WO2013005794A1 - Composition for forming fluorescent sheet - Google Patents

Composition for forming fluorescent sheet Download PDF

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Publication number
WO2013005794A1
WO2013005794A1 PCT/JP2012/067182 JP2012067182W WO2013005794A1 WO 2013005794 A1 WO2013005794 A1 WO 2013005794A1 JP 2012067182 W JP2012067182 W JP 2012067182W WO 2013005794 A1 WO2013005794 A1 WO 2013005794A1
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Prior art keywords
phosphor
phosphor sheet
forming
composition
forming composition
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PCT/JP2012/067182
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French (fr)
Japanese (ja)
Inventor
伊藤　靖
祥史 上野
啓史 谷
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デクセリアルズ株式会社
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Publication of WO2013005794A1 publication Critical patent/WO2013005794A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
    • 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
    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/422—Luminescent, fluorescent, phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil

Definitions

  • the present invention relates to a phosphor sheet-forming composition
  • a phosphor sheet-forming composition comprising a film-forming composition and a powdery phosphor that emits fluorescence when irradiated with excitation light.
  • the present invention is intended to solve the above-described conventional problems, exhibits good light resistance, low light absorption for visible light, and suppresses deterioration of the phosphor due to moisture while using a low-cost material.
  • An object of the present invention is to provide a phosphor sheet-forming composition capable of providing the phosphor sheet thus obtained at low cost.
  • the present inventors show good light resistance, low light absorption for visible light, and available at low cost. It has been found that the above-mentioned object can be achieved by using a mold compound, and the present invention has been completed.
  • the present invention is a phosphor sheet-forming composition
  • a phosphor sheet-forming composition comprising a film-forming composition and a powdered phosphor that emits fluorescence when irradiated with excitation light
  • a film forming composition provides a phosphor sheet forming composition containing a photocurable compound.
  • the present invention is a phosphor sheet in which a phosphor layer that emits fluorescence when irradiated with excitation light is sandwiched between a pair of transparent substrates, and the phosphor layer is for forming the phosphor sheet of the present invention described above.
  • a phosphor sheet formed by forming a film of the composition, and a light-emitting device having the phosphor sheet and an excitation light source that emits excitation light to irradiate the phosphor sheet.
  • the phosphor sheet-forming composition of the present invention is excellent in light resistance and low in light absorption for visible light compared to thermoplastic resins, etc., among many resins and polymerizable compounds as a film-forming composition.
  • a photocurable compound that can provide a resin and is available at a relatively low cost is used. Therefore, the phosphor sheet-forming composition of the present invention can provide a phosphor sheet that is excellent in light resistance, has low light absorbability with respect to visible light, and suppresses phosphor modification due to moisture at low cost. . Even when the phosphor sheet is used for a long period of time, the chromaticity deviation width is small, and the emission spectrum intensity is not greatly lowered.
  • FIG. 1 is a cross-sectional view of a single-layer phosphor sheet.
  • FIG. 2 is a cross-sectional view of a two-layer phosphor sheet.
  • FIG. 3 is a cross-sectional view of a preferred single-layer phosphor sheet.
  • FIG. 4 is a cross-sectional view of a preferred two-layer phosphor sheet.
  • FIG. 5 is a cross-sectional view of the sealing film.
  • the phosphor sheet-forming composition of the present invention contains a film-forming composition and a powdered phosphor that emits fluorescence when irradiated with excitation light.
  • the film-forming composition contains a photocurable compound.
  • the reason for using the photo-curing compound is that the resin produced during photo-curing adheres well to the phosphor surface, exhibits superior light resistance and low water absorption compared to thermoplastic resins, and is low in cost. Because it is available at. As a result, it is possible to prevent the phosphor from being altered by moisture.
  • a photocurable monomer can be used in combination with the photocurable compound as a diluent, it is not necessary to use a solvent such as toluene. Therefore, compared with the case where toluene etc. are used, the density
  • the photocurable compound constituting the film-forming composition preferably contains a photocurable (meth) acrylate.
  • the photocurable (meth) acrylate has an ester group that exhibits a water trapping ability. Therefore, by using the photocurable (meth) acrylate, it is possible to capture more moisture that has entered the phosphor sheet, and it is possible to further prevent the phosphor from being altered by moisture.
  • Examples of such a photo-curable (meth) acrylate include urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.
  • urethane (meth) acrylate can be preferably used from the viewpoint of heat resistance.
  • (meth) acrylate” includes acrylate and methacrylate.
  • a reaction product of a polyol preferably polyether polyol, polyolefin polyol, polyester polyol or polycarbonate polyol
  • a diisocyanate compound preferably isophorone diisocyanate
  • a hydroxyalkyl (meth) acrylate preferably , 2-hydroxypropyl acrylate
  • the film-forming composition usually contains a photopolymerization initiator.
  • photopolymerization initiators include radical photopolymerization initiators such as alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester photopolymerization initiators. And oxyphenyl acetate ester photopolymerization initiators; cationic photopolymerization initiators such as diazonium photopolymerization initiators, iodonium photopolymerization initiators, sulfonium photopolymerization initiators, and the like.
  • the amount of these photopolymerization initiators used is preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the photocurable compound.
  • a phosphor in a powder form (usually having an average particle diameter of 3 to 20 ⁇ m) that emits fluorescence (fluorescence having a wavelength longer than that of the excitation light) when irradiated with excitation light is used as the phosphor.
  • This phosphor is a sulfide-based phosphor, an oxide phosphor, or a mixed phosphor thereof.
  • the excitation light light having a wavelength capable of exciting the phosphor to be used and emitting fluorescence may be selected as appropriate.
  • the phosphor sheet emits white light, it is preferable to use blue light having a blue fluorescent peak with a wavelength of 440 to 490 nm.
  • a blue light source a known blue LED is preferably used.
  • an oxide phosphor having a red fluorescence peak with a wavelength of 590 to 620 nm by irradiation with blue excitation light preferably CaS: Eu, (BaSr) 3 SiO 5 : Eu, or wavelength 530 by irradiation with blue excitation light.
  • a sulfur-based phosphor having a green fluorescence peak of ⁇ 550 nm, preferably SrGa 2 S 4 : Eu can be mentioned.
  • the mixture of said fluorescent substance as fluorescent substance.
  • an oxide phosphor having a red fluorescence peak with a wavelength of 590 to 620 nm by irradiation with blue excitation light and a green fluorescence peak with a wavelength of 530 to 550 nm by irradiation with blue excitation light is preferable to use.
  • a mixed phosphor with a sulfide-based phosphor having A particularly preferred combination is a mixed phosphor of (BaSr) 3 SiO 5 : Eu that emits red fluorescence and SrGa 2 S 4 : Eu that emits green fluorescence.
  • the amount is preferably 1 to 10 parts by mass, more preferably 3 to 6 parts by mass with respect to 100 parts by mass of the film-forming composition.
  • the phosphor sheet-forming composition of the present invention is blended with other light-transmitting compounds such as (meth) acrylic monomers and oligomers, coloring pigments and the like within a range not impairing the effects of the present invention. be able to.
  • the phosphor sheet-forming composition of the present invention can be prepared by mixing a film-forming composition and a powdery phosphor by a conventional method.
  • the phosphor sheet of the present invention is a phosphor sheet 10 in which a phosphor layer 1 that emits fluorescence when irradiated with excitation light is a single layer sandwiched between a pair of transparent substrates 2,
  • the phosphor layer 1 is formed by depositing the phosphor sheet forming composition of the present invention described above.
  • FIG. 1 shows an example in which the phosphor layer 1 is a single layer
  • a laminated phosphor having a two-layer structure in which two phosphor layers 1 a and 1 b are laminated via a transparent separator 3.
  • the layer 20 may be used.
  • the pair of transparent base materials 2a and 2b are sandwiched.
  • one of the phosphor layers 1a and 1b emits red light containing an oxide phosphor (preferably (BaSr) 3 SiO 5 : Eu) having a red fluorescence peak with a wavelength of 590 to 620 nm when irradiated with blue excitation light.
  • an oxide phosphor preferably (BaSr) 3 SiO 5 : Eu
  • a phosphor containing a sulfur-based phosphor preferably SrGa 2 S 4 : Eu
  • SrGa 2 S 4 : Eu sulfur-based phosphor having a green fluorescence peak with a wavelength of 530 to 550 nm by irradiation with blue excitation light. It is preferable to form from the sheet forming composition.
  • the thickness of the phosphor layers 1, 1a, 1b is preferably 20 to 150 ⁇ m, more preferably 60 to 120 ⁇ m.
  • thermoplastic resin film having a thickness of 10 to 100 ⁇ m, a heat or a photocurable resin film can be used.
  • a polyester film, a polyamide film, a polyimide film, a polysulfone film, a triacetyl cellulose film, a polyolefin film, and the like can be given.
  • the surfaces of these films may be subjected to corona discharge treatment, silane coupling agent treatment or the like, if necessary.
  • the phosphor sheet 10 in FIGS. 1 and 2 can be further sealed from both sides with two sealing films 30a and 30b as shown in FIGS. preferable. Thereby, the penetration
  • sealing films 30a and 30b those in which an adhesive layer 32 is formed on a base film 31 can be used as shown in FIG. Further, in order to improve the water vapor barrier property of the sealing films 30a and 30b, a silicon oxide layer 33 having a thickness of 5 to 20 nm is deposited on the surface of the base film 31 on the adhesive layer 32 side or on the opposite surface. May be formed. In the latter case, the surface protective film 34 may be laminated on the silicon oxide layer 33 via an adhesive layer (not shown).
  • the base film 31 and the surface protection film 34 can be appropriately selected from the films exemplified for the transparent substrates 2a and 2b and the transparent separator 3 already described.
