WO2015152341A1 - 疎水化処理蛍光体及び発光装置 - Google Patents
疎水化処理蛍光体及び発光装置 Download PDFInfo
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- WO2015152341A1 WO2015152341A1 PCT/JP2015/060387 JP2015060387W WO2015152341A1 WO 2015152341 A1 WO2015152341 A1 WO 2015152341A1 JP 2015060387 W JP2015060387 W JP 2015060387W WO 2015152341 A1 WO2015152341 A1 WO 2015152341A1
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- phosphor
- light
- hydrophobized
- emitting device
- mass
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 38
- 239000002344 surface layer Substances 0.000 claims abstract description 24
- 229920002545 silicone oil Polymers 0.000 claims abstract description 20
- 150000004668 long chain fatty acids Chemical class 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 238000007789 sealing Methods 0.000 abstract description 22
- 230000007774 longterm Effects 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- 230000004907 flux Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920000995 Spectralon Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004667 medium chain fatty acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- 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
-
- 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
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
-
- 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
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
-
- 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
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Definitions
- the present invention is a hydrophobized phosphor that does not easily peel off at the interface with the sealing resin, and the use of this hydrophobized phosphor has a small change in luminance and luminescent color with time and excellent long-term stability.
- the present invention relates to a light emitting device. More specifically, a hydrophobized phosphor in which a hydrophobic surface layer is formed by attaching a specific hydrophobizing substance to the surface of ⁇ -sialon phosphor particles, and the hydrophobized phosphor as a sealing resin.
- the present invention relates to a light emitting device in which a dispersed material is applied to a light emitting surface on which a light emitting element is mounted and cured.
- a ⁇ -type sialon in which Eu 2+ is dissolved is a luminescent center having a ⁇ -type sialon represented by the general formula: Si 6-z Al z O z N 8-z (z is greater than 0 and 4.2 or less) as a host crystal.
- ⁇ -sialon phosphors activated by Eu 2+ have a small decrease in luminance with temperature rise and are excellent in durability, they are used as green light-emitting phosphors for light-emitting diodes (hereinafter referred to as LEDs) in light-emitting devices. Widely used.
- the phosphor When such a phosphor is mounted on a light-emitting device, generally, the phosphor is dispersed in a light-transmitting sealing resin such as epoxy resin, polycarbonate, or silicon rubber to form a slurry, and this slurry surrounds the light-emitting element on the light-emitting surface. Application and curing are carried out as described above.
- a light-transmitting sealing resin such as epoxy resin, polycarbonate, or silicon rubber
- hydrophobizing substance As a result of intensive studies to solve the above problems, the present inventors attached a specific hydrophobizing substance to the surface of ⁇ -type sialon phosphor particles, and provided a thin film-like surface layer made of the hydrophobizing substance. It has been found that peeling hardly occurs at the interface with the sealing resin.
- hydrophobized phosphor a phosphor having a surface layer made of this hydrophobizing substance
- the present invention Phosphor particles represented by the general formula Si 6-z Al z O z N 8-z : Eu 2+ (z is greater than 0 and 4.2 or less); A surface layer made of a hydrophobizing substance attached to the surface of the phosphor particles,
- the gist is a hydrophobized phosphor in which the hydrophobizing substance is a long chain fatty acid having 12 or more carbon atoms, a silicone oil having a viscosity of 1.5 Pa ⁇ s or less, or both.
- the gist of the present invention is a light emitting device including the above-mentioned hydrophobic treatment phosphor and a light emitting element.
- the hydrophobized phosphor of the present invention has a surface layer made of a specific hydrophobizing substance on the surface of the phosphor particles, so that it has better adhesion to the sealing resin than the conventional ⁇ -sialon phosphor. Excellent and hardly causes peeling at the interface with the sealing resin.
- the light-emitting device of the present invention has small changes over time in luminance and emission color and is excellent in long-term stability. Specifically, the deviation of the chromaticity coordinates CIEy value based on JIS Z8701 after being energized for 1000 hours at 150 mA in an environment where the temperature is 85 ° C. and the relative humidity is 85% is ⁇ 5% of the value before energization. Can be kept within the range.
- the hydrophobized phosphor of the present invention is a ⁇ -sialon phosphor represented by the general formula Si 6-z Al z O z N 8-z : Eu 2+ (z is greater than 0 and 4.2 or less).
- a hydrophobic substance is attached to the surface of the particles in the form of a thin film.
