoxyaluminum are relatively stable in aqueous solvents after hydrolysis.
- the silane coupling agent has a general formula, R 1 m Si (OR 2 ) 4-m (R 1 : an organic functional group, R 2 : an alkyl group such as CH 3 or C 2 H 5 , m: an integer of 1 to 3 ).
- Specific examples of the silane coupling agent include ethyltrimethoxysilane, vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, and ⁇ -methacrylic acid.
- Silane coupling agents such as loxypropyltrimethoxysilane and ⁇ -methacryloxypropylmethyldimethoxysilane can be used.
- known additives such as isocyanate compounds or dispersants, stabilizers, viscosity modifiers, and colorants are added as necessary within a range not impairing the gas barrier properties. It is also possible.
- the thickness of the gas barrier coating layer after drying is preferably 0.01 to 50 ⁇ m, more preferably 0.1 to 10 ⁇ m.
- the thickness of the gas barrier coating layer after drying is less than 0.01 ⁇ m, a uniform coating film cannot be obtained, so that sufficient gas barrier properties may not be obtained.
- the thickness of the gas barrier coating layer after drying exceeds 50 ⁇ m, cracks are likely to occur in the gas barrier coating layer.
- the wavelength conversion sheet protective film 300 in FIG. 3 has a reflectance of 10% or more and 20% or less at a wavelength of 450 nm in the blue region, a wavelength of 540 nm in the green region, and a wavelength of 620 nm in the red region. Is desirable.
- the reflectance correlates with optical interference caused by the first and second barrier films 50 and 60. If the reflectance exceeds 20% at each wavelength, even when the wavelength conversion sheet protective film 300 is used as a diffusion sheet on the light guide plate in the backlight unit, color unevenness due to optical interference appears greatly, resulting in poor appearance. May occur.
- the reflectance is less than 10% at each wavelength, the O / Si ratio and the refractive index of the silica deposited layers in the first and second barrier films 50 and 60 are likely to deviate from the above-described preferable value range. There is a possibility that the barrier properties of the second barrier films 50 and 60 are not sufficiently developed.
- the transmittance of the wavelength conversion sheet protective film 300 is preferably 80% or more and 95% or less for each of the blue 450 nm wavelength, the green 540 nm wavelength, and the red 620 nm wavelength.
- a transmittance of less than 80% is not preferable because the transmittance is low and the light conversion efficiency of the phosphor layer (quantum dot layer) may be lowered.
- the wavelength conversion sheet protective film 300 described above can be manufactured by the same method as the wavelength conversion sheet protective films 2 and 20 except that the configuration of each layer is the above configuration.
- the wavelength conversion sheet protective film 300 described above is used in place of the wavelength conversion sheet protection films 2 and 20, thereby providing two wavelength conversion sheets.
- a wavelength conversion sheet having a structure in which the phosphor layer 1 is encapsulated (sealed) between the protective films 300 and 300 can be obtained.
- each layer which comprises the protective film 2 for wavelength conversion sheets 2 and 20 of the wavelength conversion sheet 100, 200 shown in FIG.1 and FIG.2 is changed into the structure of each layer demonstrated in the protective film 300 for wavelength conversion sheets mentioned above. May be.
- the inorganic thin film layer 10 is a silica vapor deposition layer, and the oxygen / silicon O / Si ratio contained in the silica vapor deposition layer is 1.7 to 2.0 in atomic ratio.
- the refractive index of the silica vapor deposition layer is 1.5 or more and 1.7 or less, and the reflectivity of the wavelength conversion sheet protective film 2 or 20 is 10% or more at all wavelengths of 450 nm, 540 nm, and 620 nm.
- the transmittance may be 20% or less and 80% or more and 95% or less.
- Example 1 Preparation of protective film for wavelength conversion sheet
- silicon oxide is provided as an inorganic thin film layer (silica vapor deposition layer) to a thickness of 250 mm by vacuum vapor deposition, and a coating liquid containing tetraethoxysilane and polyvinyl alcohol is further provided.
- Coating was performed on the inorganic thin film layer by a wet coating method to form a gas barrier coating layer having a thickness of 0.3 ⁇ m.
- a coating liquid containing an acrylic resin and silica fine particles (average particle size 3 ⁇ m) is applied to the surface side (base material side) opposite to the gas barrier coating layer of one barrier film by a wet coating method.
- a coating layer having a thickness of 5 ⁇ m was formed. This obtained the barrier film with a coating layer.
- Example 1 affix the gas barrier coating layer side of the barrier film with the coating layer and the side opposite to the gas barrier coating layer (base material side) of the barrier film without the coating layer using an acrylic resin adhesive.
