WO2015115189A1 - 複フッ化物蛍光体の製造方法及び処理方法 - Google Patents
複フッ化物蛍光体の製造方法及び処理方法 Download PDFInfo
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- WO2015115189A1 WO2015115189A1 PCT/JP2015/050909 JP2015050909W WO2015115189A1 WO 2015115189 A1 WO2015115189 A1 WO 2015115189A1 JP 2015050909 W JP2015050909 W JP 2015050909W WO 2015115189 A1 WO2015115189 A1 WO 2015115189A1
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- fluoride
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical compound F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011572 manganese Substances 0.000 claims abstract description 67
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 29
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000004673 fluoride salts Chemical class 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 44
- 239000011734 sodium Substances 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 239000002245 particle Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- 239000011698 potassium fluoride Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 235000003270 potassium fluoride Nutrition 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 241000862969 Stella Species 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OJOWXSLGSMTXEO-UHFFFAOYSA-H [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] Chemical compound [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] OJOWXSLGSMTXEO-UHFFFAOYSA-H 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PDZULPOVJPPUEC-UHFFFAOYSA-H [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] Chemical compound [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] PDZULPOVJPPUEC-UHFFFAOYSA-H 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/617—Silicates
-
- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or 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
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
-
- 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
Definitions
- the present invention relates to a formula A 2 MF 6 : Mn useful as a red phosphor for a blue LED, wherein M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn. , A is selected from Li, Na, K, Rb and Cs and is at least one or two or more alkali metals containing Na and / or K.) Mn-activated double fluoride red phosphor
- the present invention relates to a method for producing (double fluoride phosphor).
- the present invention also relates to a method for treating the phosphor.
- Patent Document 1 discloses a double footing represented by a formula such as A 2 MF 6 (A is Na, K, Rb, etc., M is Si, Ge, Ti, etc.). It is described that a compound obtained by adding Mn to a compound (double fluoride phosphor) is useful.
- Patent Document 1 discloses a method in which a hydrofluoric acid solution in which all constituent elements are dissolved or dispersed is evaporated and concentrated.
- Patent Document 2 As another manufacturing method, in US Pat. No. 3,576,756 (Patent Document 2), after mixing a hydrofluoric acid solution in which each constituent element is dissolved, acetone, which is a water-soluble organic solvent, is added to lower the solubility. The method of making it precipitate by making it disclose is disclosed.
- Patent Document 3 Japanese Patent No. 4582259
- Patent Document 3 Japanese Patent Application Laid-Open No.
- Patent Document 4 disclose solutions containing hydrofluoric acid in which the element M and the element A in the above formulas are separate A method for precipitating phosphors by dissolving them in the solution and mixing them with Mn added to them is disclosed.
- the manufacturing process of the double fluoride phosphor represented by the known Mn-added A 2 MF 6 (A is Na, K, Rb, etc., M is Si, Ge, Ti, etc.) described above includes the above-mentioned literature.
- a high concentration of hydrofluoric acid is used in a considerably large amount with respect to the amount of the phosphor obtained. Since hydrofluoric acid is highly corrosive, there are restrictions on the material of the reaction apparatus and the like, which may be a problem when attempting large-scale production. In addition, since it is highly toxic to the human body, there are obstacles to increasing the scale of the chemical process that uses it, even from the viewpoint of the safety of workers handling it.
- the present inventor when producing a red phosphor that is a Mn-activated bifluoride, is not essentially wet, but is mixed with the raw material powder described later, It has been found that it is effective to adopt a dry method for producing the desired double fluoride phosphor by causing the diffusion movement of the substance by heating, and the present invention has been made by examining the conditions and the like. .
- the red phosphor which is a Mn-activated bifluoride produced by this dry method, has better moisture resistance than the double fluoride red phosphor produced by a wet method, and has already been produced. It has been found that the moisture resistance of the phosphor can be improved by adding an additive that promotes the diffusion of the substance to the double fluoride red phosphor and heat-treating it, and the present invention has been completed.
- this invention provides the manufacturing method and processing method of the following double fluoride fluorescent substance.
- the following formula (1) A 2 MF 6 : Mn (1) Wherein M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn, A is selected from Li, Na, K, Rb and Cs, and at least Na and And / or one or more alkali metals containing K.) Is a method for producing a red phosphor which is a Mn-activated double fluoride represented by the following formula (2) A 2 MF 6 (2) (In the formula, M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge, and Sn and substantially does not contain Mn, A is Li, Na, K, One or more alkali metals selected from Rb and Cs and containing at least Na and / or K.) A solid of a double fluoride represented by the following formula (3) A 2 MnF 6 (3) (In the formula, A is one or more al
- a 1 F ⁇ nHF (4) (In the formula, A 1 is one or more alkali metals or ammonium selected from Na, K, Rb and NH 4 , and n is a number of 0.7 or more and 4 or less.)
- a 2 MF 6 Mn (1)
- M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn
- A is selected from Li, Na, K, Rb and Cs, and at least Na and And / or one or more alkali metals containing K.
- a 1 F ⁇ nHF (4) In the formula, A 1 is one or more alkali metals or ammonium selected from Na, K, Rb and NH 4 , and n is a number of 0.7 or more and 4 or less.
- a method for treating a Mn-activated double fluoride phosphor comprising mixing and heating a hydrogen fluoride salt represented by the formula: [6] The method for treating a Mn-activated bifluoride phosphor according to [5], wherein the reaction raw material is heated and reacted in a ceramic container or a
- a Mn-activated bifluoride phosphor having good light emission characteristics can be obtained without using hydrofluoric acid in the main process.
- a Mn-activated double fluoride phosphor excellent in moisture resistance can be obtained.
- FIG. 2 is a powder X-ray diffraction pattern of the mixed powder obtained in Example 1.
- FIG. It is a powder X-ray-diffraction pattern of the heating unwashed powder of Example 1.
- 3 is a powder X-ray diffraction pattern of the washed dry powder of Example 1.
- FIG. It is the spectrum of the excitation light and fluorescence of the mixed powder of the same Example 1, unheated powder, and washed dry powder.
- It is a schematic sectional drawing which shows the other example of the reaction apparatus used for implementation of this invention. It is a schematic sectional drawing of the light-emitting device for a test used in the evaluation experiment 3.
- the phosphor production method according to the present invention comprises the following formula (1): A 2 MF 6 : Mn (1) Wherein M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn, A is selected from Li, Na, K, Rb and Cs, and at least Na and And / or one or more alkali metals containing K.)
- One of the double fluorides used as a raw material in the present invention is a double fluoride represented by the above formula (2). These can use a commercial item. Further, the following formula (5) corresponding to each element M H 2 MF 6 (5) (In the formula, M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge, and Sn, and substantially does not contain Mn.) And a solution of a water-soluble salt of a corresponding alkali metal A such as fluoride, chloride, nitrate, sulfate, carbonate, bicarbonate, hydroxide, or a solid, or a solid. It is also possible to use one.