- the phosphor particles used in the hydrophobized phosphor of the present invention are ⁇ -sialons represented by the general formula Si 6-z Al z O z N 8-z (z is greater than 0 and 4.2 or less). Eu 2+ which is the emission center is dissolved in the base crystal, and a well-known ⁇ -type sialon phosphor described in Patent Document 1 and the like can be used.
- the phosphor particles contain a ⁇ -sialon crystal phase with a high purity and as much as possible, and preferably consist of a single phase of ⁇ -sialon crystal. If present, it may contain some amount of inevitable amorphous phase and other crystalline phases.
- the 50% diameter (D50) in the volume-based integrated fraction of the phosphor particles is 1 ⁇ m or more and 30 ⁇ m or less.
- the hydrophobic substance adheres to the surface of the phosphor particles to form a thin surface layer, thereby improving the “hydrophobicity” that is a measure of the affinity of the phosphor particles for the hydrophobic substance.
- the “hydrophobicity” in the present invention is measured by the following method. (1) Weigh 0.2 g of the hydrophobized phosphor to be measured in a 500 ml Erlenmeyer flask. (2) Add 50 ml of ion exchange water to (1) and stir with a stirrer.
- the degree of hydrophobicity of the hydrophobized phosphor of the present invention is 10% or more, preferably 50% or more, more preferably 70% or more, and further preferably 75% or more. If the degree of hydrophobicity is 10% or more, the occurrence of peeling at the interface with the sealing resin can be sufficiently reduced.
- the hydrophobizing substance capable of making the degree of hydrophobization 10% or more one or both of a long-chain fatty acid having 12 or more carbon atoms and a silicone oil having a viscosity of 1.5 Pa ⁇ s or less can be used.
- a saturated or unsaturated higher fatty acid typically having 12 to 30 carbon atoms, more preferably 12 to 22 carbon atoms can be used.
- Examples of the long chain fatty acid having 12 or more carbon atoms that can be used in the present invention include lauric acid (C12), myristic acid (C14), oleic acid (C18), stearic acid (C18), and linoleic acid (C18). And behenic acid (C22).
- the silicone oil having a viscosity of 1.5 Pa ⁇ s or less is typically a silicone oil having a viscosity in the range of 0.01 to 1.5 Pa ⁇ s, more preferably in the range of 0.04 to 0.8 Pa ⁇ s. Can be used. If the viscosity of the silicone oil is too high, the thickness of the surface layer may not be formed uniformly. If the viscosity of the silicone oil is too low, the adhesion to the phosphor particle surface is reduced and a sufficient degree of hydrophobicity is achieved. There are cases where it is not possible. The viscosity is measured at 25 ° C.
- silicone oils having a viscosity of 1.5 Pa ⁇ s or less examples include, for example, hydroxy-terminated dimethylpolysiloxane, dimethylsilicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, poly Ether-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, and the like.
- the method of attaching the hydrophobic substance to the surface of the phosphor particles in a thin film is not particularly limited as long as the phosphor particles and the hydrophobic substance can be mixed uniformly.
- the hydrophobizing substance may be used alone, but may be used by mixing with a solvent capable of dissolving the hydrophobizing substance in order to help uniform mixing with the phosphor particles.
- a solvent capable of dissolving the hydrophobizing substance in order to help uniform mixing with the phosphor particles.
- An example of such a solvent is ethanol.
- the amount of the hydrophobizing substance added to the phosphor particles is preferably such that the thickness of the formed surface layer is 0.02 ⁇ m to 0.5 ⁇ m, more preferably 0.04 ⁇ m to 0.2 ⁇ m.
- the thickness of the surface layer can be adjusted by changing the mixing ratio of the phosphor particles and the hydrophobic substance.
- the hydrophobizing substance is preferably mixed so as to be 1.0% by mass or more and 5.0% by mass or less with respect to 100% by mass of the phosphor particles. If the adhesion amount of the hydrophobic substance or the thickness of the surface layer is too small, the effect of preventing peeling at the interface with the sealing resin tends to be insufficient when dispersed in the sealing resin. If the amount is too large, curing of the sealing resin in the vicinity of the interface is hindered, and color shift with time may occur.
- the light-emitting device of the present invention includes at least a phosphor containing the hydrophobic treatment phosphor described above and a light-emitting element.
- Examples of the light emitting device include a lighting device, a backlight device, an image display device, and a signal device.
- the light emitting element desirably emits light having a wavelength of 240 to 500 nm, and in particular, a blue LED light emitting element having a wavelength of 420 nm to 500 nm is preferable.