- the protective film for wavelength conversion sheets of Example 1 was obtained. Two protective films for wavelength conversion sheets were produced.
- the backlight unit of Example 1 was produced by combining the obtained wavelength conversion sheet with an LED light source and a light guide plate.
- Example 2 (Preparation of protective film for wavelength conversion sheet)
- Example 1 the same except that the gas barrier coating layer side of the barrier film with the coating layer and the gas barrier coating layer side of the barrier film without the coating layer were bonded together using an acrylic resin adhesive
- the protective film for wavelength conversion sheets of Example 2 was obtained by the operation. Two protective films for wavelength conversion sheets were produced.
- a backlight unit of Example 2 was produced by combining the obtained wavelength conversion sheet with an LED light source and a light guide plate.
- Example 3 In Example 1, the protective film for wavelength conversion sheets of Example 3 was obtained by the same operation except not providing a coating layer. Furthermore, the wavelength conversion sheet and backlight unit of Example 3 were obtained in the same manner as in Example 1 except that this wavelength conversion sheet protective film was used.
- Example 1 the protective film for wavelength conversion sheets of the comparative example 1 was obtained in the same manner except having used the 25-micrometer-thick polyethylene terephthalate film instead of the barrier film with a coating layer. Furthermore, the wavelength conversion sheet and the backlight unit of Comparative Example 1 were obtained in the same manner as in Example 1 except that this wavelength conversion sheet protective film was used.
- Example 2 In Example 1, a protective film for wavelength conversion sheet of Comparative Example 2 was obtained in the same manner except that a polyethylene terephthalate film having a thickness of 25 ⁇ m was used instead of the barrier film having no coating layer. Further, a wavelength conversion sheet and a backlight unit of Comparative Example 2 were obtained in the same manner as in Example 1 except that this wavelength conversion sheet protective film was used.
- Example 3 a wavelength conversion sheet protective film of Comparative Example 3 was obtained in the same manner except that a polyethylene terephthalate film having a thickness of 12 ⁇ m was used instead of the barrier film with a coating layer. Further, a wavelength conversion sheet and a backlight unit of Comparative Example 3 were obtained in the same manner as in Example 2 except that this wavelength conversion sheet protective film was used.
- silicon oxide is provided as a first inorganic thin film layer (silica vapor deposition layer) to a thickness of 250 mm by vacuum vapor deposition, and further contains tetraethoxysilane and polyvinyl alcohol.
- the coating liquid was applied onto the first inorganic thin film layer by a wet coating method to form a first gas barrier coating layer having a thickness of 0.3 ⁇ m.
- silicon oxide is provided as a second inorganic thin film layer (silica vapor deposition layer) to a thickness of 250 mm by vacuum vapor deposition, and further a coating liquid containing tetraethoxysilane and polyvinyl alcohol.
- the protective film for a wavelength conversion sheet of Comparative Example 4 was obtained by bonding the gas barrier coating layer side of the barrier film and a polyethylene terephthalate film having a thickness of 25 ⁇ m using an acrylic resin adhesive. Two protective films for wavelength conversion sheets were produced. A wavelength conversion sheet and a backlight unit of Comparative Example 4 were obtained in the same manner as in Example 2 except that this wavelength conversion sheet protective film was used.
- the wavelength conversion sheets of Comparative Examples 1 to 3 have a structure in which one barrier film and a polyester film are bonded together, the luminance is lowered because the barrier property is inferior particularly after the reliability test. In addition, not only the overall luminance was reduced but also a local luminance reduction was observed.
- Example 4 (Preparation of protective film for wavelength conversion sheet)
- the adhesive layer composition was applied to one side of a 16 ⁇ m thick PET film substrate formed using PET having a weight average molecular weight of 60,000, and an adhesive layer having a thickness of 0.1 ⁇ m was laminated.
- the 1st silica vapor deposition layer was laminated
- a first gas barrier coating layer (first composite coating layer) having a thickness of 1 ⁇ m was formed on the first silica vapor deposition layer by a wet coating method using the gas barrier coating layer composition.
- a second silica vapor deposition layer was laminated on the first gas barrier coating layer so as to have a thickness of 30 nm.
- a second gas barrier coating layer (second composite coating layer) having a thickness of 1 ⁇ m is formed on the second silica deposited layer by a wet coating method using the gas barrier coating layer composition, and the first barrier is formed.
- a film was prepared.
- the O / Si ratio in the first silica vapor deposition layer and the second silica vapor deposition layer was 1.8 in terms of atomic ratio, and the refractive index was 1.61.
- the 2nd barrier film was produced by the method similar to a 1st barrier film.
- the composition for the adhesion layer was an ethyl acetate solution of acrylic polyol and tolylene diisocyanate.