- a water-soluble salt of a corresponding alkali metal A such as fluoride, chloride, nitrate, sulfate, carbonate, bicarbonate, hydroxide, or a solid, or a solid. It is also possible to use one.
- the raw material for manganese used in the present invention is hexafluoromanganate represented by the above formula (3).
- This is a known method, namely (A) H. Bode, H. Jenssen, F.M. Bandte, Angew. Chem. 65, 304 pages (1953) (Non-patent Document 1), a method of reducing potassium permanganate with hydrogen peroxide in the presence of potassium fluoride. Hoppe, W. Liebe, W.H. Daehne, Z .; Anorg, Allg. Chem. 307, page 276 (1961) (non-patent document 2), a method of heating a mixture of manganese and anhydrous alkali metal chloride in a fluorine gas stream, (C) B.
- Non-patent Document 3 Cox, A.C. G. Sharpe, J. et al. Chem. Soc. , 1798 pages (1954) (Non-patent Document 3) and published by Maruzen Co., Ltd., edited by The Chemical Society of Japan, New Experimental Chemistry Course 8 “Synthesis of Inorganic Compounds III”, published in 1977, 1166 (Non-patent Document 4)
- a method prepared by any of the methods described above for synthesis by electrolytic reaction of a liquid containing manganese fluoride can be used.
- the mixing ratio of the raw material of the tetravalent metal M and the manganese raw material is such that M is 0.001 to 0.3 mol, preferably 0.002 to 0.2 mol, more preferably 0 with respect to 1 mol of M in moles. 0.005 to 0.15 mol. If the amount is less than 0.001 mol, the amount of the activator Mn in the product phosphor is too small, and the light emission characteristics are not sufficient. Even if the amount exceeds 0.3 mol, the light emission characteristics are deteriorated.
- To mix these ingredients put both ingredients in a polyethylene bag, shake or rotate, put it in a container with a lid made of polyethylene, put it on a rocking mixer, tumbler mixer, etc. Arbitrary methods can be used.
- a 1 F ⁇ nHF (4) (In the formula, A 1 is one or more alkali metals or ammonium selected from Li, Na, K, Rb and NH 4 , and n is 0.7 or more and 4 or less, preferably 0.9 or more. The number is 2.5 or less.)
- the reaction can be promoted by mixing and heating the hydrogen fluoride salt represented by As these hydrogen fluoride salts, commercially available products such as ammonium hydrogen fluoride (NH 4 HF 2 ), sodium hydrogen fluoride (NaHF 2 ), potassium hydrogen fluoride (KHF 2 ), and KF ⁇ 2HF may be used. it can.
- the addition amount of these hydrogen fluoride salts is preferably 0 to 2.5 mol of A 1 such as an alkali metal with respect to 1 mol of the main component metal M. More preferably, it is 0.1 to 2.0 mol. Even if the amount of the hydrogen fluoride salt is increased beyond 2.5 mol, there is no advantage in the production of the phosphor, and there is a possibility that the product becomes a lump and is difficult to be loosened.
- the method of mixing the hydrogen fluoride salt is not limited, it may generate heat during mixing. Therefore, it is desirable to avoid mixing with strong force and to mix in a short time.
- the hydrogen fluoride salt may be mixed at the same time when the double fluoride A 2 MF 6 and the manganese raw material A 2 MnF 6 are mixed. However, if the above points are taken into consideration, A 2 MF is mixed in advance. It is preferable to mix a hydrogen fluoride salt with a mixture of 6 and A 2 MnF 6 later.
- reaction accelerator it is also effective to add alkali metal nitrate, sulfate, hydrogen sulfate, and fluoride together with hydrogen fluoride in addition to hydrogen fluoride.
- the addition amount in this case is preferably in a range not exceeding the hydrogen fluoride salt in terms of moles.
- the mixed raw material is heated as described above.
- the heating temperature is 100 to 500 ° C, preferably 150 to 450 ° C, more preferably 170 to 400 ° C.
- the atmosphere during heating may be any of the air, nitrogen, argon, and vacuum. However, a reducing atmosphere containing hydrogen is not preferable because emission characteristics may be deteriorated due to reduction of manganese.
- Either a mixed raw material is put into a sealed container and the whole container is put into a dryer, an oven, or the like, or a method of directly heating with a heater from the outside using a container having a gas outlet is applicable.
- the container made from a fluororesin can be used suitably when heating temperature is 270 degrees C or less.
- heating temperature is higher than this, it is preferable to use a ceramic container.
- the ceramic in this case is preferably alumina, magnesia or magnesium aluminum spinel.
- a double vessel 1 in which an inner layer 3 made of polytetrafluoroethylene is formed on the inner wall of a stainless steel vessel main body 2 shown in FIG. 1 is used. It is preferable to make it.
- a material of the cover body 4 it is preferable to use stainless steel. It is also effective to use the reaction apparatus shown in FIG.
- the reactor shown in FIG. 6 has a ceramic inner layer 6 formed on the inner wall of a SUS (stainless steel) container 5, covered with a fluorine resin covering the upper end opening, and a gas outlet hole 7 formed in the center.
- a stainless steel cooling pipe 9a is installed on the outer peripheral upper end of the container 5 and on the outer peripheral part of the gas outflow pipe 7a projecting from the gas outflow hole 7, and the powder mixture 10 placed in the inside is installed. Is a heater 9b that is heated at the bottom of the outer periphery of the container 5.
- the reaction product obtained as described above may contain unreacted hexafluoromanganate in addition to the desired double fluoride phosphor, and when hydrogen fluoride is added, It also remains. These can be removed by washing.
- an inorganic acid solution such as hydrochloric acid, nitric acid, or hydrofluoric acid, or a fluoride salt solution such as ammonium fluoride or potassium fluoride can be used.
- a hydrofluoric acid or ammonium fluoride solution is more preferable.
- a water-soluble organic solvent such as ethanol or acetone can be added. It is also effective to dissolve the raw material A 2 MF 6 in a cleaning solution.
- the method for producing a double fluoride phosphor according to the present invention is to obtain a double fluoride phosphor by heating the mixture of the raw material powders. Is not used in the manufacture of double fluoride phosphors.
- hydrofluoric acid is used as a cleaning component for cleaning the obtained reaction product containing the double fluoride phosphor to remove unnecessary components (raw material powder and reaction by-products other than the target double fluoride phosphor). It may be used.
- the amount used is small compared to the case where it is used when the double fluoride phosphor is produced by a conventional wet method.
- the solid content is dried by a conventional method to obtain Mn activated double fluoride.
- the obtained double fluoride is excellent in light emission characteristics equivalent to the Mn-activated double fluoride obtained by a conventional wet method.