  • the adhesive layer at the time of laminating the adhesive layer 32 and the surface protective film 34 it can be appropriately selected from known adhesives such as urethane adhesives and acrylic adhesives.
  • the thickness of the adhesive layer 32 is usually 10 to 50 ⁇ m.
  • a single-layer phosphor sheet 10 of the present invention shown in FIG. 1 forms a phosphor layer 1 by forming a phosphor sheet-forming composition on a transparent substrate 2 by a conventional method, and separates the phosphor layer 1 thereon. It can manufacture by laminating
  • the photocurable compound contained in the phosphor layer 1 must be photocured (polymerized) by irradiating active energy rays such as ultraviolet rays, for example. In this case, the photocurable compound is active against the phosphor layer 1. You may irradiate an energy ray directly, or you may irradiate an active energy ray through the transparent base material 2 or the sealing film 30a or 30b.
  • the two-layer phosphor sheet 10 of the present invention shown in FIG. 2 forms a phosphor layer 1a by forming a phosphor sheet-forming composition on a transparent substrate 2a by a conventional method, and a transparent layer is formed thereon.
  • a separator 3 is laminated, and another phosphor sheet forming composition containing a phosphor different from the above phosphor sheet forming composition is formed by a conventional method to form a phosphor layer 1b. It can manufacture by laminating
  • the phosphor sheet 10 having the structure shown in FIG. 4 can be manufactured by sandwiching both surfaces of the phosphor sheet 10 with the sealing films 30a and 30b so that the adhesive layer 32 is on the inner side and thermocompressing the whole. it can.
  • the photopolymerizable compounds contained in the phosphor layers 1a and 1b need to be photocured (polymerized) by irradiating active energy rays such as ultraviolet rays, for example.
  • active energy rays such as ultraviolet rays, for example.
  • the phosphor layers 1a and 1b The active energy ray may be directly irradiated to the transparent substrate 2a, 2b, the transparent separator 3 and / or the active film 30a, 30b.
  • the phosphor sheet of the present invention described above can be preferably applied as the phosphor sheet of a light emitting device having a phosphor sheet and an excitation light source that emits excitation light applied to the phosphor sheet.
  • Other components for example, a light diffusing member
  • This light emitting device can itself be used as a lighting device. It can also be used as a backlight for liquid crystal display elements.
  • Example 1 (Production of single-layer phosphor sheet) (Preparation of composition for forming green-red mixed phosphor sheet) 100 parts by mass of photocurable urethane methacrylate (Aronix 1600M, Toa Gosei Co., Ltd.), 0.5 parts by mass of photopolymerization initiator (BASF, Darocur 1173), SrGa 2 S 4 with an average particle size of 6 ⁇ m: Eu A phosphor sheet-forming composition was prepared by uniformly dispersing 1.5 parts by mass of (sulfurized green phosphor) and (BaSr) 3 SiO 5 : Eu (oxide red phosphor).
  • a phosphor sheet-forming composition was applied to a polyethylene terephthalate film (T11, Toray Industries, Inc.) having a thickness of 25 ⁇ m so as to have a dry thickness of 115 ⁇ m, and then irradiated with ultraviolet rays (7000 mJ / cm 2 ).
  • a phosphor layer was formed by polymerizing urethane methacrylate.
  • a polyethylene terephthalate film (A4300, Toyobo Co., Ltd.) having a thickness of 38 ⁇ m is laminated on the phosphor layer, and a thermocompression treatment (100 ° C., 0.2 Pa) is performed to obtain a phosphor sheet having the structure of FIG. It was.
  • a polyolefin adhesive layer (Septon V9827, Kuraray Co., Ltd.) having a thickness of 20 to 25 ⁇ m was formed on one surface of a polyethylene terephthalate film (T-11, Toray Industries, Inc.) having a thickness of 25 ⁇ m.
  • the sealing film was created by laminating
  • the surface protective film has a thickness of 1 to 2 ⁇ m on the silicon oxide deposited layer of a 12 ⁇ m thick polyethylene terephthalate film (Tech Barrier, Mitsubishi Plastics, Inc.) on which a silicon oxide deposited layer having a thickness of about 20 nm is formed. It was created by forming a urethane adhesive layer. The moisture permeability of the obtained sealing film was 0.3 g / m 2 ⁇ 24 hr ⁇ atm.
  • the phosphor sheet sealed with the sealing film was obtained by disposing the sealing film on both surfaces of the phosphor sheet having the structure of FIG. 1 and performing thermocompression treatment (100 ° C., 0.2 Pa).
  • Example 2 (Production of two-layer phosphor sheet) (Preparation of composition for forming green phosphor sheet) 100 parts by mass of photocurable urethane methacrylate (Aronix 1600M, Toa Gosei Co., Ltd.), 0.5 parts by mass of photopolymerization initiator (BASF, Darocur 1173), SrGa 2 S 4 with an average particle size of 6 ⁇ m: Eu A green phosphor sheet-forming composition was prepared by uniformly dispersing 1.5 parts by mass of (sulfurized green phosphor).
  • composition for forming red phosphor sheet (BaSr) 3 SiO 5 with 100 parts by mass of photocurable urethane methacrylate (Aronix 1600M, Toa Gosei Co., Ltd.), 0.5 parts by mass of a photopolymerization initiator (BASF, Darocur 1173) and an average particle size of 10 ⁇ m :
  • a composition for forming a red phosphor sheet was prepared by uniformly dispersing 3 parts by mass of Eu (oxide red phosphor).
  • a 38 ⁇ m thick transparent separator polyethylene terephthalate film (A4300, Toyobo Co., Ltd.)
  • the red phosphor sheet-forming composition is 20 ⁇ m in dry thickness on the transparent separator.
  • an ultraviolet ray was irradiated (7000 mJ / cm 2 ) to polymerize urethane methacrylate to form a red phosphor layer.
  • a 25 ⁇ m thick polyethylene terephthalate film (T11, Toray Industries, Inc.) was laminated to obtain a phosphor sheet having the structure of FIG.
  • Example 3 Preparation of green single-color phosphor sheet
  • (BaSr) 3 SiO 5 : Eu oxide red phosphor
  • a phosphor sheet composition was prepared in the same manner as in Example 1, and the phosphor having the structure of FIG. 1 and FIG. 3 was further prepared. A sheet was obtained. This phosphor sheet is a single green color.
  • Comparative Example 1 A composition for forming a phosphor sheet in the same manner as in Example 1, except that butyl methacrylate-glycidyl methacrylate (BMA-GMA) copolymer (DF-242, Fujikura Kasei Co., Ltd.) is used instead of urethane methacrylate. And a phosphor sheet having the structure shown in FIG. 1 and FIG. 3 was produced.
  • BMA-GMA butyl methacrylate-glycidyl methacrylate copolymer
  • Comparative Example 2 A phosphor sheet-forming composition was prepared in the same manner as in Example 1 except that methyl methacrylate-butyl acrylate (MMA-BA) copolymer (NABSTAR N800AS, Kaneka Corporation) was used instead of urethane methacrylate. Thus, a phosphor sheet having the structure of FIG. 1 and FIG. 3 was manufactured.
  • MMA-BA methyl methacrylate-butyl acrylate copolymer
  • Comparative Example 3 Similar to Example 1 except that instead of urethane methacrylate, a hydrogenated styrene-ethylene-butylene-styrene block (hydrogenated SEBS) copolymer (Septon V9827, Kuraray Co., Ltd.) is used and no ultraviolet rays are irradiated. Thus, a phosphor sheet forming composition was prepared, and a phosphor sheet having the structure of FIG. 1 and FIG. 3 was produced.
  • hydrogenated SEBS hydrogenated styrene-ethylene-butylene-styrene block copolymer
  • Comparative Example 4 Instead of urethane methacrylate, hydrogenated styrene-ethylene-butylene-styrene block (hydrogenated SEBS) copolymer (Septon V9827, Kuraray Co., Ltd.) 40 parts by weight and maleic anhydride 0.5 parts by weight were used.
  • a phosphor sheet-forming composition was prepared in the same manner as in Example 1 except that no ultraviolet rays were irradiated, and a phosphor sheet having the structure shown in FIG. 1 and FIG. 3 was produced.
  • Comparative Example 5 Similar to Example 3 except that instead of urethane methacrylate, a hydrogenated styrene-ethylene-butylene-styrene block (hydrogenated SEBS) copolymer (Septon V9827, Kuraray Co., Ltd.) is used and no ultraviolet rays are irradiated.
  • a phosphor sheet-forming composition was prepared to produce a phosphor sheet having the structure of FIG. 1 and FIG. This phosphor sheet is a single green color.
  • Comparative Example 6 Instead of urethane methacrylate, fluorescence was used in the same manner as in Example 3 except that a butyl methacrylate-glycidyl methacrylate (BMA-GMA) copolymer (DF-242, Fujikura Kasei Co., Ltd.) was used and no ultraviolet ray was irradiated.
  • BMA-GMA butyl methacrylate-glycidyl methacrylate copolymer
  • DF-242 Fujikura Kasei Co., Ltd.
  • a composition for forming a body sheet was prepared, and a phosphor sheet having the structure of FIG. 1 and FIG. 3 was produced. This phosphor sheet is a single green color.
  • the chromaticity difference was A evaluation.
  • BMA-GMA copolymer, MMA-BA copolymer, hydrogenated SEBS, or hydrogenated instead of urethane methacrylate was B or C.
  • the fluorescent substance sheet of Example 2 arranges the green fluorescent substance and red fluorescent substance which were used in Example 1 in a separate fluorescent substance layer, the chromaticity difference which the combination of fluorescent substance influences is the same. As expected, the evaluation was A.