- the OH group of the acrylic polyol and the NCO group of tolylene diisocyanate were made equal to each other.
- the solid content concentration of the acrylic polyol and tolylene diisocyanate in the ethyl acetate solution was 5% by mass.
- the gas barrier coating composition In the preparation of the gas barrier coating composition, 10.4 g of tetraethoxysilane was added to 89.6 g of 0.1N (normal concentration) hydrochloric acid, and this hydrochloric acid solution was stirred for 30 minutes to hydrolyze tetraethoxysilane. did. The concentration of solid content after hydrolysis was 3% by mass in terms of SiO 2 .
- a composition for gas barrier coating layer was prepared by mixing a hydrolyzed solution of tetraethoxysilane and a 3% by mass aqueous solution of polyvinyl alcohol. The mixing ratio of the tetraethoxysilane hydrolyzed solution and polyvinyl alcohol was 50:50 in terms of mass%.
- suitable vapor deposition conditions were determined by changing the vapor deposition conditions such as the type of material to be vapor deposited before the formation.
- the O / Si ratio of the silica deposited layer was examined using an X-ray photoelectron spectroscopic analyzer (manufactured by JEOL Ltd., JPS-90MXV).
- X-ray photoelectron spectroscopic analyzer manufactured by JEOL Ltd., JPS-90MXV.
- the X-ray source non-monochromated MgK ⁇ (1253.6 eV) was used, and measurement was performed at an X-ray output of 100 W (10 kV-10 mA).
- Quantitative analysis for obtaining the O / Si ratio of the silica deposited layer was performed using relative sensitivity factors of 2.28 for O1s and 0.9 for Si2p, respectively.
- the refractive index of the silica vapor deposition layer was calculated by simulation using the thickness of the silica vapor deposition layer and the peak wavelength of the transmittance curve generated by light interference.
- the adhesive layer was made of a two-component curable urethane adhesive.
- the thickness of the adhesive layer after bonding was 5 ⁇ m.
- a coating layer in which olefinic particles having a particle diameter of 2 ⁇ m were dispersed in a urethane binder was applied so that the thickness thereof was 3 ⁇ m.
- a protective film for a first wavelength conversion sheet having a haze value of 60% (JIS K7136) was obtained.
- the protective film for 2nd wavelength conversion sheets was produced by the method similar to the protective film for 1st wavelength conversion sheets.
- a phosphor having a core-shell structure of CdSe / ZnS was obtained by the following method. First, a solution in which octylamine and cadmium acetate are added to octadecene and a solution in which selenium is dissolved in trioctylphosphine are mixed at a mass ratio of 1: 1, and the mixture is passed through a heated microchannel to form nuclear fine particles. As a result, a CdSe fine particle solution was obtained.
- a CdSe fine particle solution and a solution in which [(CH 3 ) 2 NCSS] 2 Zn is dissolved in trioctylphosphine are mixed at a mass ratio of 1: 1 and passed through a heated microchannel.
- a phosphor having a CdSe / ZnS structure was obtained.
- the obtained phosphor was mixed with a photosensitive resin (epoxy resin) to obtain a quantum dot layer mixture.
- the quantum dot layer mixture is applied on the base material of the first barrier film of the first wavelength conversion sheet protective film (on the surface opposite to the coating layer), and the second wavelength conversion sheet protective film is formed thereon.
- the mixture for quantum dot layers was irradiated with UV, and the photosensitive resin contained in the mixture for quantum dot layers was cured. This produced the wavelength conversion sheet
- the backlight unit of Example 4 was produced by combining the obtained wavelength conversion sheet with an LED light source and a light guide plate.
- Example 5 The adhesive layer composition was applied to one side of a 16 ⁇ m thick PET film substrate formed using PET having a weight average molecular weight of 60,000, and an adhesive layer having a thickness of 0.1 ⁇ m was laminated. Next, the 1st silica vapor deposition layer was laminated
- first composite coating layer having a thickness of 1 ⁇ m
- the O / Si ratio in the first silica vapor deposition layer was 1.8 in terms of atomic ratio, and the refractive index was 1.61.
- the 2nd barrier film was produced by the method similar to a 1st barrier film.
- Each layer in the first and second barrier films was formed in the same manner as in Example 4.
- Each of the first and second barrier films of Example 5 has a structure including a silica vapor deposition layer and a gas barrier coating layer, that is, from the first and second barrier films of Example 4, to the second silica vapor deposition layer. And it has the structure except the 2nd gas barrier coating layer.
- a protective film for first and second wavelength conversion sheets having a haze value of 60% (JIS K7136) was obtained in the same manner as in Example 4 except that the first and second barrier films produced by the above method were used. Furthermore, a wavelength conversion sheet and a backlight unit using the same were obtained in the same manner as in Example 4 except that the protective films for the first and second wavelength conversion sheets were used.