- the phosphor used in the light emitting device in addition to the hydrophobized phosphor of the present invention, other phosphors can be used in combination.
- Other phosphors that can be used in combination with the hydrophobized phosphor of the present invention are not particularly limited, and can be appropriately selected according to the luminance and color rendering properties required for the light emitting device. By mixing the hydrophobized phosphor of the present invention with phosphors of other emission colors, white having various color temperatures from white to light bulb can be realized.
- the phosphor containing the hydrophobized phosphor of the present invention is dispersed in a sealing resin to form a slurry, and this slurry is mounted on the light emitting device by molding the slurry so as to surround the light emitting element on the light emitting surface.
- a sealing resin a thermosetting resin such as a silicone resin having fluidity at room temperature can be used.
- JCR6175 manufactured by Toray Dow Corning Co., Ltd. can be used. It is preferable to mix and use the phosphor containing the hydrophobized phosphor of the present invention so as to be 30% by mass or more and 50% by mass or less with respect to the sealing resin.
- the light-emitting device of the present invention uses a hydrophobized phosphor, peeling hardly occurs at the interface with the sealing resin. For this reason, the luminance decrease with time and color shift are small, and the long-term stability is excellent.
- Comparative Example 1 is a conventional phosphor in which a surface layer made of a hydrophobic substance is not provided on the surface of the phosphor particles, and Comparative Examples 2 and 3 are made of a substance different from the hydrophobic substance defined in the present invention. It is the processed fluorescent substance.
- Examples 1 to 7 are hydrophobized phosphors in which a surface layer is formed by attaching a specific hydrophobizing substance defined in the present invention to the surface of phosphor particles.
- the phosphor of Comparative Example 1 includes a mixing step of mixing raw materials, a baking step of baking the raw materials after the mixing step, and an annealing step and an acid for post-processing the sintered body after the baking step. Manufactured through processing steps.
- ⁇ Mixing process> ⁇ -type silicon nitride (SN-E10 grade manufactured by Ube Industries, Ltd., oxygen content 1.0 mass%) 95.45 mass%, aluminum nitride (E grade manufactured by Tokuyama Corporation, oxygen content 0.8 mass%) 3 0.1% by mass, aluminum oxide (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 0.66% by mass, and europium oxide (RU grade manufactured by Shin-Etsu Chemical Co., Ltd.) 0.79% by mass.
- This raw material powder was dry-mixed for 10 minutes with a V-type mixer (S-3, manufactured by Tsutsui Chemical Co., Ltd.).
- a V-type mixer (S-3, manufactured by Tsutsui Chemical Co., Ltd.).
- those that passed through a nylon sieve having an opening of 250 ⁇ m were used in the following steps.
- ⁇ Baking process> The mixture after classification is filled into a cylindrical boron nitride container with a lid (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.), and is heated at 2000 ° C. in a pressurized nitrogen atmosphere of 0.8 MPa in an electric furnace of a carbon heater. It stood for time and baked. After baking, the container was taken out and left to reach room temperature. The obtained massive fired product was crushed with a roll crusher in order to obtain the particle size and particle shape required for the phosphor. The powder that passed through a sieve having an opening of 150 ⁇ m was used in the following steps.
- Acid treatment was performed by immersing the powder after the annealing step in a mixed acid of hydrofluoric acid and nitric acid for 30 minutes.
- the powder together with the mixed acid is passed through a synthetic resin filter, and the powder remaining on the filter is washed with water to obtain Si 6-z Al z O z N 8-z : Eu
- Example 1 The phosphor particles of Comparative Example 1 and oleic acid (manufactured by Kanto Chemical Co., Ltd., deer grade 1) are blended so as to have a ratio of 1.0% by mass of oleic acid to 100% by mass of the phosphor particles. Mixed for minutes. After mixing, the mixture was classified using a sieve having an opening of 75 ⁇ m to obtain a hydrophobized phosphor of Example 1 having a surface layer made of oleic acid having a thickness of 0.04 ⁇ m.
- Example 2 to 7 and Comparative Examples 2 to 3 were produced by the same method and conditions as in Example 1 except that the hydrophobizing substances used and the blending amounts were changed as follows.
- the blending amount of oleic acid was 3.0% by mass and 5.0% by mass with respect to 100% by mass of the phosphor particles, respectively.
- Example 4 1.0% by mass of lauric acid (manufactured by Kanto Chemical Co., Inc.) diluted with ethanol with respect to 100% by mass of the phosphor particles was used as a hydrophobizing substance.