- the red phosphor used is the above formula (1) A 2 MF 6 : Mn (1) Wherein M is one or more tetravalent elements selected from Si, Ti, Zr, Hf, Ge and Sn, A is selected from Li, Na, K, Rb and Cs, and at least Na and And / or one or more alkali metals containing K.) It is a red fluorescent substance which is Mn activation double fluoride represented by these. Any of the conventionally known wet methods and those produced by any of the dry methods described in the present invention can be used.
- a 1 F ⁇ nHF (4) (In the formula, A 1 is one or more alkali metals or ammonium selected from Li, Na, K, Rb and NH 4 , and n is a number of 0.7 or more and 4 or less.)
- a hydrogen fluoride salt represented by the following formula is mixed with a solid and heated.
- commercially available products such as ammonium hydrogen fluoride (NH 4 HF 2 ), sodium hydrogen fluoride (NaHF 2 ), potassium hydrogen fluoride (KHF 2 ), and KF ⁇ 2HF may be used. it can.
- the addition amount of these hydrogen fluoride salts is preferably 0.01 to 2.0 mol of A 1 such as an alkali metal with respect to 1 mol of the main component metal M. More preferably, it is 0.03 to 1.5 mol. There is no advantage in increasing the amount of hydrogen fluoride beyond 2.0 mol.
- the method of mixing the hydrogen fluoride salt is not limited, it may generate heat during mixing. Therefore, it is desirable to avoid mixing with strong force and to mix in a short time.
- Example 1 26.43 g of potassium silicofluoride (manufactured by Morita Chemical Co., Ltd., K 2 SiF 6 ) powder and 2.46 g of potassium hexafluoromanganate (produced by the method described in Reference Example 1 described later, K 2 MnF 6 ) powder Placed in the same polyethylene zippered bag. The mixture was shaken by hand or slowly rotated for 5 minutes. The mixing ratio corresponds to 0.083 mol of Mn relative to 1 mol of Si. To this mixed powder, powder 14.06 g of potassium hydrogen fluoride (acidic potassium fluoride manufactured by Stella Chemifa, KHF 2 ) was further added and mixed in the same manner as described above.
- potassium hydrogen fluoride acidic potassium fluoride manufactured by Stella Chemifa, KHF 2
- the ratio corresponds to 1.5 mol of KHF 2 with respect to 1 mol of Si.
- 2.0 g (mixed powder) was reserved for later evaluation.
- the powder mixture was placed in a double container 1 shown in FIG. 1 and sealed.
- a double container 1 is formed by forming an inner layer 3 made of polytetrafluoroethylene on the inner wall of a stainless steel (SUS) container body 2, and the double container 1 contains powder.
- the mixture 10 was put in, sealed with a lid 4 made of SUS, and heated in an oven. The temperature was 250 ° C. and the time was maintained for 12 hours, followed by natural cooling.
- the cooled reaction product was partly powdery, most of it was agglomerated, so it was roughly crushed and mixed, and a part of 2.0 g was taken out for evaluation. The taken out portion was further ground in a mortar (heated unwashed powder).
- a cleaning solution a solution in which 4.1 g of potassium silicofluoride was dissolved in 100 cm 3 of 50% by mass hydrofluoric acid (SA-X manufactured by Stella Chemifa, 50% by mass HF) was prepared. Of these, the remainder of the reaction product was added to 75 cm 3 and allowed to stand for 10 minutes with stirring. The massive part was loosened and became powdery. The powdery precipitate was filtered off with a Buchner funnel and washed with the rest of the previously prepared cleaning solution.
- the powder X-ray diffraction pattern of the mixed powder is shown in FIG.
- the assignment of peaks identified with reference to the database is indicated by marks.
- K 2 SiF 6 K 2 MnF 6 and KHF 2 are observed.
- the powder X-ray diffraction pattern of the washed dry powder is shown in FIG. It matches the pattern of K 2 SiF 6 in PDF01-075-0694 of the ICDD (International Center for Diffraction Data) powder X-ray diffraction database, and no impurities are observed. It can be seen that KHF 2 was removed by washing.
- the emission spectra of the powder samples at these stages were measured at an excitation wavelength of 450 nm using a quantum efficiency measurement device QE1100 (manufactured by Otsuka Electronics Co., Ltd.).
- the excitation light and fluorescence spectra are shown in FIG.
- the mixed powder does not emit light, but the heated unwashed powder exhibits red light emission.
- the luminescence is strengthened by washing and drying. Table 1 shows the absorptance and internal quantum efficiency at 450 nm excitation measured with the same apparatus.
- the phosphor is produced in the heating step before washing, combining X-ray diffraction and emission characteristics.
- Both electrodes were connected to a power source, and electrolysis was performed at a voltage of 3 V and a current of 0.75 A. After the electrolysis, an excessive solution of potassium fluoride saturated with an aqueous hydrofluoric acid solution was added to the reaction solution on the anode side. The produced yellow solid product was separated by filtration and recovered to obtain K 2 MnF 6 .
- Example 4 26.43 g of K 2 SiF 6 powder and 1.23 g of the same K 2 MnF 6 powder as in Example 1 were put in the same bag with polyethylene chuck. The mixture was shaken by hand or slowly rotated for 5 minutes. The mixing ratio corresponds to 0.042 mol of Mn with respect to 1 mol of Si. This mixture was put into a magnesia crucible, and further put into an outer container of SUS, and then put into a temperature-controlled tube furnace. The furnace was placed in a draft chamber, and a SUS container was provided with a port through which gas was generated, and a hole was also made in the lid of the magnesia crucible.
- Example 5 K 2 SiF 6 and K 2 MnF 6 were mixed in the same amount as in Example 4. To this, 6.85 g of ammonium hydrogen fluoride (acidic ammonium fluoride manufactured by Stella Chemifa, NH 4 HF 2 ) was further mixed. This was charged in the same apparatus of FIG. 6 as in Example 4 and heated at 350 ° C. for 6 hours. The removed after cooling 35 wt% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd. electronic industry, HCl) was added and stirred in a mixture of 10 cm 3 of ethanol 70cm 3. The solution was filtered with a Buchner funnel, washed with acetone, collected, and dried in vacuo.
- ammonium hydrogen fluoride acidic ammonium fluoride manufactured by Stella Chemifa, NH 4 HF 2
- a powder product of 32.7 g of K 2 SiF 6 : Mn was obtained.
- Example 7 Potassium hexafluorotitanate (Morita Chemical Co., Ltd., K 2 TiF 6 ) powder was used in an amount of 28.8 g, the same K 2 MnF 6 as in Example 1 was used in an amount of 1.48 g, and KHF 2 was used in an amount of 9.37 g. Other than the above, mixing was performed in the same manner as in Example 1, and heating was performed under the same conditions. The removed after cooling and stirred for 10 minutes added to a mixture of 50 wt% HF10cm 3 and acetone 70cm 3. The powdered precipitate was filtered off with a Buchner funnel, washed with acetone, collected, and dried in vacuo.