- Example 6 By changing the O / Si ratio of the SiO vapor deposition material and adjusting the conditions of physical vapor deposition, the O / Si ratio of the silica vapor deposition layer is 1.7 in atomic ratio and the refractive index is 1.55. Two silica deposited layers were prepared. A protective film for wavelength conversion sheet, a wavelength conversion sheet, and a backlight unit were obtained in the same manner as in Example 4 except for the values of the O / Si ratio and the refractive index of the silica deposited layer.
- Table 2 is a table showing the evaluation results of the reflectance and transmittance of the protective films for wavelength conversion sheets produced in Examples 4 to 6.
- Table 3 is a table showing the water vapor transmission rate of the protective films for wavelength conversion sheets produced in Examples 4 to 6, and the evaluation results of the luminance and appearance of the backlight unit.
- the reflectance and transmittance of the protective film for wavelength conversion sheet were measured at wavelengths of 450 nm, 540 nm, and 620 nm using a spectrophotometer (trade name: SHIMAZU UV-2450). In the measurement, measurement light was irradiated from the surface opposite to the coating layer of the protective film for wavelength conversion sheet.
- the water vapor transmission rate (g / m 2 ⁇ day) of the protective film for wavelength conversion sheet was measured in a 40 ° C./90% RH atmosphere using a water vapor transmission measuring device (Permatran 3/33 manufactured by Modern Control).
- the measurement of the luminance of the backlight unit and the evaluation of the appearance were performed before and after a 1,000 hour storage experiment in an atmosphere of 60 ° C./90% RH.
- “initial” indicates before the storage experiment, and “after storage” indicates after the storage experiment.
- the luminance of the backlight unit was measured using a luminance meter (LS-100 manufactured by Konica Minolta).
- the appearance of the backlight unit is evaluated as “A” when it has an appearance that can withstand the display application as the backlight unit. When there was a reproduction failure, it was evaluated as “B”.
- the appearance evaluation 2 of the backlight unit was performed by the following method. That is, the appearance of the backlight unit was visually confirmed in the LED emission state, and the presence / absence of foreign matters (splash, scratches, wrinkles, etc.) and the occurrence of interference fringes were evaluated. The case where foreign matter and interference fringes were not confirmed was judged as “A”, and the case where foreign matter and interference fringes were confirmed was judged as “B”. This appearance evaluation was performed both at the initial stage and after storage for 500 hours in an environment of 60 ° C. and 90% RH.
- the protective film for wavelength conversion sheets which is the laminate film which laminated
- the backlight unit By using the backlight unit, it is possible to manufacture an excellent high-definition display.
- SYMBOLS 1 Phosphor layer, 2, 20, 300 ... Protective film for wavelength conversion sheet, 3 ... Phosphor, 4 ... Sealing resin, 5 ... Barrier film, 6 ... Adhesive layer, 7 ... Coating layer, 8 ... Base material, DESCRIPTION OF SYMBOLS 9 ... Barrier layer, 10 ... Inorganic thin film layer, 11 ... Gas barrier coating layer, 31 ... Coating layer, 50 ... 1st barrier film, 51 ... Base material, 52 ... Adhesion layer, 53 ... 1st silica vapor deposition layer, 54 ... First gas barrier coating layer, 55 ... second silica vapor deposition layer, 56 ... second gas barrier coating layer, 60 ...
- second barrier film 61 ... base material, 62 ... adhesion layer, 63 ... first silica vapor deposition layer, 64 ... 1st gas barrier coating layer, 65 ... 2nd silica vapor deposition layer, 66 ... 2nd gas barrier coating layer, 100,200 ... wavelength conversion sheet.