- Example 5 1.0% by mass of stearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) diluted with ethanol with respect to 100% by mass of the phosphor particles was used as a hydrophobizing substance.
- Example 6 1.0% by mass of behenic acid (manufactured by Kanto Chemical Co., Inc.) diluted with ethanol with respect to 100% by mass of the phosphor particles was used as a hydrophobizing substance.
- Example 7 a silicone oil having a viscosity of 0.08 Pa ⁇ s (YF3800 manufactured by Momentive Performance Materials Japan Godo Kaisha, Ltd.) having a viscosity of 0.08 Pa ⁇ s with respect to 100% by mass of the phosphor particles is hydrophobized. Used as.
- Hexanoic acid is a medium chain fatty acid having 6 carbon atoms.
- Comparative Example 3 a silicone oil (KF-96-3000cs, manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 3.0 Pa ⁇ s and 1.0% by mass with respect to 100% by mass of the phosphor particles was used as a hydrophobic substance. Using.
- the film thickness ( ⁇ m) of the surface layer is the thickness of the surface layer formed by the hydrophobic substance adhered to the surface of the phosphor particles, and was calculated from the following equation.
- Film thickness ( ⁇ m) [volume of surface layer (m 3 ) / surface area of phosphor (m 2 )] ⁇ 10 6
- Volume of surface layer (m 3 ) mass of surface layer (g) / [density of surface layer (g / cm 3 ) ⁇ 10 6 ]
- Surface area of phosphor (m 2 ) specific surface area of phosphor (m 2 / g) ⁇ mass of phosphor (g)
- the quantum efficiency of the hydrophobized phosphor was evaluated at room temperature by the following method.
- a standard reflector (Spectralon manufactured by Labsphere) having a reflectivity of 99% was set in the side opening ( ⁇ 10 mm) of the integrating sphere ( ⁇ 60 mm).
- Monochromatic light dispersed at a wavelength of 455 nm from an Xe lamp as a light source was introduced into this integrating sphere with an optical fiber, and the spectrum of reflected light was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.).
- the number of excitation light photons was calculated from the spectrum in the wavelength range of 450 to 465 nm.
- a concave cell filled with a hydrophobic treatment phosphor so as to have a smooth surface is set in the opening of the integrating sphere, irradiated with monochromatic light having a wavelength of 455 nm, and reflected excitation light and fluorescence spectra.
- the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) were calculated from the obtained spectrum data.
- ⁇ Chromaticity CIEx and Chromaticity CIEy> The chromaticity coordinates were measured using a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). Blue light having a wavelength of 455 nm was used as excitation light. The sample portion of the spectrophotometer was filled with the phosphor to be measured, the surface was smoothed, and an integrating sphere was attached. Monochromatic light obtained by splitting light from a Xe lamp as a light source into blue light having a wavelength of 455 nm was introduced into the integrating sphere using an optical fiber. Measurement was performed by irradiating the phosphor with the monochromatic light. Chromaticity coordinates CIEx and CIEy in the XYZ color system defined by JIS Z8701 were calculated from data in the wavelength range of 465 to 780 nm in the measurement results according to JIS Z8724.
- ⁇ Relative peak intensity> As the relative peak intensity (%), the relative intensity when the peak height of the emission spectrum of YAG: Ce phosphor (P46Y3 manufactured by Kasei Optonics Co., Ltd.) was set to 100% was determined.
- the luminous flux retention rate (%) is a value for evaluating the decay of light intensity (luminance) over time.
- the luminous flux retention rate (%) is a comparison of the luminous flux before and after driving a light emitting device with the hydrophobic treated phosphor to be measured mounted on the light emitting surface side of the LED and driving this light emitting device in a high temperature and high humidity environment for a certain period of time.
- the high-speed holding ratio is a value obtained by multiplying 100 by the value obtained by dividing the luminous flux of the LED after 500 hours and the luminous flux of the LED after 1000 hours by the luminous flux before starting energization (elapsed 0 hours).
- the passing value after 1000 hours is 90% or more.
- the chromaticity CIEy retention rate (%) is a value for evaluating the color shift over time.
- the chromaticity CIEy retention rate (%) was evaluated by comparing the chromaticity CIEy before and after being driven for a certain period of time in a high temperature and high humidity environment using the same light emitting device and measurement conditions as those for measuring the luminous flux retention rate. Specifically, the chromaticity CIEy after the lapse of 500 hours and the chromaticity CIEy after the lapse of 1000 hours divided by the chromaticity CIEy before the start of energization (elapsed 0 hours) are multiplied by 100.