- a powder product of 32.7 g of K 2 TiF 6 : Mn was obtained.
- Example 8 Sodium hexafluoromanganate (produced by the method of Reference Example 2 described later, Na 2 MnF 6 ) 2.14 g using sodium silicofluoride (Morita Chemical Co., Ltd., Na 2 SiF 6 ) powder , Except that 9.36 g of sodium hydrogen fluoride (Stella Chemifa acid sodium fluoride, NaHF 2 ) was used instead of potassium hydrogen fluoride, mixing was performed in the same manner as in Example 1, and heating was performed under the same conditions. did. After cooling, the reaction product was recovered and crushed roughly. Separately, a solution prepared by dissolving 2.8 g of potassium silicofluoride in 50% by mass of HF of 100 cm 3 was prepared.
- KHF 2 potassium hydrogen fluoride
- Example 10 First, 234 cm 3 of 40 mass% hydrofluoric acid (H 2 SiF 6 ) aqueous solution (Morita Chemical Industry Co., Ltd.), 50 mass% hydrofluoric acid (HF) (SA-X, manufactured by Stella Chemifa Corporation) ) Mixed with 2,660 cm 3 . To this, 13.32 g of K 2 MnF 6 powder prepared in advance by the aforementioned method was added and stirred to dissolve (first solution). Separately, potassium hydrogen fluoride (KHF 2) 210.5g of 50 wt% hydrofluoric acid aqueous solution 680 cm 3, were dissolved and mixed with purified water 1,270cm 3 (second solution).
- KHF 2 potassium hydrogen fluoride
- FIG. 7 The test light emitting device shown in FIG. 7 was produced.
- 11 is an opaque base housing having a recess 12, and a chip 13 is arranged on the inner bottom surface of the recess 12.
- the chip 13 is an InGaN blue light emitting diode having a light emission peak wavelength of 450 nm and a peak half-value width of 20 nm.
- reference numerals 14 and 15 denote electrical connection portions embedded in the base housing 11.
- One electrical connection portion 14 is in electrical contact with the lower electrode of the chip 13, and the other electrical connection portion 15 is connected to the chip 13.
- the upper electrode is connected to the upper electrode via a bonding wire 16.
- the wall surface 17 of the recess 12 of the base housing 11 reflects visible light, and the recess 12 is filled with a cured product 19 of a liquid thermosetting resin previously kneaded with the phosphor 18.
- the chip 13 is sealed.
- 10 parts by mass of a silicone resin (LPS-5547 manufactured by Shin-Etsu Chemical Co., Ltd.) as a thermosetting resin and 4 parts by mass of a double fluoride red phosphor obtained in Examples and Comparative Examples were mixed. Used. After this was poured into the recess of the base housing, it was cured by heating at 150 ° C. for 4 hours. The emission color of the prepared LED was first measured with an Otsuka Electronics total luminous flux measuring device.
- the color is represented by CIE chromaticity coordinates (x, y).
- a current of 0.2 A was continuously supplied for 100 hours, and then the emission color was measured in the same manner.
- the product dxdy of the change dx of x and the change dy of y after 100 hours was observed.
- the same test was conducted at 60 ° C. and a relative humidity of 90%. The results are shown in Table 4.
- Table 5 shows the results of comparing the amount of 50% by mass hydrofluoric acid used when converted to 100 g of a phosphor (K 2 SiF 6 : Mn, etc.) between the known method and the present invention.
- the present invention accounts for hydrofluoric acid used for cleaning.
- Each example does not include the amount used for producing a manganese intermediate as a raw material for producing a phosphor.
- Comparative Example 1 is also Example 1 of Patent Document 4
- Reference Example 3 is Example 5 of Patent Document 2
- Reference Example 4 is Examples 1 to 9 of Patent Document 3.