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Abstract
Description
先ず、本発明の第1実施形態について説明する。図1は、本発明の第1実施形態に係る波長変換シートの模式断面図である。図1に示した波長変換シートは、量子ドット等の蛍光体を含んでおり、例えばLED波長変換用として、バックライトユニットに用いることができるものである。
蛍光体層1は、封止樹脂4及び蛍光体3を含む数十~数百μmの厚みの薄膜である。封止樹脂4としては、例えば、感光性樹脂又は熱硬化性樹脂を使用することができる。封止樹脂4の内部には、蛍光体3が1種以上混合された状態で封止されている。封止樹脂4は、蛍光体層1と一対の保護フィルム2,2とを積層する際に、これらを接合するとともに、これらの空隙を埋める役割を果たす。また、蛍光体層1は、1種類の蛍光体3のみが封止された蛍光体層が2層以上積層されたものであってもよい。それら1層又は2層以上の蛍光体層に用いられる2種類以上の蛍光体3は、励起波長が同一のものが選択される。この励起波長は、LED光源が照射する光の波長に基づいて選択される。2種類以上の蛍光体3の蛍光色は相互に異なる。使用する蛍光体3が2種類の場合、各蛍光色は、好ましくは、赤色、緑色である。各蛍光の波長、及びLED光源が照射する光の波長は、カラーフィルタの分光特性に基づき選択される。蛍光のピーク波長は、例えば赤色が610nm、緑色が550nmである。
波長変換シート用保護フィルム2は、基材8とバリア層9とを有するバリアフィルム5を2枚と、接着層6と、コーティング層7とを有している。そして、基材8の一方の面8a上に設けられたバリア層9が接着層6を介してもう一方の基材8に対向するように積層されている。また、本実施形態の保護フィルム2を形成する際には、図1に示すように、それぞれの保護フィルム2,2は、バリア層9を蛍光体層1側に向けて積層する。
波長変換シート用保護フィルム2,2の製造工程では、先ず、第1の基材8の片方の面8bに、コーティング層7を形成する。具体的には、第1の基材8片方の面8b上に、バインダー樹脂と微粒子と必要に応じて溶剤とを混合したコーティング液を塗布し、乾燥することで、コーティング層7を形成する。次に、第1の基材8の、コーティング層7が設けられた面とは反対側の面8a上に、無機薄膜層10を例えば蒸着法等によって積層する。次いで、水酸基含有高分子化合物、金属アルコキシド、金属アルコキシド加水分解物及び金属アルコキシド重合物からなる群より選択される少なくとも1種の成分等を含む水溶液あるいは水/アルコール混合溶液を主剤とするコーティング剤を無機薄膜層10の表面上に塗布し、乾燥することで、ガスバリア性被覆層11を形成する。これにより、第1の基材8の一方の面上にコーティング層7が、他方の面に無機薄膜層10及びガスバリア性被覆層11からなるバリア層9がそれぞれ設けられた、コーティング層7付きの第1のバリアフィルム5が得られる。
蛍光体層1の製造工程では、先ず、蛍光体3と封止樹脂4と必要に応じて溶剤とを混合して混合液を調製する。次いで、調製した混合液を、波長変換シート用保護フィルム2のコーティング層7が設けられていない側の表面に塗布する。次に、別に作製した他方の波長変換シート用保護フィルム2を積層する。この際、蛍光体層1の表面1a,1bと、2枚の波長変換シート用保護フィルム2のコーティング層7が設けられていない側の表面とがそれぞれ対向するように配置する。次いで、封止樹脂4が感光性樹脂である場合、紫外線の照射によって感光性樹脂を硬化(UV硬化)させることで、本実施形態の波長変換シート100を得ることができる。なお、感光性樹脂は、UV硬化の後に更に熱硬化させてもよい。また、封止樹脂4としては、感光性樹脂以外にも、熱硬化性樹脂や化学硬化性樹脂等を用いてもよい。
次に、本発明の第2実施形態について説明する。図2は、本発明の第2実施形態に係る波長変換シートの模式断面図である。第2実施形態の波長変換シート200は、第1実施形態の波長変換シート100とは、波長変換シート用保護フィルム20の構成のみが異なっている。したがって、第2実施形態の波長変換シート200については、第1実施形態と同一の構成部分については同じ符号を付すると共に説明を省略する。
本実施形態の波長変換シート用保護フィルム20は、基材8とバリア層9とを有するバリアフィルム5を2枚と、接着層6と、コーティング層7とを有している。そして、2枚のバリアフィルム5は、蛍光体層1から遠い方を第1のバリアフィルム5、蛍光体層1に近い方を第2のバリアフィルム5とした場合、図2に示すように、第1のバリアフィルム5の第1の基材8の一方の面8a上に設けられたバリア層9と、第2のバリアフィルム5の第2の基材8の一方の面8a上に設けられたバリア層9とが、接着層6を介して対向するように積層されている。換言すると、波長変換シート用保護フィルム20は、第1の基材8と第2の基材8との間に、2つのバリアフィルム5のそれぞれのバリア層9を挟み込むように、バリアフィルム5同士が積層された構造を有している。この波長変換シート用保護フィルム20の構成によれば、バリア層9と保護する蛍光体層1の間に基材8が配置されているため、蛍光体層1上に凹凸や異物が存在する場合でも、基材8によって衝撃が緩和され、バリア層9が損傷することを抑制することができる。