- the pass value after the elapse of 500 hours is 90%, and the pass value after the elapse of 1000 hours is 95%.
- the hydrophobized phosphors of Examples 1 to 7 have the fluorescence of Comparative Examples 1 and 2 with respect to internal quantum efficiency, external quantum efficiency, chromaticity CIEx, chromaticity CIEy, and relative peak intensity. There was no significant difference from the body. However, in the phosphors of Comparative Examples 1 and 2, the luminous flux retention rate and chromaticity CIEy retention rate after 1000 hours did not reach the acceptance criteria, whereas the hydrophobic treatment phosphors of Examples 1 to 7 Also satisfied the acceptance criteria, and it was confirmed that changes over time in luminance and emission color were small. Comparative Example 3 was not evaluated because the silicone oil used as the hydrophobizing substance had a high viscosity and a surface layer having a uniform film thickness could not be formed on the surface of the phosphor particles.
- Example 8> A light emitting device in which the hydrophobized phosphor of Example 1 was mounted on the light emitting surface of a blue light emitting LED as a light emitting light source was manufactured. Since this light-emitting device uses the hydrophobized phosphor of Example 1, the luminance and emission color are less changed with time than the light-emitting device using the phosphor of Comparative Example 1, and excellent in long-term stability. .
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Abstract
Description
一般式Si6-zAlzOzN8-z:Eu2+(zは0より大きく4.2以下である)で表される蛍光体粒子と、
蛍光体粒子の表面に付着させた疎水化物質からなる表面層とを有し、
疎水化物質が炭素数12以上の長鎖脂肪酸、粘度1.5Pa・s以下のシリコーンオイル、又はこれらの両方からなる、疎水化処理蛍光体を要旨とする。
本発明の疎水化処理蛍光体は、一般式Si6-zAlzOzN8-z:Eu2+(zは0より大きく4.2以下である)で表されるβ型サイアロンの蛍光体粒子の表面に疎水化物質を薄膜状に付着させたものである。
本発明の疎水化処理蛍光体に用いられる蛍光体粒子は、一般式Si6-zAlzOzN8-z(zは0より大きく4.2以下である)で示されるβ型サイアロンの母体結晶に、発光中心であるEu2+が固溶したものであり、上記特許文献1等に記載される周知のβ型サイアロン蛍光体を用いることができる。
疎水化物質は、蛍光体粒子の表面に付着して薄膜状の表面層を形成することにより、蛍光体粒子の疎水性物質に対する親和性の尺度である「疎水化度」を向上させる。疎水化度を向上させることにより、封止樹脂との濡れ性が改善され、封止樹脂との界面における剥離の発生が抑制される。
本発明における「疎水化度」は、以下の方法によって測定される。
(1)500mlの三角フラスコに測定対象の疎水化処理蛍光体0.2gを秤量する。
(2)イオン交換水50mlを(1)に加え、スターラーにて撹拌する。
(3)撹拌をしたままビュレットよりメタノールを滴下させ、疎水化処理蛍光体の全量がイオン交換水に懸濁された時の滴下量を測定する。
(4)次式より疎水化度を求める。
疎水化度(%)=[メタノール滴下量(ml)]×100/[メタノール滴下量(ml)+イオン交換水量(ml)]