  • the phosphor sheets of Example 3 and Comparative Examples 5 and 6 emit green monochromatic light, they are suitable as examples for measuring the emission spectrum intensity ratio.
  • the emission spectrum intensity ratio is A evaluation
  • the emission spectrum intensity ratio is B evaluation or C evaluation. It was.
  • the phosphor sheet-forming composition of the present invention is excellent in light resistance and low in light absorption for visible light compared to thermoplastic resins, etc., among many resins and polymerizable compounds as a film-forming composition.
  • a photocurable compound that can provide a resin and is available at a relatively low cost is used. Therefore, the phosphor sheet-forming composition of the present invention is excellent in light resistance, has a low light absorption property for visible light, suppresses phosphor alteration due to moisture, and is useful as a raw material for producing a low-cost phosphor sheet. is there.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

This composition—which is for forming a fluorescent sheet and can, at a low cost, provide a fluorescent sheet that exhibits favorable light resistance, has a low light absorbance of visible light, uses a low-cost material, and at the same time has suppressed alteration by means of water of a fluorescent body—contains a composition for film formation, and a particulate fluorescent body that releases fluorescent light by means of irradiation by excitation light. A photocurable compound is used as the composition for film formation. A photocurable (meth)acrylate, preferably a urethane (meth)acrylate, can be cited as the photocurable compound. The result of esterification by means of 2-hydroxypropyl acrylate of the reaction product of a polyol and isophorone diisocyanate can be cited as the urethane (meth)acrylate.

Description

蛍光体シート形成用組成物Composition for forming phosphor sheet
　本発明は、成膜用組成物と、励起光の照射により蛍光を発する粉末状の蛍光体とを含有する蛍光体シート形成用組成物に関する。 The present invention relates to a phosphor sheet-forming composition comprising a film-forming composition and a powdery phosphor that emits fluorescence when irradiated with excitation light.
　従来、青色光の照射により赤色蛍光を発する粉状の赤色蛍光体と緑色蛍光を発する緑色蛍光体とを、可視光透過性に優れた樹脂材料に分散させてなる蛍光体シートに対し、青色発光ダイオード（青色ＬＥＤ）から光を照射して赤色光と緑色光とを発光させ、それらと青色光とを混色させることにより白色光を得ることが試みられている（特許文献１）。 Conventionally, blue light emission is applied to a phosphor sheet in which a powdery red phosphor that emits red fluorescence and green phosphor that emits green fluorescence are dispersed in a resin material having excellent visible light transmission. Attempts have been made to obtain white light by emitting light from a diode (blue LED) to emit red light and green light and mixing them with blue light (Patent Document 1).
特開２００８－４１７０６号公報JP 2008-41706 A
　しかしながら、このような蛍光体シートにおいて、樹脂材料として低コストの汎用熱可塑性樹脂等を使用した場合、青色光により樹脂材料が黄変し、青色ＬＥＤの光出力の損失や、発光した蛍光の吸収が生じるという問題があった。また、樹脂材料に侵入した水分のために蛍光体が変質し、蛍光体シートの発光色に色変化が生ずるという問題があった。このため、樹脂材料として耐光性・耐水蒸気透過性に優れているが高コストのシリコーン樹脂を使用したり、蛍光体シートの両面を高コストのガラス基板で挟持したりしなければならず、蛍光体シートの製造コストを圧縮することが困難になるという問題もあった。 However, in such a phosphor sheet, when a low-cost general-purpose thermoplastic resin or the like is used as the resin material, the resin material is yellowed by the blue light, and the light output loss of the blue LED or the absorption of the emitted fluorescence is absorbed. There was a problem that occurred. In addition, there is a problem that the phosphor changes in quality due to moisture that has entered the resin material, causing a color change in the emission color of the phosphor sheet. For this reason, it is necessary to use a high-cost silicone resin that is excellent in light resistance and water vapor transmission resistance as a resin material, or to sandwich both sides of a phosphor sheet between high-cost glass substrates. There is also a problem that it is difficult to compress the manufacturing cost of the body sheet.
　本発明は、以上の従来の課題を解決しようとするものであり、良好な耐光性を示し、可視光に対する光吸収性が低く、低コストの材料を用いつつ、水分による蛍光体の変質が抑制された蛍光体シートを低コストで与え得る蛍光体シート形成用組成物を提供することを目的とする。 The present invention is intended to solve the above-described conventional problems, exhibits good light resistance, low light absorption for visible light, and suppresses deterioration of the phosphor due to moisture while using a low-cost material. An object of the present invention is to provide a phosphor sheet-forming composition capable of providing the phosphor sheet thus obtained at low cost.
　本発明者らは、蛍光体シート形成用組成物を構成する成膜用組成物の主成分として、良好な耐光性を示し、可視光に対する光吸収性が低く、低コストで入手可能な光硬化型化合物を使用することにより、上述の目的を達成できることを見出し、本発明を完成させるに至った。 As a main component of the film-forming composition constituting the phosphor sheet-forming composition, the present inventors show good light resistance, low light absorption for visible light, and available at low cost. It has been found that the above-mentioned object can be achieved by using a mold compound, and the present invention has been completed.
　即ち、本発明は、成膜用組成物と、励起光の照射により蛍光を発する粉末状の蛍光体とを含有する蛍光体シート形成用組成物であって、
　成膜用組成物が、光硬化型化合物を含有する蛍光体シート形成用組成物を提供する。 That is, the present invention is a phosphor sheet-forming composition comprising a film-forming composition and a powdered phosphor that emits fluorescence when irradiated with excitation light,
A film forming composition provides a phosphor sheet forming composition containing a photocurable compound.
　また、本発明は、励起光の照射により蛍光を発する蛍光体層が一対の透明基材に挟持されている蛍光体シートであって、蛍光体層が、上述の本発明の蛍光体シート形成用組成物を成膜したものである蛍光体シート、また、この蛍光体シートと、蛍光体シートに照射する励起光を発する励起光源とを有する発光装置を提供する。 Further, the present invention is a phosphor sheet in which a phosphor layer that emits fluorescence when irradiated with excitation light is sandwiched between a pair of transparent substrates, and the phosphor layer is for forming the phosphor sheet of the present invention described above. Provided is a phosphor sheet formed by forming a film of the composition, and a light-emitting device having the phosphor sheet and an excitation light source that emits excitation light to irradiate the phosphor sheet.
　本発明の蛍光体シート形成用組成物は、成膜用組成物として、多数の樹脂や重合性化合物の中から、熱可塑性樹脂などに比べ、耐光性に優れ、可視光に対する光吸収性が低い樹脂を与えることができ、しかも比較的低コストで入手可能な光硬化型化合物を使用する。よって、本発明の蛍光体シート形成用組成物から、耐光性に優れ、可視光に対する光吸収性が低く、水分による蛍光体の変質が抑制された蛍光体シートを低コストで提供することができる。この蛍光体シートは、長期使用しても、色度のズレ幅が小さく、発光スペクトル強度の低下も小さいものとなる。 The phosphor sheet-forming composition of the present invention is excellent in light resistance and low in light absorption for visible light compared to thermoplastic resins, etc., among many resins and polymerizable compounds as a film-forming composition. A photocurable compound that can provide a resin and is available at a relatively low cost is used. Therefore, the phosphor sheet-forming composition of the present invention can provide a phosphor sheet that is excellent in light resistance, has low light absorbability with respect to visible light, and suppresses phosphor modification due to moisture at low cost. . Even when the phosphor sheet is used for a long period of time, the chromaticity deviation width is small, and the emission spectrum intensity is not greatly lowered.
図１は、単層型の蛍光体シートの断面図である。FIG. 1 is a cross-sectional view of a single-layer phosphor sheet. 図２は、２層型の蛍光体シートの断面図である。FIG. 2 is a cross-sectional view of a two-layer phosphor sheet. 図３は、好ましい単層型の蛍光体シートの断面図である。FIG. 3 is a cross-sectional view of a preferred single-layer phosphor sheet. 図４は、好ましい２層型の蛍光体シートの断面図である。FIG. 4 is a cross-sectional view of a preferred two-layer phosphor sheet. 図５は、封止フィルムの断面図である。FIG. 5 is a cross-sectional view of the sealing film.
　本発明の蛍光体シート形成用組成物は、成膜用組成物と、励起光の照射により蛍光を発する粉末状の蛍光体とを含有する。 The phosphor sheet-forming composition of the present invention contains a film-forming composition and a powdered phosphor that emits fluorescence when irradiated with excitation light.
　成膜用組成物は、光硬化型化合物を含有する。ここで、光硬化型化合物を使用する理由は、光硬化の際に生成した樹脂が蛍光体表面に十分に密着し、熱可塑性樹脂に比べ優れた耐光性と低い吸水率を示し、しかも低コストで入手可能だからである。その結果、水分による蛍光体の変質を防止することが可能になる。また、光硬化型化合物には、希釈剤として光硬化型モノマーを併用することができるので、トルエンなどの溶媒の使用は不必要である。従って、トルエンなどを使用した場合に比べ、蛍光体並びに硬化成分である光硬化型化合物の濃度をそれぞれ高く設定することができる。よって、所定の厚みの蛍光体層を形成する際の蛍光体シート形成用組成物の塗工回数を少なくすることができる。 The film-forming composition contains a photocurable compound. Here, the reason for using the photo-curing compound is that the resin produced during photo-curing adheres well to the phosphor surface, exhibits superior light resistance and low water absorption compared to thermoplastic resins, and is low in cost. Because it is available at. As a result, it is possible to prevent the phosphor from being altered by moisture. Moreover, since a photocurable monomer can be used in combination with the photocurable compound as a diluent, it is not necessary to use a solvent such as toluene. Therefore, compared with the case where toluene etc. are used, the density | concentration of the fluorescent substance and the photocurable compound which is a hardening component can each be set high. Therefore, the frequency | count of application of the composition for fluorescent substance sheet formation at the time of forming the fluorescent substance layer of predetermined thickness can be decreased.