- Example 6 does not use hydrofluoric acid, the amount of 40% by mass ammonium fluoride solution used is described as a reference.
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Abstract
Description
しかし、更に耐湿性を向上させる有利な方法が望まれる。
〔1〕 下記式(1)
A2MF6:Mn (1)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるMn賦活複フッ化物である赤色蛍光体を製造する方法であって、反応原料として下記式(2)
A2MF6 (2)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素であって実質的にはMnは含まない、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表される複フッ化物の固体と、下記式(3)
A2MnF6 (3)
(式中、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるマンガン化合物の固体とを混合し、100℃以上500℃以下で加熱することを特徴とするMn賦活複フッ化物蛍光体の製造方法。
〔2〕 更に、上記混合物に下記式(4)
A1F・nHF (4)
(式中、A1はNa、K、Rb及びNH4から選ばれる、1種又は2種以上のアルカリ金属又はアンモニウムであり、nは0.7以上4以下の数である。)
で表されるフッ化水素塩を固体で混合して加熱することを特徴とする〔1〕記載のMn賦活複フッ化物蛍光体の製造方法。
〔3〕 反応原料をセラミックス容器、又は反応物と接する部分がフッ素樹脂にて形成された反応容器内で加熱反応させることを特徴とする〔1〕又は〔2〕記載のMn賦活複フッ化物蛍光体の製造方法。
〔4〕 加熱によって得られた反応混合物を、無機酸溶液又はフッ化塩溶液で洗浄して不要成分を除去したのち、固液分離し、固形分を乾燥することを特徴とする〔1〕~〔3〕のいずれかに記載のMn賦活複フッ化物蛍光体の製造方法。
〔5〕 下記式(1)
A2MF6:Mn (1)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるMn賦活複フッ化物である赤色蛍光体に、下記式(4)
A1F・nHF (4)
(式中、A1はNa、K、Rb及びNH4から選ばれる、1種又は2種以上のアルカリ金属又はアンモニウムであり、nは0.7以上4以下の数である。)
で表されるフッ化水素塩を固体で混合して加熱することを特徴とするMn賦活複フッ化物蛍光体の処理方法。
〔6〕 反応原料をセラミックス容器、又は反応物と接する部分がフッ素樹脂にて形成された反応容器内で加熱反応させることを特徴とする〔5〕記載のMn賦活複フッ化物蛍光体の処理方法。
〔7〕 加熱によって得られた反応混合物を無機酸溶液又はフッ化塩溶液で洗浄して不要成分を除去したのち、固液分離し、固形分を乾燥することを特徴とする〔5〕又は〔6〕記載のMn賦活複フッ化物蛍光体の処理方法。
本発明に係る蛍光体の製造方法は、下記式(1)
A2MF6:Mn (1)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるMn賦活複フッ化物である赤色蛍光体を製造する方法であって、下記式(2)
A2MF6 (2)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素であって実質的にMnは含まない、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表される複フッ化物の固体と、下記式(3)
A2MnF6 (3)
(式中、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるマンガン化合物の固体とを混合し、100℃以上500℃以下で加熱することを特徴とするものである。
H2MF6 (5)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素であって実質的にMnは含まない。)
で表される化合物の溶液に、フッ化物、塩化物、硝酸塩、硫酸塩、炭酸塩、炭酸水素塩、水酸化物などの対応するアルカリ金属Aの水溶性塩の溶液又は固体を加えて製造したものを用いることも可能である。
これら原料の混合には、両原料をポリエチレンなどの袋に入れて振ったり回転させたりする方法、ポリエチレン等でできた蓋付きの容器に入れて、ロッキングミキサー、タンブラーミキサーなどにかける、乳鉢で一緒にすりまぜるなど任意の方法が用いることができる。
A1F・nHF (4)
(式中、A1はLi、Na、K、Rb及びNH4から選ばれる、1種又は2種以上のアルカリ金属又はアンモニウムであり、nは0.7以上4以下、好ましくは0.9以上2.5以下の数である。)
で表されるフッ化水素塩を固体で混合して加熱することで、反応を促進させることができる。これらフッ化水素塩としては、フッ化水素アンモニウム(NH4HF2)、フッ化水素ナトリウム(NaHF2)、フッ化水素カリウム(KHF2)などの市販品や、KF・2HFなどを用いることができる。
このフッ化水素塩の混合の方法は限定的でないが、混合中に発熱するおそれもあるので、強い力で擦り混ぜるような方法は避け、短時間で混合することが望ましい。
混合された原料を密閉容器に入れ、容器ごと乾燥機、オーブンなどに入れるか、ガスの抜け口を持つ容器を用いて外からヒーターで直接加熱する方法のいずれかが適用できる。密閉容器を用いる場合は、反応物に接する部分がフッ素樹脂でできているものを用いることが好ましい。これに限らずフッ素樹脂製の容器は加熱温度が270℃以下の場合に好適に用いることができる。加熱温度がこれより高い場合、セラミックス製の容器を用いることが好ましい。この場合のセラミックスはアルミナ、マグネシア又はマグネシウムアルミニウムスピネルなどが好適である。
得られた複フッ化物は、従来の湿式法によって得られるMn賦活複フッ化物と同等の発光特性に優れたものである。
A2MF6:Mn (1)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるMn賦活複フッ化物である赤色蛍光体である。従来公知の湿式法のそれぞれの方法や、本発明で述べた乾式法のいずれかで製造されたものを用いることができる。
A1F・nHF (4)
(式中、A1はLi、Na、K、Rb及びNH4から選ばれる、1種又は2種以上のアルカリ金属又はアンモニウムであり、nは0.7以上4以下の数である。)
で表されるフッ化水素塩を固体で混合して加熱する。これらフッ化水素塩としては、フッ化水素アンモニウム(NH4HF2)、フッ化水素ナトリウム(NaHF2)、フッ化水素カリウム(KHF2)などの市販品や、KF・2HFなどを用いることができる。
このフッ化水素塩の混合の方法は限定的でないが、混合中に発熱するおそれもあるので、強い力で擦り混ぜるような方法は避け、短時間で混合することが望ましい。
ケイフッ化カリウム(森田化学工業(株)製、K2SiF6)粉末26.43gと、ヘキサフルオロマンガン酸カリウム(後述の参考例1記載の方法で作製、K2MnF6)粉末2.46gを同一のポリエチレン製チャック付袋に入れた。手で振ったりゆっくり回転させたりして5分間かけて混合した。混合比率はSi1モルに対し、Mnが0.083モルに相当する。
この混合粉に、更にフッ化水素カリウム(ステラケミファ製酸性フッ化カリウム、KHF2)の粉末14.06gを加え、上記と同様にして混合した。比率はSi 1モルに対し、KHF2は1.5モルに相当する。粉体混合物のうち2.0g(混合粉)を後の評価のためにとっておいた。
粉体混合物を図1に示す二重容器1に入れて密閉した。ここで、図1において、二重容器1はステンレススチール(SUS)製の容器本体2の内壁にポリテトラフルオロエチレン製の内層3を形成してなるもので、この二重容器1内に粉体混合物10を入れ、SUS製の蓋体4で密閉し、オーブンに入れて加熱した。温度は250℃で時間は12時間保持し、自然冷却した。
洗浄液として、4.1gのケイフッ化カリウムを100cm3の50質量%フッ化水素酸(ステラケミファ製SA-X、50質量%HF)に溶解した液を用意しておいた。このうち75cm3に上記の反応物の残りを加え、撹拌をしながら10分間おいた。塊状の部分はほぐれて粉末状になった。