本発明の疎水化処理蛍光体の疎水化度は、10%以上であり、好ましくは50%以上、より好ましくは70%以上、さらに好ましくは75%以上である。疎水化度が10%以上であれば、封止樹脂との界面における剥離の発生を十分に減少させることができる。
炭素数12以上の長鎖脂肪酸としては、典型的には炭素数が12~30、より好ましくは炭素数が12~22の、飽和又は不飽和の高級脂肪酸を用いることができる。本発明で使用することができる炭素数12以上の長鎖脂肪酸としては、例えば、ラウリン酸(C12)、ミリスチン酸(C14)、オレイン酸(C18)、ステアリン酸(C18)、リノール酸(C18)、及びベヘン酸(C22)を挙げることができる。
本発明で使用することができる粘度1.5Pa・s以下のシリコーンオイルとしては、例えば、ヒドロキシ末端ジメチルポリシロキサン、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイル、アルキル変性シリコーンオイル、ポリエーテル変性シリコーンオイル、アミノ変性シリコーンオイル、エポキシ変性シリコーンオイル、エポキシ・ポリエーテル変性シリコーンオイル、カルボキシル変性シリコーンオイル、メルカプト変性シリコーンオイル等が挙げられる。
蛍光体粒子の表面に、疎水化物質を薄膜状に付着させる方法は、蛍光体粒子と疎水化物質とを均一に混合することができれば特に限定されるものではない。
また、疎水化物質は、単独で使用してもよいが、蛍光体粒子との均一な混合を助けるために、疎水化物質を溶解できる溶媒に混合して使用してもよい。このような溶媒としては、例えば、エタノール等が挙げられる。
本発明の発光装置は、少なくとも上記の疎水化処理蛍光体を含む蛍光体と、発光素子とを備える。発光装置としては、照明装置、バックライト装置、画像表示装置及び信号装置等がある。
発光素子は240~500nmの波長の光を発するものが望ましく、なかでも420nm以上500nm以下の青色LED発光素子が好ましい。
封止樹脂としては、常温で流動性を有するシリコーン樹脂等の熱硬化性樹脂を用いることができ、例えば、東レ・ダウコーニング株式会社製JCR6175を挙げることができる。
本発明の疎水化処理蛍光体を含む蛍光体は、封止樹脂に対して30質量%以上50質量%以下となるように混合して用いることが好ましい。
実施例1~7及び比較例1~3は、いずれもSi6-zAlzOzN8-z:Eu2+(z=0.04)で表されるβ型サイアロン蛍光体に基づくものである。比較例1は、蛍光体粒子の表面に疎水化物質からなる表面層を設けていない従来の蛍光体であり、比較例2及び3は、本発明に規定する疎水化物質とは異なる物質で表面処理した蛍光体である。一方、実施例1~7は蛍光体粒子の表面に本発明に規定する特定の疎水化物質を付着させて表面層を形成した疎水化処理蛍光体である。
比較例1の蛍光体を、以下に記載するように、原料を混合する混合工程、混合工程後の原料を焼成する焼成工程、並びに、焼成工程後の焼結体を後処理するアニール工程及び酸処理工程を経て製造した。
α型窒化ケイ素(宇部興産株式会社製SN-E10グレード、酸素含有量1.0質量%)95.45質量%、窒化アルミニウム(株式会社トクヤマ製Eグレード、酸素含有量0.8質量%)3.1質量%、酸化アルミニウム(大明化学株式会社製TM-DARグレード)0.66質量%、及び酸化ユーロピウム(信越化学工業株式会社製RUグレード)0.79質量%となるように秤量した。当該原料の配合比は、β型サイアロンの一般式:Si6-zAlzOzN8-zにおいて、酸化ユーロピウムを除いて、z=0.04となるように設計した。この原料粉末をV型混合機(筒井理化学器械株式会社製S-3)で10分間乾式混合した。原料の大きさを揃えるため、混合後の原料のうち、目開き250μmのナイロン製篩を通過したものを以下の工程に用いた。
分級後の混合物を蓋付きの円筒型窒化ホウ素製容器(電気化学工業株式会社製N-1グレード)に充填し、カーボンヒーターの電気炉で0.8MPaの加圧窒素雰囲気中、2000℃で15時間放置して焼成を行った。焼成終了後、容器を取り出し、室温になるまで放置した。得られた塊状の焼成物を、蛍光体として要求される粒子サイズ及び粒子形態にするため、ロールクラッシャーで解砕した。目開き150μmの篩を通過した粉体を以下の工程に用いた。
焼成工程後の分級された粉体を、アルゴンガス雰囲気下1450℃に8時間放置した。
アニール工程後の粉体を、フッ化水素酸と硝酸の混酸に30分間浸すことにより酸処理を行った。酸処理後の粉体から酸を分離するため、粉体を混酸ごと合成樹脂製フィルタに流し、フィルタ上に残った粉体を水洗いしてSi6-zAlzOzN8-z:Eu2+(z=0.04)で表される比較例1の蛍光体を得た。
比較例1の蛍光体粒子と、オレイン酸(関東化学株式会社製、鹿1級)とを、蛍光体粒子100質量%に対しオレイン酸1.0質量%の比率となるように配合し、10分間混合した。混合後に目開き75μmの篩を用いて分級し、オレイン酸からなる厚み0.04μmの表面層を有する実施例1の疎水化処理蛍光体を得た。
実施例2~7及び比較例2~3は、使用する疎水化物質及び配合量を、それぞれ以下のように変更したこと以外は実施例1と同じ方法及び条件で製造した。
次に、得られた疎水化処理蛍光体(又は蛍光体)を以下の方法で評価した。評価結果を表1に示す。
表面層の膜厚(μm)は、蛍光体粒子の表面に付着させた疎水化物質によって形成された表面層の厚みであり、次式より算出した。