上述した波長変換シート100又は200を用いて、液晶ディスプレイ用のバックライトユニットを提供することができる。本実施形態に係るバックライトユニットは、LED(発光ダイオード)光源と、導光板と、波長変換シート100又は200とを備える。LED光源は、導光板の側面に設置され、導光板上(光の進行方向)に波長変換シート100又は200が配置される。
図1及び図2に示した波長変換シート100,200において、波長変換シート用保護フィルムとして、図3に示す構成を有する波長変換シート用保護フィルム300を用いてもよい。以下、波長変換シート用保護フィルム300について説明する。
(波長変換シート用保護フィルムの作製)
基材としての厚み25μmのポリエチレンテレフタレートフィルムの片面に、無機薄膜層(シリカ蒸着層)として酸化珪素を真空蒸着法により250Åの厚みに設け、さらに、テトラエトキシシランとポリビニルアルコールとを含む塗液をウエットコーティング法により無機薄膜層上に塗工し、0.3μmの厚みのガスバリア性被覆層を形成した。これにより、基材の一方の面上に無機薄膜層及びガスバリア性被覆層からなるバリア層が設けられたバリアフィルムを得た。このバリアフィルムを2枚作製した。
量子ドットとしてのCdSe/ZnS 530(商品名、SIGMA-ALDRICH社製)をエポキシ系感光性樹脂と混合後、混合液を上述した波長変換シート用保護フィルムのガスバリア性被覆層側に塗布し、そこに同じ構成の波長変換シート用保護フィルムを積層し、UV硬化ラミネートにより、図1に示した構造を有する実施例1の波長変換シートを得た。
得られた波長変換シートに、LED光源と導光板とを組み合わせて、実施例1のバックライトユニットを作製した。
(波長変換シート用保護フィルムの作製)
実施例1において、コーティング層付きバリアフィルムのガスバリア性被覆層側と、コーティング層を持たないバリアフィルムのガスバリア性被覆層側とを、アクリル樹脂接着剤を用いて貼り合わせたこと以外は、同様の操作にて実施例2の波長変換シート用保護フィルムを得た。この波長変換シート用保護フィルムを2枚作製した。
CdSe/ZnS 530(商品名、SIGMA-ALDRICH社製)をエポキシ系感光性樹脂と混合後、混合液を上述した波長変換シート用保護フィルムの基材側(コーティング層とは反対の面側)に塗布し、そこに同じ構成の波長変換シート用保護フィルムを積層し、UV硬化ラミネートにより、図2に示した構造を有する実施例2の波長変換シートを得た。
得られた波長変換シートに、LED光源と導光板とを組み合わせて、実施例2のバックライトユニットを作製した。
実施例1において、コーティング層を設けない以外は、同様の操作にて実施例3の波長変換シート用保護フィルムを得た。更に、この波長変換シート用保護フィルムを用いたこと以外は実施例1と同様の操作にて、実施例3の波長変換シート及びバックライトユニットを得た。
実施例1において、コーティング層付きバリアフィルムの代わりに、厚み25μmのポリエチレンテレフタレートフィルムを用いたこと以外は、同様の操作にて比較例1の波長変換シート用保護フィルムを得た。更に、この波長変換シート用保護フィルムを用いたこと以外は実施例1と同様の操作にて、比較例1の波長変換シート及びバックライトユニットを得た。
実施例1において、コーティング層を持たないバリアフィルムの代わりに、厚み25μmのポリエチレンテレフタレートフィルムを用いたこと以外は、同様の操作にて比較例2の波長変換シート用保護フィルムを得た。更に、この波長変換シート用保護フィルムを用いたこと以外は実施例1と同様の操作にて、比較例2の波長変換シート及びバックライトユニットを得た。
実施例2において、コーティング層付きバリアフィルムの代わりに、厚み12μmのポリエチレンテレフタレートフィルムを用いたこと以外は、同様の操作にて比較例3の波長変換シート用保護フィルムを得た。更に、この波長変換シート用保護フィルムを用いたこと以外は実施例2と同様の操作にて、比較例3の波長変換シート及びバックライトユニットを得た。