　成膜用組成物を構成する光硬化型化合物は、好ましくは光硬化型（メタ）アクリレートを含有する。光硬化型（メタ）アクリレートは、水分捕捉能を示すエステル基を有する。従って、光硬化型（メタ）アクリレートの使用により、蛍光体シートに侵入した水分をより捕捉することが可能となり、水分による蛍光体の変質をより防止することが可能となる。 The photocurable compound constituting the film-forming composition preferably contains a photocurable (meth) acrylate. The photocurable (meth) acrylate has an ester group that exhibits a water trapping ability. Therefore, by using the photocurable (meth) acrylate, it is possible to capture more moisture that has entered the phosphor sheet, and it is possible to further prevent the phosphor from being altered by moisture.
　このような光硬化型（メタ）アクリレートとしては、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレートなどを挙げることができる。これらの中でも、耐熱性の点からウレタン（メタ）アクリレートを好ましく使用することができる。ここで、“（メタ）アクリレート”には、アクリレートとメタクリレートとが包含される。 Examples of such a photo-curable (meth) acrylate include urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. Among these, urethane (meth) acrylate can be preferably used from the viewpoint of heat resistance. Here, “(meth) acrylate” includes acrylate and methacrylate.
　好ましいウレタン（メタ）アクリレートとしては、ポリオール（好ましくはポリエーテルポリオール、ポリオレフィンポリオール、ポリエステルポリオールもしくはポリカーボネートポリオール）とジイソシアネート化合物（好ましくはイソホロンジイソシアネート）との反応物を、ヒドロキシアルキル（メタ）アクリレート（好ましくは、２－ヒドロキシプロピルアクリレート）でエステル化したものが挙げられる。 As a preferable urethane (meth) acrylate, a reaction product of a polyol (preferably polyether polyol, polyolefin polyol, polyester polyol or polycarbonate polyol) and a diisocyanate compound (preferably isophorone diisocyanate) is used as a hydroxyalkyl (meth) acrylate (preferably , 2-hydroxypropyl acrylate).
　本発明において、光硬化型（メタ）アクリレート中にウレタン（メタ）アクリレートの含有量が少なすぎると、接着性が低下する傾向があるので、光硬化型（メタ）アクリレート１００質量部中に少なくとも１０質量部含有されていることが好ましく、少なくとも３０質量部含有されていることがより好ましい。 In this invention, since there exists a tendency for adhesiveness to fall when there is too little content of urethane (meth) acrylate in photocurable (meth) acrylate, at least 10 in 100 mass parts of photocurable (meth) acrylates. It is preferably contained in part by mass, and more preferably at least 30 parts by mass.
　また、成膜用組成物は、通常、光重合開始剤を含有する。このような光重合開始剤としては、ラジカル光重合開始剤、例えば、アルキルフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤、チタノセン系光重合開始剤、オキシムエステル系光重合開始剤、オキシフェニル酢酸エステル系光重合開始剤等；カチオン光重合開始剤、例えば、ジアゾニウム系光重合開始剤、ヨードニウム系光重合開始剤、スルホニウム系光重合開始剤等を挙げることができる。これらの光重合開始剤の使用量は、光硬化型化合物１００質量部に対し、好ましくは０．１～１０質量部、より好ましくは１～１０質量部である。 The film-forming composition usually contains a photopolymerization initiator. Examples of such photopolymerization initiators include radical photopolymerization initiators such as alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester photopolymerization initiators. And oxyphenyl acetate ester photopolymerization initiators; cationic photopolymerization initiators such as diazonium photopolymerization initiators, iodonium photopolymerization initiators, sulfonium photopolymerization initiators, and the like. The amount of these photopolymerization initiators used is preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the photocurable compound.
　本発明においては、蛍光体として、励起光の照射により蛍光（励起光よりも長波長の蛍光）を発する粉末状（通常、平均粒径が３～２０μｍ）の蛍光体を使用する。この蛍光体は、硫化系蛍光体、酸化物蛍光体またはそれらの混合系蛍光体である。ここで、励起光としては、使用する蛍光体を励起して蛍光を発することのできる波長の光を適宜選択すればよい。蛍光体シートを白色で発光させる場合には、波長４４０～４９０ｎｍの青色蛍光ピークを有する青色光を使用することが好ましい。青色光の光源としては、公知の青色ＬＥＤを使用することが好ましい。 In the present invention, a phosphor in a powder form (usually having an average particle diameter of 3 to 20 μm) that emits fluorescence (fluorescence having a wavelength longer than that of the excitation light) when irradiated with excitation light is used as the phosphor. This phosphor is a sulfide-based phosphor, an oxide phosphor, or a mixed phosphor thereof. Here, as the excitation light, light having a wavelength capable of exciting the phosphor to be used and emitting fluorescence may be selected as appropriate. When the phosphor sheet emits white light, it is preferable to use blue light having a blue fluorescent peak with a wavelength of 440 to 490 nm. As a blue light source, a known blue LED is preferably used.
　蛍光体としては、青色励起光の照射により波長５９０～６２０ｎｍの赤色蛍光ピークを有する酸化物蛍光体、好ましくはＣａＳ：Ｅｕ、（ＢａＳｒ）３ＳｉＯ５：Ｅｕや、青色励起光の照射により波長５３０～５５０ｎｍの緑色蛍光ピークを有する硫化系蛍光体、好ましくはＳｒＧａ２Ｓ４：Ｅｕを挙げることができる。 As the phosphor, an oxide phosphor having a red fluorescence peak with a wavelength of 590 to 620 nm by irradiation with blue excitation light, preferably CaS: Eu, (BaSr) 3 SiO 5 : Eu, or wavelength 530 by irradiation with blue excitation light. A sulfur-based phosphor having a green fluorescence peak of ˜550 nm, preferably SrGa 2 S 4 : Eu can be mentioned.
　また、蛍光体として上記の蛍光体の混合物を使用してもよい。この場合、蛍光体シートを白色で発光させるために、青色励起光の照射により波長５９０～６２０ｎｍの赤色蛍光ピークを有する酸化物蛍光体と、青色励起光の照射により波長５３０～５５０ｎｍの緑色蛍光ピークを有する硫化系蛍光体との混合蛍光体を使用することが好ましい。特に好ましい組み合わせは、赤色蛍光を発する（ＢａＳｒ）３ＳｉＯ５：Ｅｕと、緑色蛍光を発するＳｒＧａ２Ｓ４：Ｅｕとの混合蛍光体である。 Moreover, you may use the mixture of said fluorescent substance as fluorescent substance. In this case, in order to cause the phosphor sheet to emit white light, an oxide phosphor having a red fluorescence peak with a wavelength of 590 to 620 nm by irradiation with blue excitation light and a green fluorescence peak with a wavelength of 530 to 550 nm by irradiation with blue excitation light. It is preferable to use a mixed phosphor with a sulfide-based phosphor having A particularly preferred combination is a mixed phosphor of (BaSr) 3 SiO 5 : Eu that emits red fluorescence and SrGa 2 S 4 : Eu that emits green fluorescence.
　本発明において、成膜用組成物に対する蛍光体の混合割合は、少なすぎると、塗布膜が厚くなり使用する溶剤量が多くなる傾向があり、多すぎると、塗布膜が薄くなり、色度ムラが大きくなる傾向があるので、成膜用組成物１００質量部に対し好ましくは１～１０質量部、より好ましくは３～６質量部である。 In the present invention, if the mixing ratio of the phosphor to the film-forming composition is too small, the coating film tends to be thick and the amount of the solvent to be used tends to be large. Therefore, the amount is preferably 1 to 10 parts by mass, more preferably 3 to 6 parts by mass with respect to 100 parts by mass of the film-forming composition.
　本発明の蛍光体シート形成用組成物には、必要に応じ、本発明の効果を損なわない範囲で、（メタ）アクリル系モノマー、オリゴマー等の他の光透過性化合物、着色顔料等を配合することができる。 If necessary, the phosphor sheet-forming composition of the present invention is blended with other light-transmitting compounds such as (meth) acrylic monomers and oligomers, coloring pigments and the like within a range not impairing the effects of the present invention. be able to.
　本発明の蛍光体シート形成用組成物は、成膜用組成物と粉状の蛍光体とを、常法により混合することにより調製することができる。 The phosphor sheet-forming composition of the present invention can be prepared by mixing a film-forming composition and a powdery phosphor by a conventional method.
　次に、本発明の蛍光体シート形成用組成物を使用した蛍光体シートについて図面を参照しながら説明する。 Next, a phosphor sheet using the phosphor sheet forming composition of the present invention will be described with reference to the drawings.
　本発明の蛍光体シートは、図１に示すように、励起光の照射により蛍光を発する蛍光体層１が単層で一対の透明基材２に挟持されている蛍光体シート１０であって、蛍光体層１が、先述した本発明の蛍光体シート形成用組成物を成膜したものである。 As shown in FIG. 1, the phosphor sheet of the present invention is a phosphor sheet 10 in which a phosphor layer 1 that emits fluorescence when irradiated with excitation light is a single layer sandwiched between a pair of transparent substrates 2, The phosphor layer 1 is formed by depositing the phosphor sheet forming composition of the present invention described above.