膜厚(μm)=[表面層の体積(m3)/蛍光体の表面積(m2)]×106
表面層の体積(m3)=表面層の質量(g)/[表面層の密度(g/cm3)×106]
蛍光体の表面積(m2)=蛍光体の比表面積(m2/g)×蛍光体全体の質量(g)
疎水化度(%)は、上述したとおり、以下の方法によって測定した。
(1)500mlの三角フラスコに測定対象の疎水化処理蛍光体0.2gを秤量する。
(2)イオン交換水50mlを(1)に加え、スターラーにて撹拌する。
(3)撹拌をしたままビュレットよりメタノールを滴下させ、前記疎水化処理蛍光体の全量がイオン交換水に懸濁された時の滴下量を測定する。
(4)次式より疎水化度を求める。
疎水化度(%)=[メタノール滴下量(ml)]×100/[メタノール滴下量(ml)+イオン交換水量(ml)]
疎水化処理蛍光体の量子効率を次の方法により、常温で評価した。
積分球(φ60mm)の側面開口部(φ10mm)に反射率が99%の標準反射板(Labsphere社製スペクトラロン)をセットした。この積分球に、発光光源としてのXeランプから455nmの波長に分光した単色光を光ファイバーにより導入し、反射光のスペクトルを分光光度計(大塚電子株式会社製MCPD-7000)により測定した。その際、450~465nmの波長範囲のスペクトルから励起光フォトン数(Qex)を算出した。
次に、凹型のセルに表面が平滑になるように疎水化処理蛍光体を充填したものを積分球の開口部にセットし、波長455nmの単色光を照射し、励起の反射光及び蛍光のスペクトルを分光光度計により測定した。得られたスペクトルデータから励起反射光フォトン数(Qref)及び蛍光フォトン数(Qem)を算出した。
励起反射光フォトン数は、励起光フォトン数と同じ波長範囲で、蛍光フォトン数は、465~800nmの範囲で算出した。
得られた三種類のフォトン数から、外部量子効率(%)=Qem/Qex×100、内部量子効率(%)=Qem/(Qex-Qref)×100を求めた。
色度座標を分光光度計(大塚電子社製MCPD-7000)を用いて測定した。励起光として波長455nmの青色光を用いた。
分光光度計の試料部に測定対象の蛍光体を充填し、表面を平滑にして、積分球を取り付けた。この積分球に、発光光源としてのXeランプからの光から波長455nmの青色光に分光した単色光を、光ファイバーを用いて導入した。この単色光を蛍光体に照射し測定した。測定結果のうちの465~780nmの波長範囲のデータから、JIS Z8724に準じJIS Z8701で規定されるXYZ表色系における色度座標CIExとCIEyを算出した。
相対ピーク強度(%)として、YAG:Ce蛍光体(化成オプトニクス株式会社製P46Y3)の発光スペクトルのピーク高さを100%としたときの相対的な強度を求めた。
光束保持率(%)は、光の強さ(輝度)の経時的な減衰を評価する値である。光束保持率(%)は、測定対象の疎水化処理蛍光体をLEDの発光面側に搭載した発光装置を製造し、この発光装置を高温高湿度環境下で一定時間駆動させる前後の光束を比較することによって評価した。
発光装置は、測定対象の疎水化処理蛍光体50質量%とシリコーン樹脂(東レ・ダウコーニング株式会社製JCR6175)50質量%とを撹拌混合したスラリー3.4μLを、LEDチップを有する2個のトップビュータイプパッケージに注入し、150℃で2時間加熱してスラリーを硬化させることによって製造した。LEDチップは、波長460nmにピークを有する青色発光のものを用いた。
光束の測定は、LED測定装置(Instrument System社製CAS140B)を用いた。
測定対象の疎水化処理蛍光体を実装した発光装置を、温度85℃、湿度85%の環境下で通電(150mA)し、500時間、1000時間駆動させた後の光束を測定した。高速保持率は、500時間経過後のLEDの光束、1000時間経過後のLEDの光束を、通電開始前(0時間経過)の光束で割った値に100を乗じた値である。1000時間経過時での合格値は90%以上である。
色度CIEy保持率(%)は、経時的な色ズレを評価する値である。色度CIEy保持率(%)は、光束保持率の測定方法と同じ発光装置と測定条件を用いて、高温高湿度環境下で一定時間駆動させる前後の色度CIEyを比較することによって評価した。具体的には、500時間経過後の色度CIEy、1000時間経過後の色度CIEyを、通電開始前(0時間経過)の色度CIEyで割った値に100を乗じた値である。500時間経過時での合格値は90%であり、1000時間経過時での合格値は95%である。
なお、比較例3は、疎水化物質として用いたシリコーンオイルが高粘度であり、蛍光体粒子の表面に均一な膜厚の表面層を形成できなかったことから、評価を行わなかった。
実施例1の疎水化処理蛍光体を、発光光源としての青色発光LEDの発光表面に搭載した発光装置を製造した。この発光装置は、実施例1の疎水化処理蛍光体を用いているので、比較例1の蛍光体を用いた発光装置よりも輝度及び発光色の経時的変化が小さく長期安定性に優れていた。
Claims (2)
- 一般式Si6-zAlzOzN8-z:Eu2+(zは0より大きく4.2以下である)で表される蛍光体粒子と、
蛍光体粒子の表面に付着させた疎水化物質からなる表面層とを有し、
疎水化物質が炭素数12以上の長鎖脂肪酸、粘度1.5Pa・s以下のシリコーンオイル、又はこれらの両方からなる、疎水化処理蛍光体。 - 請求項1に記載の疎水化処理蛍光体と発光素子とを備える発光装置。