粉末状になった沈殿物をブフナー漏斗でろ別し、先に作成した洗浄液の残りで振りかけ洗浄した。更にアセトンで洗浄して回収後、真空乾燥した。28.2gの粉末製品が得られた(洗浄乾燥粉)。この粉末製品の粒度分布を、気流分散式レーザー回折法粒度分布測定器(HELOS&RODOS、Sympatec社製)によって測定した。その結果、粒径8.6μm以下の粒子が全体積の10%(D10=8.6μm)、粒径21.3μm以下の粒子が全体積の50%(D50=21.3μm)、粒径33.7μm以下の粒子が全体積の90%を占めた(D90=33.7μm)。
次に、加熱未洗浄粉の粉末X線回折パターンを図3に示す。KHF2のピークの比が大きくなっているのに対し、K2MnF6のピークは混合粉の図2に比べて大幅に弱くなっている。他の化合物のピークと重ならない、2θ=34°付近のピークを見るとそれがはっきりわかる。MnはK2SiF6に取り込まれていって、K2MnF6が減っていると推定できる。
これら各段階の粉末試料の発光スペクトルを、量子効率測定装置QE1100(大塚電子(株)製)を用いて、励起波長450nmで測定した。励起光と蛍光のスペクトルを図5に示す。混合粉は発光を示さないが、加熱未洗浄粉は赤色の発光を示している。その発光が洗浄・乾燥により強まっている。
同装置で測定した450nm励起での吸収率と内部量子効率は表1のとおりである。
[K2MnF6の調製]
非特許文献4に記載されている方法に準拠し、以下の方法で調製した。
塩化ビニル樹脂製の反応槽の中央にフッ素樹脂系イオン交換膜の仕切り(隔膜)を設け、イオン交換膜を挟む2室の各々に、いずれも白金板からなる陽極と陰極を設置した。反応槽の陽極側に、フッ化マンガン(II)を溶解させたフッ化水素酸水溶液、陰極側にフッ化水素酸水溶液を入れた。両極を電源につなぎ、電圧3V、電流0.75Aで電解を行った。電解を終えた後、陽極側の反応液に、フッ化水素酸水溶液に飽和させたフッ化カリウムの溶液を過剰に加えた。生成した黄色の固体生成物をろ別、回収し、K2MnF6を得た。
フッ化水素カリウムの14.06gを11.72gに代え、硫酸水素カリウム(和光純薬試薬特級、KHSO4)を4.08g加えることのほかは、実施例1と同様にして、31.0gのK2SiF6:Mnの粉末製品を得た。実施例1と同様にして測定した粒度分布の結果は、D10=8.2μm、D50=22.1μm、D90=35.4μmであった。
フッ化水素カリウムの14.06gを11.72gに代え、硝酸カリウム(和光純薬試薬特級、KNO3)を3.03g加えることのほかは、実施例1と同様にして、30.4gのK2SiF6:Mnの粉末製品を得た。実施例1と同様にして測定した粒度分布の結果は、D10=6.9μm、D50=20.0μm、D90=31.0μmであった。
K2SiF6粉末26.43gと、実施例1と同じK2MnF6粉末1.23gを同一のポリエチレン製チャック付袋に入れた。手で振ったりゆっくり回転させたりして5分間かけて混合した。混合比率はSi1モルに対し、Mnが0.042モルに相当する。
この混合物をマグネシアるつぼに入れ、更にSUSの外容器に入れてから温度制御付管状炉に入れた。炉はドラフトチャンバー中に置き、SUS容器には内部でガスが発生した場合に抜ける口を設け、マグネシアるつぼのふたにも穴をあけておいた。また管状炉の中に入っていないSUS容器の出口部分は、SUSの管を巻いて水を流して冷却できるようにしておいた。この反応装置は図6に示した。この装置を用いて、300℃で8時間加熱し、自然冷却した。反応物を取り出し、すりつぶして回収した。30.2gのK2SiF6:Mnの粉末製品が得られた。実施例1と同様にして測定した粒度分布の結果は、D10=7.3μm、D50=16.7μm、D90=37.5μmであった。
実施例4と同じ仕込み量でK2SiF6とK2MnF6を混合した。これに更に6.85gのフッ化水素アンモニウム(ステラケミファ製酸性フッ化アンモニウム、NH4HF2)を混合した。実施例4と同じ図6の装置にこれを仕込み、350℃で6時間加熱した。冷却後に取り出し、35質量%塩酸(和光純薬製電子工業用、HCl)10cm3とエタノール70cm3の混合液に加えて撹拌した。ブフナー漏斗でろ別し、アセトンで洗浄して回収後、真空乾燥した。32.7gのK2SiF6:Mnの粉末製品が得られた。実施例1と同様にして測定した粒度分布の結果は、D10=9.1μm、D50=18.0μm、D90=32.5μmであった。
実施例4と同じ仕込み量でK2SiF6とK2MnF6を混合した。これに更に7.03gのKHF2を混合した。実施例5と同様に加熱した。冷却後に取り出し、40質量%フッ化アンモニウム溶液(森田化学工業(株)製半導体用、NH4F)80cm3に加えて撹拌した。ブフナー漏斗でろ別し、アセトンで洗浄して回収後、真空乾燥した。32.3gのK2SiF6:Mnの粉末製品が得られた。実施例1と同様にして測定した粒度分布の結果は、D10=8.9μm、D50=18.6μm、D90=28.1μmであった。
ヘキサフルオロチタン酸カリウム(森田化学工業(株)製、K2TiF6)粉末28.8gを用い、実施例1と同じK2MnF6を1.48g用い、KHF2は9.37g用いたことのほかは、実施例1と同じように混合を行い、同条件で加熱した。冷却後に取り出し、50質量%HF10cm3とアセトン70cm3の混合液に加えて10分間撹拌した。粉末状になった沈殿物をブフナー漏斗でろ別し、アセトンで洗浄して回収後、真空乾燥した。32.7gのK2TiF6:Mnの粉末製品が得られた。実施例1と同様にして測定した粒度分布の結果は、D10=9.9μm、D50=38.2μm、D90=72.6μmであった。
ケイフッ化ナトリウム(森田化学工業(株)製、Na2SiF6)粉末22.56gを用い、ヘキサフルオロマンガン酸ナトリウム(後述の参考例2の方法で作製、Na2MnF6)2.14gを用い、フッ化水素カリウムに代えてフッ化水素ナトリウム(ステラケミファ製酸性フッ化ナトリウム、NaHF2)9.36gを用いたことのほかは、実施例1と同じように混合を行い、同条件で加熱した。冷却後反応物を回収し粗く砕いた。
別に2.8gのケイフッ化カリウムを100cm3の50質量%HFに溶解した液を用意しておいた。このうち75cm3に上記の反応物を加え、撹拌をしながら10分間おいた。塊状の部分はほぐれて粉末状になった。粉末状になった沈殿物をブフナー漏斗でろ別し、先に作成した洗浄液の残りで振りかけ洗浄した。更にアセトンで洗浄して回収後、真空乾燥した。25.6gのNa2SiF6:Mnの粉末製品が得られた。実施例1と同様にして測定した粒度分布の結果は、D10=6.2μm、D50=29.7μm、D90=56.1μmであった。
[Na2MnF6の調製]
参考例1のK2MnF6の調製と同様の電解反応槽を用い、フッ化カリウムの代わりにフッ化ナトリウムを加えることのほかは同様に反応させ、生成した黄色の固体生成物をろ別、回収し、Na2MnF6を得た。
フッ化水素カリウム(KHF2)に代えてKF・2HFで表されるフッ化水素塩(森田化学工業(株)製)11.77gを加えること、及びヘキサフルオロマンガン酸カリウム粉末の添加量を0.99gに代えることのほかは、実施例1と同様にして、29.9gのK2SiF6:Mnの粉末製品を得た。実施例1と同様にして測定した粒度分布の結果は、D10=18.1μm、D50=27.8μm、D90=40.9μmであった。
40質量%のケイフッ化水素酸(H2SiF6)水溶液(森田化学工業(株)製)15.6cm3を、まず50質量%HF100cm3と混合した。これに、実施例1と同じK2MnF6粉末を1.19g加えて撹拌して溶解させ、Si、FとMnを含む水溶液(第1溶液)を調製した。また、13.95gのフッ化カリウムを40cm3の50質量%HFに溶解させ、室温まで放冷し、フッ化カリウムを含む水溶液(第2溶液)を調製した。次に、撹拌した第1溶液に、第2溶液を約3分間かけて少しずつ加え、10分間程度撹拌し、淡橙色の固体が生成した。この固体生成物をろ別し、アセトンで洗浄し真空乾燥して、15.64gのK2SiF6:Mnの粉末製品を得た。実施例1と同様にして測定した粒度分布の結果は、D10=15.1μm、D50=36.9μm、D90=60.3μmであった。
40質量%のチタンフッ化水素酸(H2SiF6)水溶液(森田化学工業(株)製)15.6cm3を、まず50質量%HF100cm3HFと混合した。これに、実施例1と同じK2MnF6粉末を0.74g加えて撹拌して溶解させ、Ti、FとMnを含む水溶液(第1溶液)を調製した。また、23.43gのKHF2を22cm3の50質量%HFと34cm3の純水に溶解させ、フッ化カリウムを含む水溶液(第2溶液)を調製した。次に、撹拌した第1溶液に、第2溶液を約2分間かけて少しずつ加え、10分間程度撹拌し、淡橙色の固体が生成した。この固体生成物をろ別し、アセトンで洗浄し真空乾燥して、13.73gのK2TiF6:Mnの粉末製品を得た。実施例1と同様にして測定した粒度分布の結果は、D10=13.6μm、D50=46.5μm、D90=103.2μmであった。