　図１では蛍光体層１が単層である例を示したが、図２に示すように、透明セパレータ３を介して２層の蛍光体層１ａ及び１ｂを積層した２層構造の積層蛍光体層２０としてもよい。この場合も一対の透明基材２ａ、２ｂに挟持させる。このように２層構造とすることにより、互いに反応し易い蛍光体同士（例えばＣａＳ：ＥｕとＳｒＣａ２Ｓ４：Ｅｕ）、蛍光体と成膜用組成物成分とを別々の層に配置でき、その結果、それらの意図しない反応を抑制することができ、蛍光体シートの寿命を長くすることができる。この場合、蛍光体層１ａと１ｂの一方を、青色励起光の照射により波長５９０～６２０ｎｍの赤色蛍光ピークを有する酸化物蛍光体（好ましくは（ＢａＳｒ）３ＳｉＯ５：Ｅｕ）を含有する赤色発光の蛍光体シート形成用組成物から形成し、他方を、青色励起光の照射により波長５３０～５５０ｎｍの緑色蛍光ピークを有する硫化系蛍光体（好ましくはＳｒＧａ２Ｓ４：Ｅｕ）を含有する蛍光体シート形成用組成物から形成することが好ましい。 Although FIG. 1 shows an example in which the phosphor layer 1 is a single layer, as shown in FIG. 2, a laminated phosphor having a two-layer structure in which two phosphor layers 1 a and 1 b are laminated via a transparent separator 3. The layer 20 may be used. In this case as well, the pair of transparent base materials 2a and 2b are sandwiched. By adopting a two-layer structure in this way, phosphors that easily react with each other (for example, CaS: Eu and SrCa 2 S 4 : Eu), the phosphor and the film-forming composition component can be arranged in separate layers, As a result, these unintended reactions can be suppressed, and the lifetime of the phosphor sheet can be extended. In this case, one of the phosphor layers 1a and 1b emits red light containing an oxide phosphor (preferably (BaSr) 3 SiO 5 : Eu) having a red fluorescence peak with a wavelength of 590 to 620 nm when irradiated with blue excitation light. A phosphor containing a sulfur-based phosphor (preferably SrGa 2 S 4 : Eu) having a green fluorescence peak with a wavelength of 530 to 550 nm by irradiation with blue excitation light. It is preferable to form from the sheet forming composition.
　蛍光体層１、１ａ、１ｂの厚みは、薄すぎると相応して蛍光体の絶対量が少なくなるので十分な発光強度を得ることができず、他方、厚すぎるとターゲットとなる色度が得られないので、好ましくは２０～１５０μｍ、より好ましくは６０～１２０μｍである。 If the thickness of the phosphor layers 1, 1a, 1b is too thin, the absolute amount of the phosphor is correspondingly reduced, so that sufficient light emission intensity cannot be obtained. On the other hand, if the thickness is too thick, target chromaticity is obtained. Therefore, the thickness is preferably 20 to 150 μm, more preferably 60 to 120 μm.
　透明基材２ａ、２ｂや透明セパレータ３としては、厚さ１０～１００μｍの熱可塑性樹脂フィルム、熱又は光硬化性樹脂フィルムを使用することができる。例えば、ポリエステルフィルム、ポリアミドフィルム、ポリイミドフィルム、ポリスルホンフィルム、トリアセチルセルロースフィルム、ポリオレフィンフィルム等を挙げることができる。これらのフィルムの表面には、蛍光体シート形成用組成物に対する密着性を改善するために、必要に応じて、コロナ放電処理、シランカップリング剤処理等を施してもよい。 As the transparent substrates 2a and 2b and the transparent separator 3, a thermoplastic resin film having a thickness of 10 to 100 μm, a heat or a photocurable resin film can be used. For example, a polyester film, a polyamide film, a polyimide film, a polysulfone film, a triacetyl cellulose film, a polyolefin film, and the like can be given. In order to improve the adhesion to the phosphor sheet-forming composition, the surfaces of these films may be subjected to corona discharge treatment, silane coupling agent treatment or the like, if necessary.
　本発明においては、更に、図１及び図２の蛍光体シート１０を、その両面から、更に、図３及び図４に示すように、２枚の封止フィルム３０ａ、３０ｂで封止することが好ましい。これにより蛍光体層１、１ａ、１ｂへの水分の侵入をより防止することができる。この場合、蛍光体シート１０の側面も露出しないように封止することが好ましい。 In the present invention, the phosphor sheet 10 in FIGS. 1 and 2 can be further sealed from both sides with two sealing films 30a and 30b as shown in FIGS. preferable. Thereby, the penetration | invasion of the water | moisture content to the fluorescent substance layers 1, 1a, 1b can be prevented more. In this case, it is preferable to seal so that the side surface of the phosphor sheet 10 is not exposed.
　このような封止フィルム３０ａ、３０ｂとしては、図５に示すように、ベースフィルム３１に接着層３２が形成されたものを使用することができる。また、封止フィルム３０ａ、３０ｂの水蒸気バリアー性を向上させるために、接着層３２側のベースフィルム３１の表面またはその反対側の表面に、厚さ５～２０ｎｍの酸化ケイ素層３３を蒸着法等により形成してもよい。後者の場合、酸化ケイ素層３３上に、接着層（図示せず）を介して表面保護フィルム３４を積層してもよい。 As such sealing films 30a and 30b, those in which an adhesive layer 32 is formed on a base film 31 can be used as shown in FIG. Further, in order to improve the water vapor barrier property of the sealing films 30a and 30b, a silicon oxide layer 33 having a thickness of 5 to 20 nm is deposited on the surface of the base film 31 on the adhesive layer 32 side or on the opposite surface. May be formed. In the latter case, the surface protective film 34 may be laminated on the silicon oxide layer 33 via an adhesive layer (not shown).
　ベースフィルム３１や表面保護フィルム３４としては、既に説明した透明基材２ａ、２ｂや透明セパレータ３で例示したフィルムの中から適宜選択して使用することができる。 The base film 31 and the surface protection film 34 can be appropriately selected from the films exemplified for the transparent substrates 2a and 2b and the transparent separator 3 already described.
　接着層３２並びに表面保護フィルム３４の積層の際の接着層としては、ウレタン系接着剤、アクリル系接着剤等、公知の接着剤の中から適宜選択して使用することができる。接着層３２の厚みは、通常１０～５０μｍである。 As the adhesive layer at the time of laminating the adhesive layer 32 and the surface protective film 34, it can be appropriately selected from known adhesives such as urethane adhesives and acrylic adhesives. The thickness of the adhesive layer 32 is usually 10 to 50 μm.
　図１に示す、本発明の単層型の蛍光体シート１０は、透明基材２に蛍光体シート形成用組成物を常法により成膜して蛍光体層１を形成し、その上に別の透明基材２を積層することにより製造することができる。更に、蛍光体シート１０の両面を接着層３２が内側となるように封止フィルム３０ａ、３０ｂで挟み、全体を熱圧着することにより、図３に示す構造の蛍光体シート１０を製造することができる。 A single-layer phosphor sheet 10 of the present invention shown in FIG. 1 forms a phosphor layer 1 by forming a phosphor sheet-forming composition on a transparent substrate 2 by a conventional method, and separates the phosphor layer 1 thereon. It can manufacture by laminating | stacking the transparent base material 2 of. Furthermore, the phosphor sheet 10 having the structure shown in FIG. 3 can be manufactured by sandwiching both surfaces of the phosphor sheet 10 with the sealing films 30a and 30b so that the adhesive layer 32 is on the inner side and thermocompressing the whole. it can.
　なお、蛍光体層１に含まれる光硬化型化合物に対して、例えば紫外線等の活性エネルギー線を照射して光硬化（重合）させる必要があるが、この場合、蛍光体層１に対して活性エネルギー線を直接照射してもよいし、又は透明基材２越し若しくは封止フィルム３０ａ又は３０ｂ越しに活性エネルギー線を照射してもよい。 The photocurable compound contained in the phosphor layer 1 must be photocured (polymerized) by irradiating active energy rays such as ultraviolet rays, for example. In this case, the photocurable compound is active against the phosphor layer 1. You may irradiate an energy ray directly, or you may irradiate an active energy ray through the transparent base material 2 or the sealing film 30a or 30b.
　図２に示す、本発明の２層型の蛍光体シート１０は、透明基材２ａに蛍光体シート形成用組成物を常法により成膜して蛍光体層１ａを形成し、その上に透明セパレータ３を積層し、更に、先の蛍光体シート形成用組成物と異なる蛍光体を含む別の蛍光体シート形成用組成物を常法により成膜して蛍光体層１ｂを形成し、その上に透明基材２ｂを積層することにより製造することができる。更に、蛍光体シート１０の両面を接着層３２が内側となるように封止フィルム３０ａ、３０ｂで挟み、全体を熱圧着することにより、図４に示す構造の蛍光体シート１０を製造することができる。 The two-layer phosphor sheet 10 of the present invention shown in FIG. 2 forms a phosphor layer 1a by forming a phosphor sheet-forming composition on a transparent substrate 2a by a conventional method, and a transparent layer is formed thereon. A separator 3 is laminated, and another phosphor sheet forming composition containing a phosphor different from the above phosphor sheet forming composition is formed by a conventional method to form a phosphor layer 1b. It can manufacture by laminating | stacking the transparent base material 2b. Furthermore, the phosphor sheet 10 having the structure shown in FIG. 4 can be manufactured by sandwiching both surfaces of the phosphor sheet 10 with the sealing films 30a and 30b so that the adhesive layer 32 is on the inner side and thermocompressing the whole. it can.