基材としての厚み25μmのポリエチレンテレフタレートフィルムの片面に、第1の無機薄膜層(シリカ蒸着層)として酸化珪素を真空蒸着法により250Åの厚みに設け、さらに、テトラエトキシシランとポリビニルアルコールとを含む塗液をウエットコーティング法により第1の無機薄膜層上に塗工し、0.3μmの厚みの第1のガスバリア性被覆層を形成した。次いで、第1のガスバリア性被覆層上に、第2の無機薄膜層(シリカ蒸着層)として酸化珪素を真空蒸着法により250Åの厚みに設け、さらに、テトラエトキシシランとポリビニルアルコールとを含む塗液をウエットコーティング法により第2の無機薄膜層上に塗工し、0.3μmの厚みの第2のガスバリア性被覆層を形成した。これにより、基材の一方の面上に、第1の無機薄膜層、第1のガスバリア性被覆層、第2の無機薄膜層及び第2のガスバリア性被覆層からなるバリア層が設けられたバリアフィルムを得た。
実施例1~3及び比較例1~4で作製したバックライトユニットについて、輝度計(コニカミノルタ社製、商品名:LS-100)を用いてLED発光時の輝度(初期輝度)を測定した。次に、信頼性試験として、バックライトユニットを60℃、90%RHの環境下で500時間保存した後、輝度を測定した。初期輝度と500時間保存後の輝度との差が小さいほど、波長変換シート用保護フィルムのバリア性が優れていることを意味する。得られた結果を表1に示す。
実施例1~3及び比較例1~4で作製したバックライトユニットについて、LED発光状態で外観を目視確認し、異物(スプラッシュ、キズ、シワ等)の有無、及び、干渉縞の発生の有無をそれぞれ評価した。異物及び干渉縞が確認されなかったものを「A」、異物及び干渉縞が確認されたものを「B」と判定した。この外観評価は、輝度測定と同様に、初期及び60℃、90%RHの環境下で500時間保存した後の両方で行った。得られた結果を表1に示す。
(波長変換シート用保護フィルムの作製)
重量平均分子量6万のPETを用いて形成された厚み16μmのPETフィルムの基材の片面に、密着層用組成物を塗工して、厚み0.1μmの密着層を積層した。次に、密着層の上に、無機薄膜層として第1シリカ蒸着層をその厚みが30nmとなるように物理蒸着法によって積層した。第1シリカ蒸着層の上に、ガスバリア性被覆層用組成物を用いたウエットコーティング法によって、厚み1μmの第1ガスバリア性被覆層(第1複合被膜層)を形成した。更に、第1ガスバリア性被覆層の上に、第2シリカ蒸着層をその厚みが30nmとなるように積層した。続いて、第2シリカ蒸着層の上に、ガスバリア性被覆層用組成物を用いたウエットコーティング法によって、厚み1μmの第2ガスバリア性被覆層(第2複合被膜層)を形成し、第1バリアフィルムを作製した。第1シリカ蒸着層及び第2シリカ蒸着層におけるO/Si比は原子比で1.8とし、屈折率は1.61とした。また、第1バリアフィルムと同様の方法で、第2バリアフィルムを作製した。
CdSe/ZnSのコア・シェル構造をもつ蛍光体を以下の方法で得た。初めに、オクタデセンに、オクチルアミン及び酢酸カドミウムを添加した溶液と、トリオクチルホスフィンにセレンを溶解させた溶液とを質量比1:1で混合し、加熱したマイクロ流路を通過させて、核微粒子としてのCdSe微粒子溶液を得た。続いて、CdSe微粒子溶液と、[(CH3)2NCSS]2Znをトリオクチルホスフィンに溶解させた溶液とを質量比で1:1となるように混合し、加熱されたマイクロ流路を通過させて、CdSe/ZnS構造の蛍光体を得た。得られた蛍光体を感光性樹脂(エポキシ樹脂)に混合し、量子ドット層用混合物を得た。続いて、第1波長変換シート保護フィルムの第1バリアフィルムの基材上(コーティング層とは反対側の面上)に量子ドット層用混合物を塗布し、その上に第2波長変換シート保護フィルムを、その第1バリアフィルムの基材側(コーティング層とは反対側)が第1波長変換シート保護フィルムと対向するように積層した。量子ドット層用混合物にUV照射を行い、量子ドット層用混合物に含まれる感光性樹脂を硬化させた。これにより、量子ドット層(蛍光体層)が第1及び第2波長変換シート保護フィルムによって挟まれた波長変換シートを作製した。
得られた波長変換シートに、LED光源と導光板とを組み合わせて、実施例4のバックライトユニットを作製した。
重量平均分子量6万のPETを用いて形成された厚み16μmのPETフィルムの基材の片面に、密着層用組成物を塗工して、厚み0.1μmの密着層を積層した。次に、密着層の上に、無機薄膜層として第1シリカ蒸着層をその厚みが30nmとなるように物理蒸着法によって積層した。第1シリカ蒸着層の上に、ガスバリア性被覆層用組成物を用いたウエットコーティング法によって、厚み1μmの第1ガスバリア性被覆層(第1複合被膜層)を形成し、第1バリアフィルムを作製した。第1シリカ蒸着層におけるO/Si比は原子比で1.8とし、屈折率は1.61とした。また、第1バリアフィルムと同様の方法で、第2バリアフィルムを作製した。第1及び第2バリアフィルムにおける各層は、実施例4と同様の方法で形成した。実施例5の第1及び第2バリアフィルムはいずれも、シリカ蒸着層及びガスバリア性被覆層を1層ずつ有する構成、すなわち、実施例4の第1及び第2バリアフィルムから、第2シリカ蒸着層及び第2ガスバリア性被覆層を除いた構成を有する。