40質量%のケイフッ化水素酸(H2SiF6)水溶液(森田化学工業(株)製)234cm3を、まず50質量%フッ化水素酸(HF)(SA-X、ステラケミファ(株)製)2,660cm3と混合した。これに、予め前述の方法で作製したK2MnF6粉末を13.32g加えて攪拌し溶解させた(第1溶液)。
これとは別に、フッ化水素カリウム(KHF2)210.5gを50質量%フッ化水素酸水溶液680cm3、純水1,270cm3と混合し溶解させた(第2溶液)。
第1溶液を攪拌しながら、第2溶液を少しずつ加えていったところ、淡橙色の沈殿が生じた。この沈殿をブフナー漏斗でろ別し、十分脱液した後、アセトンをふりかけて洗浄し、脱液して回収し、更に真空乾燥した。184.9gの粉末製品が得られた。
この粉末のうちの26.43gをとり、これにKF・2HFで表されるフッ化水素塩1.96gを混合し、実施例1と同様の容器に入れて同条件で加熱し、以下も同様の操作を行って26.87gの蛍光体を得た。実施例1と同様にして測定した粒度分布の結果はD10=13.1μm、D50=25.8μm、D90=39.7μmであった。
実施例10で、沈殿析出、ろ別、洗浄、真空乾燥のみ行った、熱処理に用いなかった残りをとった。実施例1と同様にして測定した粒度分布の結果はD10=8.4μm、D50=19.2μm、D90=29.3μmであった。
実施例及び比較例によって得られた蛍光体の発光特性を実施例1で述べた、量子効率測定装置QE1100(大塚電子(株)製)で測定した。励起波長450nmでの吸収率と量子効率を表2に示す。
実施例及び比較例によって得られた蛍光体の耐久性試験を行った。
蛍光体を粉末のまま、蓋のない小皿に入れ、耐久性試験として、温度65℃、相対湿度90%に維持した恒温恒湿器(エスペック(株)製)中で30分間及び7日間静置し、実験例2と同様にして内部量子効率を測定した。その結果を表3に示す。
図7に示す試験用発光装置を作製した。図7中、11は凹部12を有する不透明なベースハウジングで、凹部12の内底面にチップ13が配置されている。チップ13は、InGaN系青色発光ダイオードで、発光ピーク波長450nm、ピーク半価幅20nmのものである。図中、14、15はそれぞれベースハウジング11に埋め込まれた電気接続部で、一方の電気接続部14はチップ13の下側電極と電気的に接しており、他方の電気接続部15はチップ13の上部電極とボンディングワイヤ16を介して接続されている。上記ベースハウジング11の凹部12の壁面17は可視光を反射するようになっており、また凹部12内には、蛍光体18を予め混練した液状の熱硬化性樹脂の硬化物19が充填され、チップ13が封止されている。
実験では、熱硬化性樹脂としてシリコーン樹脂(信越化学工業(株)製LPS-5547)10質量部と、蛍光体として実施例及び比較例で得られた複フッ化物赤色蛍光体4質量部を混合して用いた。これをベースハウジングの凹部に注入したのち、150℃で4時間加熱して硬化させた。
作成したLEDの発光色を大塚電子製全光束測定装置でまず測定した。色はCIE色度座標(x,y)で表される。次に、85℃の恒温器中で、0.2Aの電流を100時間流し続けた後、同様に発光色を測定した。初期と100時間後のxの変化dxとyの変化dyの積dxdyを見た。また、60℃、相対湿度90%でも同様の試験を行った。その結果を表4に示す。
2 容器本体
3 内層
4 蓋体
5 容器
6 内層
7 ガス流出孔
7a ガス流出管
8 蓋体
9a 冷却管
9b ヒーター
10 粉体混合物
11 ベースハウジング
12 凹部
13 チップ
14 電気接続部
15 電気接続部
16 ボンディングワイヤ
17 壁面
18 蛍光体
19 熱硬化性樹脂
Claims (7)
- 下記式(1)
A2MF6:Mn (1)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるMn賦活複フッ化物である赤色蛍光体を製造する方法であって、反応原料として下記式(2)
A2MF6 (2)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素であって実質的にはMnは含まない、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表される複フッ化物の固体と、下記式(3)
A2MnF6 (3)
(式中、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるマンガン化合物の固体とを混合し、100℃以上500℃以下で加熱することを特徴とするMn賦活複フッ化物蛍光体の製造方法。 - 更に、上記混合物に下記式(4)
A1F・nHF (4)
(式中、A1はNa、K、Rb及びNH4から選ばれる、1種又は2種以上のアルカリ金属又はアンモニウムであり、nは0.7以上4以下の数である。)
で表されるフッ化水素塩を固体で混合して加熱することを特徴とする請求項1記載のMn賦活複フッ化物蛍光体の製造方法。 - 反応原料をセラミックス容器、又は反応物と接する部分がフッ素樹脂にて形成された反応容器内で加熱反応させることを特徴とする請求項1又は2記載のMn賦活複フッ化物蛍光体の製造方法。
- 加熱によって得られた反応混合物を、無機酸溶液又はフッ化塩溶液で洗浄して不要成分を除去したのち、固液分離し、固形分を乾燥することを特徴とする請求項1~3のいずれか1項記載のMn賦活複フッ化物蛍光体の製造方法。
- 下記式(1)
A2MF6:Mn (1)
(式中、MはSi、Ti、Zr、Hf、Ge及びSnから選ばれる1種又は2種以上の4価元素、AはLi、Na、K、Rb及びCsから選ばれ、かつ少なくともNa及び/又はKを含む1種又は2種以上のアルカリ金属である。)
で表されるMn賦活複フッ化物である赤色蛍光体に、下記式(4)
A1F・nHF (4)
(式中、A1はNa、K、Rb及びNH4から選ばれる、1種又は2種以上のアルカリ金属又はアンモニウムであり、nは0.7以上4以下の数である。)
で表されるフッ化水素塩を固体で混合して加熱することを特徴とするMn賦活複フッ化物蛍光体の処理方法。 - 反応原料をセラミックス容器、又は反応物と接する部分がフッ素樹脂にて形成された反応容器内で加熱反応させることを特徴とする請求項5記載のMn賦活複フッ化物蛍光体の処理方法。
- 加熱によって得られた反応混合物を無機酸溶液又はフッ化塩溶液で洗浄して不要成分を除去したのち、固液分離し、固形分を乾燥することを特徴とする請求項5又は6記載のMn賦活複フッ化物蛍光体の処理方法。
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KR20170020648A (ko) * | 2015-08-13 | 2017-02-23 | 한국화학연구원 | 형광체의 제조방법 및 이에 따라 제조되는 형광체를 포함하는 발광소자 |
KR20170044043A (ko) | 2015-10-14 | 2017-04-24 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Mn 부활 복불화물 형광체 및 그의 제조 방법 |
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US9698314B2 (en) * | 2013-03-15 | 2017-07-04 | General Electric Company | Color stable red-emitting phosphors |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3576756A (en) | 1968-06-12 | 1971-04-27 | Mallinckrodt Chemical Works | Fluocomplexes of titanium, silicon, tin and germanium, activated by tetravalent manganese |
JP2009528429A (ja) | 2006-02-28 | 2009-08-06 | ルミネイション リミテッド ライアビリティ カンパニー | 発光ダイオード応用における使用のための赤色線放出蛍光体 |
JP2009280763A (ja) | 2008-05-26 | 2009-12-03 | Sharp Corp | 蛍光体調製物およびそれを用いた発光装置 |