　なお、蛍光体層１ａ、１ｂに含まれる光重合型化合物に対して、例えば紫外線等の活性エネルギー線を照射して光硬化（重合）させる必要があるが、この場合、蛍光体層１ａ、１ｂに対して活性エネルギー線を直接照射してもよいし、又は透明基材２ａ、２ｂ、透明セパレータ３及び／若しくは封止フィルム３０ａ、３０ｂ越しに活性エネルギー線を照射させてもよい。 The photopolymerizable compounds contained in the phosphor layers 1a and 1b need to be photocured (polymerized) by irradiating active energy rays such as ultraviolet rays, for example. In this case, the phosphor layers 1a and 1b The active energy ray may be directly irradiated to the transparent substrate 2a, 2b, the transparent separator 3 and / or the active film 30a, 30b.
　以上説明した本発明の蛍光体シートは、蛍光体シートとそれに対して照射する励起光を発する励起光源とを有する発光装置の当該蛍光体シートとして好ましく適用することができる。このような光学装置を構成する他の構成要素（例えば、光拡散部材）は、公知の光学装置（特開２０１０－２２５３７３号公報の図６参照）の構成と同様とすることができる。この発光装置は、それ自体照明装置として使用することができる。また、液晶表示素子のバックライトとしても使用することができる。 The phosphor sheet of the present invention described above can be preferably applied as the phosphor sheet of a light emitting device having a phosphor sheet and an excitation light source that emits excitation light applied to the phosphor sheet. Other components (for example, a light diffusing member) constituting such an optical device can be the same as the configuration of a known optical device (see FIG. 6 of JP 2010-225373 A). This light emitting device can itself be used as a lighting device. It can also be used as a backlight for liquid crystal display elements.
　以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
　　実施例１（単層型蛍光体シートの製造）
（緑赤混色蛍光体シート形成用組成物の調製）
　光硬化型のウレタンメタクリレート（アロニックス　１６００Ｍ、東亜合成（株））１００質量部に、光重合開始剤（ＢＡＳＦ社製、ダロキュア１１７３）０．５質量部、平均粒径６μｍのＳｒＧａ２Ｓ４：Ｅｕ（硫化系緑色蛍光体）と（ＢａＳｒ）３ＳｉＯ５：Ｅｕ（酸化物赤色蛍光体）をそれぞれ１．５質量部、均一に分散させることにより、蛍光体シート形成用組成物を調製した。 Example 1 (Production of single-layer phosphor sheet)
(Preparation of composition for forming green-red mixed phosphor sheet)
100 parts by mass of photocurable urethane methacrylate (Aronix 1600M, Toa Gosei Co., Ltd.), 0.5 parts by mass of photopolymerization initiator (BASF, Darocur 1173), SrGa 2 S 4 with an average particle size of 6 μm: Eu A phosphor sheet-forming composition was prepared by uniformly dispersing 1.5 parts by mass of (sulfurized green phosphor) and (BaSr) 3 SiO 5 : Eu (oxide red phosphor).
（図１の構造の蛍光体シートの作成）
　厚さ２５μｍのポリエチレンテレフタレートフィルム（Ｔ１１、東レ（株））に、蛍光体シート形成用組成物を乾燥厚さが１１５μｍとなるように塗布し、次に紫外線を照射して（７０００ｍＪ／ｃｍ２）ウレタンメタクリレートを重合させることにより蛍光体層を形成した。その蛍光体層上に厚さ３８μｍのポリエチレンテレフタレートフィルム（Ａ４３００、東洋紡（株））を積層し、熱圧着処理（１００℃、０．２Ｐａ）を行うことにより図１の構造の蛍光体シートを得た。 (Preparation of phosphor sheet having the structure of FIG. 1)
A phosphor sheet-forming composition was applied to a polyethylene terephthalate film (T11, Toray Industries, Inc.) having a thickness of 25 μm so as to have a dry thickness of 115 μm, and then irradiated with ultraviolet rays (7000 mJ / cm 2 ). A phosphor layer was formed by polymerizing urethane methacrylate. A polyethylene terephthalate film (A4300, Toyobo Co., Ltd.) having a thickness of 38 μm is laminated on the phosphor layer, and a thermocompression treatment (100 ° C., 0.2 Pa) is performed to obtain a phosphor sheet having the structure of FIG. It was.
（封止フィルムの作成）
　厚さ２５μｍのポリエチレンテレフタレートフィルム（Ｔ－１１、東レ（株））の片面に厚さ２０～２５μｍのポリオレフィン系接着層（セプトンＶ９８２７、（株）クラレ）を形成した。このポリエチレンテレフタレートフィルムの他面に、ウレタン系接着層が形成された表面保護フィルムを、ウレタン系接着層を介して積層することにより封止フィルムを作成した。表面保護フィルムは、厚さ約２０ｎｍの酸化ケイ素蒸着層が形成された厚さ１２μｍのポリエチレンテレフタレートフィルム（テックバリア、三菱樹脂（株））の当該酸化ケイ素蒸着層上に、厚さ１～２μｍのウレタン系接着層を形成することにより作成したものである。得られた封止フィルムの透湿度は０．３ｇ／ｍ２・２４ｈｒ・ａｔｍであった。 (Creation of sealing film)
A polyolefin adhesive layer (Septon V9827, Kuraray Co., Ltd.) having a thickness of 20 to 25 μm was formed on one surface of a polyethylene terephthalate film (T-11, Toray Industries, Inc.) having a thickness of 25 μm. The sealing film was created by laminating | stacking the surface protection film in which the urethane type adhesive layer was formed on the other surface of this polyethylene terephthalate film through the urethane type adhesive layer. The surface protective film has a thickness of 1 to 2 μm on the silicon oxide deposited layer of a 12 μm thick polyethylene terephthalate film (Tech Barrier, Mitsubishi Plastics, Inc.) on which a silicon oxide deposited layer having a thickness of about 20 nm is formed. It was created by forming a urethane adhesive layer. The moisture permeability of the obtained sealing film was 0.3 g / m 2 · 24 hr · atm.
（図３の構造の蛍光体シートの作成）
　図１の構造の蛍光体シートの両面に封止フィルムを配し、熱圧着処理（１００℃、０．２Ｐａ）することにより、封止フィルムで封止された蛍光体シートを得た。 (Preparation of phosphor sheet having the structure of FIG. 3)
The phosphor sheet sealed with the sealing film was obtained by disposing the sealing film on both surfaces of the phosphor sheet having the structure of FIG. 1 and performing thermocompression treatment (100 ° C., 0.2 Pa).
　　実施例２（２層型蛍光体シートの製造）
（緑色蛍光体シート形成用組成物の調製）
　光硬化型のウレタンメタクリレート（アロニックス　１６００Ｍ、東亜合成（株））１００質量部に、光重合開始剤（ＢＡＳＦ社製、ダロキュア１１７３）０．５質量部、平均粒径６μｍのＳｒＧａ２Ｓ４：Ｅｕ（硫化系緑色蛍光体）を１．５質量部、均一に分散させることにより、緑色蛍光体シート形成用組成物を調製した。 Example 2 (Production of two-layer phosphor sheet)
(Preparation of composition for forming green phosphor sheet)
100 parts by mass of photocurable urethane methacrylate (Aronix 1600M, Toa Gosei Co., Ltd.), 0.5 parts by mass of photopolymerization initiator (BASF, Darocur 1173), SrGa 2 S 4 with an average particle size of 6 μm: Eu A green phosphor sheet-forming composition was prepared by uniformly dispersing 1.5 parts by mass of (sulfurized green phosphor).
（赤色蛍光体シート形成用組成物の調製）
　光硬化型のウレタンメタクリレート（アロニックス　１６００Ｍ、東亜合成（株））１００質量部に、光重合開始剤（ＢＡＳＦ社製、ダロキュア１１７３）０．５質量部、平均粒径１０μｍの（ＢａＳｒ）３ＳｉＯ５：Ｅｕ（酸化物赤色蛍光体）を３質量部、均一に分散させることにより、赤色蛍光体シート形成用組成物を調製した。 (Preparation of composition for forming red phosphor sheet)
(BaSr) 3 SiO 5 with 100 parts by mass of photocurable urethane methacrylate (Aronix 1600M, Toa Gosei Co., Ltd.), 0.5 parts by mass of a photopolymerization initiator (BASF, Darocur 1173) and an average particle size of 10 μm : A composition for forming a red phosphor sheet was prepared by uniformly dispersing 3 parts by mass of Eu (oxide red phosphor).
（図２の構造の蛍光体シートの作成）
　厚さ２５μｍのポリエチレンテレフタレートフィルム（Ｔ１１、東レ（株））に、緑色蛍光体シート形成用組成物を乾燥厚さが１１５μｍとなるように塗布し、次に紫外線を照射して（７０００ｍＪ／ｃｍ２）ウレタンメタクリレートを重合させて緑色蛍光体層を形成した。 (Preparation of phosphor sheet having the structure of FIG. 2)
A green phosphor sheet forming composition was applied to a polyethylene terephthalate film (T11, Toray Industries, Inc.) having a thickness of 25 μm so that the dry thickness was 115 μm, and then irradiated with ultraviolet rays (7000 mJ / cm 2). ) Urethane methacrylate was polymerized to form a green phosphor layer.
　その上に、厚さ３８μｍの透明セパレータ（ポリエチエレンテレフタレートフィルム（Ａ４３００、東洋紡（株）））を積層し、当該透明セパレータ上に、赤色蛍光体シート形成用組成物を乾燥厚さで２０μｍとなるように塗布し、次に紫外線を照射して（７０００ｍＪ／ｃｍ２）ウレタンメタクリレートを重合させることにより赤色蛍光体層を形成した。更に、厚さ２５μｍのポリエチレンテレフタレートフィルム（Ｔ１１、東レ（株））を積層することにより図２の構造の蛍光体シートを得た。 A 38 μm thick transparent separator (polyethylene terephthalate film (A4300, Toyobo Co., Ltd.)) is laminated thereon, and the red phosphor sheet-forming composition is 20 μm in dry thickness on the transparent separator. Then, an ultraviolet ray was irradiated (7000 mJ / cm 2 ) to polymerize urethane methacrylate to form a red phosphor layer. Further, a 25 μm thick polyethylene terephthalate film (T11, Toray Industries, Inc.) was laminated to obtain a phosphor sheet having the structure of FIG.