SiO蒸着材料のO/Si比を変更し、物理蒸着の条件を調整することにより、シリカ蒸着層のO/Si比を原子比で1.7、屈折率を1.55として、第1及び第2シリカ蒸着層を作製した。シリカ蒸着層のO/Si比と屈折率との値以外は、実施例4と同様の方法によって、波長変換シート用保護フィルム、波長変換シート及びバックライトユニットを得た。
表2は、実施例4~6において作製した波長変換シート用保護フィルムの反射率及び透過率の評価結果を示す表である。表3は、実施例4~6において作製した波長変換シート用保護フィルムの水蒸気透過度、及び、バックライトユニットの輝度及び外観の評価結果を示す表である。
Claims (12)
- 波長変換シートにおける蛍光体を保護するための波長変換シート用保護フィルムであって、
基材と、該基材の少なくとも一方の面上に設けられた1以上のバリア層と、を有するバリアフィルムが、2以上積層された構造を有する、波長変換シート用保護フィルム。 - 2以上の前記バリアフィルムは、接着層を用いて積層されており、
隣接する2つの前記バリアフィルムの前記バリア層同士が、前記接着層を介して対向するように配置された構造を有する、請求項1に記載の波長変換シート用保護フィルム。 - 光学的機能を有するコーティング層を更に有し、前記コーティング層が波長変換シート用保護フィルムの少なくとも一方の表面に配置されている、請求項1又は2に記載の波長変換シート用保護フィルム。
- 前記光学的機能が干渉縞防止機能である、請求項3に記載の波長変換シート用保護フィルム。
- 前記コーティング層が、バインダー樹脂と、該バインダー樹脂中に分散された微粒子とを含む、請求項3又は4に記載の波長変換シート用保護フィルム。
- 前記バリア層が、前記基材の一方の面上に積層された無機薄膜層と、該無機薄膜層上に積層されたガスバリア性被覆層とを含む、請求項1~5のいずれか一項に記載の波長変換シート用保護フィルム。
- 前記バリア層が、前記無機薄膜層と前記ガスバリア性被覆層とが交互に2層ずつ以上積層された構造を有する、請求項6に記載の波長変換シート用保護フィルム。
- 前記ガスバリア性被覆層が、水酸基含有高分子化合物、金属アルコキシド、金属アルコキシド加水分解物及び金属アルコキシド重合物のうちの少なくとも一種を含有する層である、請求項6又は7に記載の波長変換シート用保護フィルム。
- 少なくとも一方の表面に配置された光学的機能を有するコーティング層を更に有し、
前記バリア層が無機薄膜層としてシリカ蒸着層を含み、
前記シリカ蒸着層に含まれる酸素とケイ素のO/Si比が原子比で1.7以上2.0以下であり、
前記シリカ蒸着層の屈折率が1.5以上1.7以下であり、
波長450nm、波長540nm、及び波長620nmの全ての波長において、前記波長変換シート用保護フィルムの反射率が10%以上20%以下であり、且つ、透過率が80%以上95%以下である、請求項1~8のいずれか一項に記載の波長変換シート用保護フィルム。 - 蛍光体を含む蛍光体層と、該蛍光体層の少なくとも一方の面上に積層された請求項1~9のいずれか一項に記載の波長変換シート用保護フィルムと、を備える波長変換シート。
- 前記波長変換シート用保護フィルムが、前記蛍光体層と対向する側とは反対側の面上に、光学的機能を有するコーティング層を有する、請求項10に記載の波長変換シート。
- LED光源と、導光板と、請求項10又は11に記載の波長変換シートと、を備えるバックライトユニット。
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KR20160098191A (ko) | 2016-08-18 |
JP6705213B2 (ja) | 2020-06-03 |
JP5900719B1 (ja) | 2016-04-06 |
EP3171072A4 (en) | 2018-04-04 |
EP3171072A1 (en) | 2017-05-24 |
TW201606336A (zh) | 2016-02-16 |
KR101760225B1 (ko) | 2017-07-20 |
JP2016122211A (ja) | 2016-07-07 |
JPWO2016010116A1 (ja) | 2017-04-27 |
TWI661216B (zh) | 2019-06-01 |
KR20170060193A (ko) | 2017-05-31 |
CN105793034A (zh) | 2016-07-20 |
US20160327690A1 (en) | 2016-11-10 |
CN107817540B (zh) | 2020-04-14 |
CN107817540A (zh) | 2018-03-20 |
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