JP2010045328A (ja) | 2008-07-18 | 2010-02-25 | Sharp Corp | 発光装置および発光装置の製造方法 |
JP2010209311A (ja) * | 2008-09-05 | 2010-09-24 | Mitsubishi Chemicals Corp | 蛍光体及びその製造方法と、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた画像表示装置及び照明装置 |
JP2012224536A (ja) | 2011-04-08 | 2012-11-15 | Shin-Etsu Chemical Co Ltd | 複フッ化物及び複フッ化物蛍光体の製造方法 |
WO2013158929A1 (en) * | 2012-04-18 | 2013-10-24 | Nitto Denko Corporation | Phosphor ceramics and methods of making the same |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7648649B2 (en) | 2005-02-02 | 2010-01-19 | Lumination Llc | Red line emitting phosphors for use in led applications |
CN101939857B (zh) | 2008-02-07 | 2013-05-15 | 三菱化学株式会社 | 半导体发光装置、背光源、彩色图像显示装置以及这些中使用的荧光体 |
US9765257B2 (en) * | 2012-03-12 | 2017-09-19 | Nitto Denko Corporation | Emissive compacts and method of making the same |
CN102827601B (zh) * | 2012-09-17 | 2014-08-20 | 中国科学院福建物质结构研究所 | 氟化物荧光粉体材料及其半导体发光器件 |
JP2014177586A (ja) * | 2013-03-15 | 2014-09-25 | Toshiba Corp | 蛍光体、およびその製造方法、ならびにその蛍光体を用いた発光装置 |
-
2014
- 2014-07-02 JP JP2014136703A patent/JP5804149B2/ja active Active
-
2015
- 2015-01-15 CN CN201580006435.XA patent/CN105980523B/zh active Active
- 2015-01-15 US US15/113,889 patent/US10214687B2/en active Active
- 2015-01-15 EP EP15742915.0A patent/EP3101090B1/en active Active
- 2015-01-15 KR KR1020167022445A patent/KR102185621B1/ko active IP Right Grant
- 2015-01-15 WO PCT/JP2015/050909 patent/WO2015115189A1/ja active Application Filing
- 2015-01-29 TW TW104103050A patent/TWI640603B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3576756A (en) | 1968-06-12 | 1971-04-27 | Mallinckrodt Chemical Works | Fluocomplexes of titanium, silicon, tin and germanium, activated by tetravalent manganese |
JP2009528429A (ja) | 2006-02-28 | 2009-08-06 | ルミネイション リミテッド ライアビリティ カンパニー | 発光ダイオード応用における使用のための赤色線放出蛍光体 |
JP2009280763A (ja) | 2008-05-26 | 2009-12-03 | Sharp Corp | 蛍光体調製物およびそれを用いた発光装置 |
JP2010045328A (ja) | 2008-07-18 | 2010-02-25 | Sharp Corp | 発光装置および発光装置の製造方法 |
JP2010209311A (ja) * | 2008-09-05 | 2010-09-24 | Mitsubishi Chemicals Corp | 蛍光体及びその製造方法と、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた画像表示装置及び照明装置 |
JP4582259B2 (ja) | 2008-09-05 | 2010-11-17 | 三菱化学株式会社 | 蛍光体及びその製造方法と、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた画像表示装置及び照明装置 |
JP2012224536A (ja) | 2011-04-08 | 2012-11-15 | Shin-Etsu Chemical Co Ltd | 複フッ化物及び複フッ化物蛍光体の製造方法 |
WO2013158929A1 (en) * | 2012-04-18 | 2013-10-24 | Nitto Denko Corporation | Phosphor ceramics and methods of making the same |
Non-Patent Citations (5)
Title |
---|
B. COX; A.G. SHARPE, J. CHEM. SOC.,, 1954, pages 1798 |
H. BODE; H. JENSSEN; F. BANDTE, ANGEW. CHEM., vol. 65, 1953, pages 304 |
R. HOPPE; W. LIEBE; W. DAEHNE, Z. ANORG. ALLG. CHEM., vol. 307, 1961, pages 276 |
See also references of EP3101090A4 |
THE CHEMICAL SOCIETY OF JAPAN: "Shin Jikken Kagaku Koza 8 [New experimental chemistry series 8]", 1977, MARUZEN, INC, article "Inorganic Compound Synthesis III", pages: 1166 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170020648A (ko) * | 2015-08-13 | 2017-02-23 | 한국화학연구원 | 형광체의 제조방법 및 이에 따라 제조되는 형광체를 포함하는 발광소자 |
KR101722052B1 (ko) * | 2015-08-13 | 2017-04-03 | 한국화학연구원 | 형광체의 제조방법 및 이에 따라 제조되는 형광체를 포함하는 발광소자 |
KR20170044043A (ko) | 2015-10-14 | 2017-04-24 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Mn 부활 복불화물 형광체 및 그의 제조 방법 |
JP2018012825A (ja) * | 2015-10-14 | 2018-01-25 | 信越化学工業株式会社 | Mn賦活複フッ化物蛍光体及びその製造方法 |
US10266763B2 (en) | 2015-10-14 | 2019-04-23 | Shin-Etsu Chemical Co., Ltd. | Mn-activated complex fluoride phosphor and method of producing thereof |
KR20240049529A (ko) | 2015-10-14 | 2024-04-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Mn 부활 복불화물 형광체 및 그의 제조 방법 |
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