（図４の構造の蛍光体シートの作成）
　図２の構造の蛍光体シートの両面に、実施例１で使用したものと同じ封止フィルムを配し、熱圧着処理（１００℃、０．２Ｐａ）することにより、封止フィルムで封止された蛍光体シートを得た。 (Preparation of phosphor sheet having the structure of FIG. 4)
The same sealing film as that used in Example 1 is disposed on both sides of the phosphor sheet having the structure shown in FIG. 2, and is sealed with the sealing film by thermocompression treatment (100 ° C., 0.2 Pa). A phosphor sheet was obtained.
　　実施例３（緑色単色の単層型蛍光体シートの作成）
　（ＢａＳｒ）３ＳｉＯ５：Ｅｕ（酸化物赤色蛍光体）を使用しない以外は、実施例１と同様にして、蛍光体シート用組成物を調整し、図１及び更に図３の構造の蛍光体シートを得た。この蛍光体シートは、緑色単色である。 Example 3 (Preparation of green single-color phosphor sheet)
Except not using (BaSr) 3 SiO 5 : Eu (oxide red phosphor), a phosphor sheet composition was prepared in the same manner as in Example 1, and the phosphor having the structure of FIG. 1 and FIG. 3 was further prepared. A sheet was obtained. This phosphor sheet is a single green color.
　　比較例１
　ウレタンメタクリレートに代えて、ブチルメタクリレート－グリシジルメタクリレート（ＢＭＡ－ＧＭＡ）共重合体（ＤＦ－２４２、藤倉化成（株））を使用すること以外、実施例１と同様にして蛍光体シート形成用組成物を調製し、図１、更に図３の構造の蛍光体シートを製造した。 Comparative Example 1
A composition for forming a phosphor sheet in the same manner as in Example 1, except that butyl methacrylate-glycidyl methacrylate (BMA-GMA) copolymer (DF-242, Fujikura Kasei Co., Ltd.) is used instead of urethane methacrylate. And a phosphor sheet having the structure shown in FIG. 1 and FIG. 3 was produced.
　　比較例２
　ウレタンメタクリレートに代えて、メチルメタクリレート－ブチルアクリレート（ＭＭＡ－ＢＡ）共重合体（ＮＡＢＳＴＡＲ　Ｎ８００ＡＳ、（株）カネカ）を使用すること以外、実施例１と同様にして蛍光体シート形成用組成物を調製し、図１、更に図３の構造の蛍光体シートを製造した。 Comparative Example 2
A phosphor sheet-forming composition was prepared in the same manner as in Example 1 except that methyl methacrylate-butyl acrylate (MMA-BA) copolymer (NABSTAR N800AS, Kaneka Corporation) was used instead of urethane methacrylate. Thus, a phosphor sheet having the structure of FIG. 1 and FIG. 3 was manufactured.
　　比較例３
　ウレタンメタクリレートに代えて、水添スチレン－エチレン－ブチレン－スチレンブロック（水添ＳＥＢＳ）共重合体（セプトンＶ９８２７、（株）クラレ）を使用することと紫外線を照射しないこと以外、実施例１と同様にして蛍光体シート形成用組成物を調製し、図１、更に図３の構造の蛍光体シートを製造した。 Comparative Example 3
Similar to Example 1 except that instead of urethane methacrylate, a hydrogenated styrene-ethylene-butylene-styrene block (hydrogenated SEBS) copolymer (Septon V9827, Kuraray Co., Ltd.) is used and no ultraviolet rays are irradiated. Thus, a phosphor sheet forming composition was prepared, and a phosphor sheet having the structure of FIG. 1 and FIG. 3 was produced.
　　比較例４
　ウレタンメタクリレートに代えて、水添スチレン－エチレン－ブチレン－スチレンブロック（水添ＳＥＢＳ）共重合体（セプトンＶ９８２７、（株）クラレ）４０重量部と無水マレイン酸０．５重量部の割合で使用したことと、紫外線を照射しないこと以外、実施例１と同様にして蛍光体シート形成用組成物を調製し、図１、更に図３の構造の蛍光体シートを製造した。 Comparative Example 4
Instead of urethane methacrylate, hydrogenated styrene-ethylene-butylene-styrene block (hydrogenated SEBS) copolymer (Septon V9827, Kuraray Co., Ltd.) 40 parts by weight and maleic anhydride 0.5 parts by weight were used. A phosphor sheet-forming composition was prepared in the same manner as in Example 1 except that no ultraviolet rays were irradiated, and a phosphor sheet having the structure shown in FIG. 1 and FIG. 3 was produced.
　　比較例５
　ウレタンメタクリレートに代えて、水添スチレン－エチレン－ブチレン－スチレンブロック（水添ＳＥＢＳ）共重合体（セプトンＶ９８２７、（株）クラレ）を使用することと紫外線を照射しないこと以外、実施例３と同様にして蛍光体シート形成用組成物を調整し、図１、更に図３の構造の蛍光体シートを製造した。この蛍光体シートは、緑色単色である。 Comparative Example 5
Similar to Example 3 except that instead of urethane methacrylate, a hydrogenated styrene-ethylene-butylene-styrene block (hydrogenated SEBS) copolymer (Septon V9827, Kuraray Co., Ltd.) is used and no ultraviolet rays are irradiated. Thus, a phosphor sheet-forming composition was prepared to produce a phosphor sheet having the structure of FIG. 1 and FIG. This phosphor sheet is a single green color.
　　比較例６
　ウレタンメタクリレートに代えて、ブチルメタクリレート－グリシジルメタクリレート（ＢＭＡ－ＧＭＡ）共重合体（ＤＦ－２４２、藤倉化成（株））を使用することと紫外線を照射しないこと以外、実施例３と同様にして蛍光体シート形成用組成物を調製し、図１、更に図３の構造の蛍光体シートを製造した。この蛍光体シートは、緑色単色である。 Comparative Example 6
Instead of urethane methacrylate, fluorescence was used in the same manner as in Example 3 except that a butyl methacrylate-glycidyl methacrylate (BMA-GMA) copolymer (DF-242, Fujikura Kasei Co., Ltd.) was used and no ultraviolet ray was irradiated. A composition for forming a body sheet was prepared, and a phosphor sheet having the structure of FIG. 1 and FIG. 3 was produced. This phosphor sheet is a single green color.
（評価）
　各実施例及び各比較例の封止された蛍光体シートについて、以下のように色度差と発光スペクトル強度比とを測定し、評価した。得られた結果を表１、表２に示す。 (Evaluation)
For the sealed phosphor sheets of each Example and each Comparative Example, the chromaticity difference and the emission spectrum intensity ratio were measured and evaluated as follows. The obtained results are shown in Tables 1 and 2.
＜色度差（色度ズレ）＞
　得られた封止された蛍光体シートを、６０℃、９０％Ｒｈの環境中に５００時間放置した。放置前後の色度差（ＪＩＳ　Ｚ８５１８）Δｕ′ｖ′を求め、以下の基準で評価した。 <Chromaticity difference (chromaticity deviation)>
The obtained sealed phosphor sheet was left in an environment of 60 ° C. and 90% Rh for 500 hours. The difference in chromaticity before and after standing (JIS Z8518) Δu′v ′ was determined and evaluated according to the following criteria.
ランク　　基準
　Ａ：　Δｕ′ｖ′＜０．００５
　Ｂ：　０．００５≦Δｕ′ｖ′＜０．０１０
　Ｃ：　０．０１０≦Δｕ′ｖ′ Rank criterion A: Δu′v ′ <0.005
B: 0.005 ≦ Δu′v ′ <0.010
C: 0.010 ≦ Δu′v ′
＜発光スペクトル強度比＞
　得られた封止された蛍光体シートを、８５℃、８５％Ｒｈの環境中に４８時間放置し、放置前と放置後の発光スペクトル強度（ＳＲ）を分光放射計（トプコンＳＲ－３、（株）トプコン）を用いて測定し、放置前の発光スペクトル強度（ＳＲ）に対する放置後の発光スペクトル強度（ＳＲ）の比を求め、以下の基準で評価した。実用上、ＳＲ比は０．７以上（Ａ評価）であることが望まれる。 <Emission spectrum intensity ratio>
The obtained sealed phosphor sheet was left in an environment of 85 ° C. and 85% Rh for 48 hours, and the emission spectrum intensity (SR) before and after being left was measured with a spectroradiometer (Topcon SR-3, ( The ratio of the emission spectrum intensity (SR) after being left to the emission spectrum intensity (SR) before being left is determined and evaluated according to the following criteria. In practice, the SR ratio is desired to be 0.7 or higher (A evaluation).