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JP (1) | JP6546583B2 (ja) |
KR (1) | KR102352808B1 (ja) |
CN (1) | CN106133114B (ja) |
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Cited By (3)
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JP2018150431A (ja) * | 2017-03-10 | 2018-09-27 | デンカ株式会社 | 緑色蛍光体および発光装置 |
JP2020132814A (ja) * | 2019-02-25 | 2020-08-31 | デンカ株式会社 | β型サイアロン蛍光体の製造方法 |
JP2020132813A (ja) * | 2019-02-25 | 2020-08-31 | デンカ株式会社 | β型サイアロン蛍光体、発光部材および発光装置 |
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KR102639166B1 (ko) * | 2015-01-20 | 2024-02-22 | 덴카 주식회사 | 형광체 및 발광 장치 |
US10978619B2 (en) * | 2016-12-02 | 2021-04-13 | Toyoda Gosei Co., Ltd. | Light emitting device |
WO2022256520A1 (en) * | 2021-06-04 | 2022-12-08 | Meta Platforms Technologies, Llc | Optical coating with low refractive index film deposition |
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- 2015-04-01 US US15/300,676 patent/US10145989B2/en active Active
- 2015-04-01 DE DE112015001628.7T patent/DE112015001628B4/de active Active
- 2015-04-01 CN CN201580017795.XA patent/CN106133114B/zh active Active
- 2015-04-01 WO PCT/JP2015/060387 patent/WO2015152341A1/ja active Application Filing
- 2015-04-01 JP JP2016511983A patent/JP6546583B2/ja active Active
- 2015-04-02 TW TW104110911A patent/TWI655272B/zh active
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JP2018150431A (ja) * | 2017-03-10 | 2018-09-27 | デンカ株式会社 | 緑色蛍光体および発光装置 |
JP2020132814A (ja) * | 2019-02-25 | 2020-08-31 | デンカ株式会社 | β型サイアロン蛍光体の製造方法 |
JP2020132813A (ja) * | 2019-02-25 | 2020-08-31 | デンカ株式会社 | β型サイアロン蛍光体、発光部材および発光装置 |
JP7141351B2 (ja) | 2019-02-25 | 2022-09-22 | デンカ株式会社 | β型サイアロン蛍光体、発光部材および発光装置 |
JP7208056B2 (ja) | 2019-02-25 | 2023-01-18 | デンカ株式会社 | β型サイアロン蛍光体の製造方法 |
Also Published As
Publication number | Publication date |
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KR102352808B1 (ko) | 2022-01-18 |
TW201542770A (zh) | 2015-11-16 |
KR20160140822A (ko) | 2016-12-07 |
TWI655272B (zh) | 2019-04-01 |
US20170176647A1 (en) | 2017-06-22 |
DE112015001628B4 (de) | 2021-07-22 |
CN106133114A (zh) | 2016-11-16 |
CN106133114B (zh) | 2018-12-18 |
DE112015001628T5 (de) | 2017-02-09 |
JP6546583B2 (ja) | 2019-07-17 |
US10145989B2 (en) | 2018-12-04 |
JPWO2015152341A1 (ja) | 2017-04-13 |
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