ランク　　基準
　Ａ：　０．７≦ＳＲ比
　Ｂ：　０．５≦ＳＲ比＜０．７
　Ｃ：　ＳＲ比＜０．５ Rank Criteria A: 0.7 ≦ SR ratio B: 0.5 ≦ SR ratio <0.7
C: SR ratio <0.5
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１からわかるように、実施例１の蛍光体シートの場合、色度差がＡ評価であった。それに対し、比較例１～４の蛍光体シートの場合、成膜用組成物主成分としてウレタンメタクリレートに代えて、ＢＭＡ－ＧＭＡ共重合体、ＭＭＡ－ＢＡ共重合体、水添ＳＥＢＳ、または水添ＳＥＢＳに無水マレイン酸を加えたものを使用した結果、色度差の評価がＢ又はＣであった。また、実施例２の蛍光体シートは、実施例１で使用した緑色蛍光体及び赤色蛍光体を別々の蛍光体層に配置したものであるから、蛍光体同士の組み合わせが影響する色度差は予想通りＡ評価であった。 As can be seen from Table 1, in the case of the phosphor sheet of Example 1, the chromaticity difference was A evaluation. In contrast, in the case of the phosphor sheets of Comparative Examples 1 to 4, BMA-GMA copolymer, MMA-BA copolymer, hydrogenated SEBS, or hydrogenated instead of urethane methacrylate as the film forming composition main component. As a result of using SEBS added with maleic anhydride, the evaluation of the chromaticity difference was B or C. Moreover, since the fluorescent substance sheet of Example 2 arranges the green fluorescent substance and red fluorescent substance which were used in Example 1 in a separate fluorescent substance layer, the chromaticity difference which the combination of fluorescent substance influences is the same. As expected, the evaluation was A.
　次に、表２からわかるように、実施例３、比較例５及び６の蛍光体シートは、緑色単色発光するものであるから、発光スペクトル強度比を測定する例として適切である。実際、実施例３の蛍光体シートの場合、発光スペクトル強度比はＡ評価であり、それに対して、比較例５及び６の蛍光体シートの場合、発光スペクトル強度比はＢ評価又はＣ評価であった。 Next, as can be seen from Table 2, since the phosphor sheets of Example 3 and Comparative Examples 5 and 6 emit green monochromatic light, they are suitable as examples for measuring the emission spectrum intensity ratio. In fact, in the case of the phosphor sheet of Example 3, the emission spectrum intensity ratio is A evaluation, whereas in the case of the phosphor sheets of Comparative Examples 5 and 6, the emission spectrum intensity ratio is B evaluation or C evaluation. It was.
　本発明の蛍光体シート形成用組成物は、成膜用組成物として、多数の樹脂や重合性化合物の中から、熱可塑性樹脂などに比べ、耐光性に優れ、可視光に対する光吸収性が低い樹脂を与えることができ、しかも比較的低コストで入手可能な光硬化型化合物を使用する。よって、本発明の蛍光体シート形成用組成物は、耐光性に優れ、可視光に対する光吸収性が低く、水分による蛍光体の変質が抑制され、低コストの蛍光体シートの製造原料として有用である。 The phosphor sheet-forming composition of the present invention is excellent in light resistance and low in light absorption for visible light compared to thermoplastic resins, etc., among many resins and polymerizable compounds as a film-forming composition. A photocurable compound that can provide a resin and is available at a relatively low cost is used. Therefore, the phosphor sheet-forming composition of the present invention is excellent in light resistance, has a low light absorption property for visible light, suppresses phosphor alteration due to moisture, and is useful as a raw material for producing a low-cost phosphor sheet. is there.
　１、１ａ、１ｂ　蛍光体層
　２、２ａ、２ｂ　透明基材
　３　透明セパレータ
　１０　蛍光体シート
　２０　積層蛍光体層
　３０ａ、３０ｂ　封止フィルム
　３１　ベースフィルム
　３２　接着層
　３３　酸化ケイ素層
　３４　表面保護フィルム DESCRIPTION OF SYMBOLS 1, 1a, 1b Phosphor layer 2, 2a, 2b Transparent base material 3 Transparent separator 10 Phosphor sheet 20 Laminated phosphor layer 30a, 30b Sealing film 31 Base film 32 Adhesive layer 33 Silicon oxide layer 34 Surface protective film

Claims (16)

  1. 　成膜用組成物と、励起光の照射により蛍光を発する粉末状の蛍光体とを含有する蛍光体シート形成用組成物であって、
    　成膜用組成物が、光硬化型化合物を含有する蛍光体シート形成用組成物。     A phosphor sheet-forming composition comprising a film-forming composition and a powdered phosphor that emits fluorescence when irradiated with excitation light,
    A phosphor sheet-forming composition, wherein the film-forming composition contains a photocurable compound.
  2. 　光硬化型化合物が、光硬化型（メタ）アクリレートを含有する請求項１記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 1, wherein the photocurable compound contains a photocurable (meth) acrylate.
  3. 　光硬化型（メタ）アクリレートが、ウレタン（メタ）アクリレートを含有する請求項２記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 2, wherein the photocurable (meth) acrylate contains urethane (meth) acrylate.
  4. 　ウレタン（メタ）アクリレートが、ポリオールとイソホロンジイソシアネートとの反応物を２－ヒドロキシプロピルアクリレートでエステル化したものである請求項３記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 3, wherein the urethane (meth) acrylate is obtained by esterifying a reaction product of a polyol and isophorone diisocyanate with 2-hydroxypropyl acrylate.
  5. 　光硬化型（メタ）アクリレート１００質量部中に、ウレタン（メタ）アクリレートが少なくとも１０質量部含有されている請求項３又は４記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 3 or 4, wherein at least 10 parts by mass of urethane (meth) acrylate is contained in 100 parts by mass of photocurable (meth) acrylate.
  6. 　蛍光体が、青色励起光の照射により波長５９０～６２０ｎｍの赤色蛍光ピークを有する酸化物蛍光体を少なくとも含む請求項１～５のいずれかに記載の蛍光体シート形成用組成物。 6. The phosphor sheet forming composition according to claim 1, wherein the phosphor includes at least an oxide phosphor having a red fluorescence peak with a wavelength of 590 to 620 nm when irradiated with blue excitation light.
  7. 　酸化物蛍光体が、（ＢａＳｒ）３ＳｉＯ５：Ｅｕである請求項６記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 6, wherein the oxide phosphor is (BaSr) 3 SiO 5 : Eu.
  8. 　蛍光体が、青色励起光の照射により波長５３０～５５０ｎｍの緑色蛍光ピークを有する硫化系蛍光体を少なくとも含む請求項１～５のいずれかに記載の蛍光体シート形成用組成物。 6. The phosphor sheet forming composition according to claim 1, wherein the phosphor includes at least a sulfur-based phosphor having a green fluorescence peak with a wavelength of 530 to 550 nm when irradiated with blue excitation light.
  9. 　硫化系蛍光体が、ＳｒＧａ２Ｓ４：Ｅｕである請求項８記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 8, wherein the sulfur-based phosphor is SrGa 2 S 4 : Eu.
  10. 　蛍光体が、青色励起光の照射により波長５９０～６２０ｎｍの赤色蛍光ピークを有する酸化物蛍光体と、青色励起光の照射により波長５３０～５５０ｎｍの緑色蛍光ピークを有する硫化系蛍光体との混合蛍光体である請求項１～５のいずれかに記載の蛍光体シート形成用組成物。 The phosphor is a mixed fluorescence of an oxide phosphor having a red fluorescence peak with a wavelength of 590 to 620 nm when irradiated with blue excitation light and a sulfide-based phosphor having a green fluorescence peak with a wavelength of 530 to 550 nm upon irradiation with blue excitation light. 6. The phosphor sheet-forming composition according to claim 1, wherein the phosphor sheet-forming composition is a body.
  11. 　赤色蛍光ピークを有する酸化物蛍光体が（ＢａＳｒ）３ＳｉＯ５：Ｅｕであり、緑色蛍光ピークを有する硫化系蛍光体がＳｒＧａ２Ｓ４：Ｅｕである請求項１０記載の蛍光体シート形成用組成物。 The composition for forming a phosphor sheet according to claim 10, wherein the oxide phosphor having a red fluorescence peak is (BaSr) 3 SiO 5 : Eu, and the sulfur-based phosphor having a green fluorescence peak is SrGa 2 S 4 : Eu. object.
  12. 　励起光の照射により蛍光を発する蛍光体層が一対の透明基材に挟持されている蛍光体シートであって、蛍光体層が、請求項１の蛍光体シート形成用組成物を成膜したものである蛍光体シート。 A phosphor sheet in which a phosphor layer that emits fluorescence when irradiated with excitation light is sandwiched between a pair of transparent substrates, wherein the phosphor layer is formed by forming the phosphor sheet forming composition according to claim 1 A phosphor sheet.
  13. 　蛍光体層が、請求項１０又は１１記載の蛍光体シート形成用組成物を単層で成膜したものである請求項１２記載の蛍光体シート。 The phosphor sheet according to claim 12, wherein the phosphor layer is formed by forming a single layer of the phosphor sheet forming composition according to claim 10 or 11.
  14. 　蛍光体層が、透明セパレータの片面に請求項６もしくは７記載の蛍光体シート形成用組成物を単層で成膜した赤色蛍光体層と、透明セパレータの他面に請求項８もしくは９記載の蛍光体シート形成用組成物を単層で成膜した緑色蛍光体層とが積層された構造となっている請求項１１記載の蛍光体シート。 The phosphor layer comprises: a red phosphor layer in which the phosphor sheet forming composition according to claim 6 or 7 is formed as a single layer on one side of the transparent separator; and the other side of the transparent separator according to claim 8 or 9. The phosphor sheet according to claim 11, wherein the phosphor sheet has a structure in which a green phosphor layer in which the phosphor sheet-forming composition is formed as a single layer is laminated.
  15. 　片面に接着剤層を有する封止フィルム２枚で、更に、両側から封止した請求項１２～１４のいずれかに記載の蛍光体シート。 The phosphor sheet according to any one of claims 12 to 14, further comprising two sealing films each having an adhesive layer on one side and further sealed from both sides.
  16. 　請求項１２～１５のいずれかに記載の蛍光体シートと、蛍光体シートに照射する励起光を発する励起光源とを有する発光装置。 A light-emitting device comprising: the phosphor sheet according to any one of claims 12 to 15; and an excitation light source that emits excitation light applied to the phosphor sheet.
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