JP5168017B2 - Phosphor and fluorescent lamp using the same - Google Patents
Phosphor and fluorescent lamp using the same Download PDFInfo
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- JP5168017B2 JP5168017B2 JP2008200392A JP2008200392A JP5168017B2 JP 5168017 B2 JP5168017 B2 JP 5168017B2 JP 2008200392 A JP2008200392 A JP 2008200392A JP 2008200392 A JP2008200392 A JP 2008200392A JP 5168017 B2 JP5168017 B2 JP 5168017B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 136
- 229910052693 Europium Inorganic materials 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 32
- 238000004381 surface treatment Methods 0.000 claims description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 27
- DYRWWVFQQONJJK-UHFFFAOYSA-K scandium(3+);phosphate Chemical compound [Sc+3].[O-]P([O-])([O-])=O DYRWWVFQQONJJK-UHFFFAOYSA-K 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229910052771 Terbium Inorganic materials 0.000 claims description 10
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 5
- 230000004907 flux Effects 0.000 description 38
- 239000000243 solution Substances 0.000 description 29
- 238000012423 maintenance Methods 0.000 description 28
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- -1 europium-activated strontium Chemical class 0.000 description 18
- 239000011572 manganese Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 10
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
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- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 238000010979 pH adjustment Methods 0.000 description 4
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- 239000011701 zinc Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000000020 Nitrocellulose Substances 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- 150000003326 scandium compounds Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- UAHZTKVCYHJBJQ-UHFFFAOYSA-N [P].S=O Chemical compound [P].S=O UAHZTKVCYHJBJQ-UHFFFAOYSA-N 0.000 description 2
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- 150000002823 nitrates Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
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- CJRWSNPGHPBPPH-UHFFFAOYSA-N [Ba+2].B([O-])([O-])[O-].[Ca+2] Chemical compound [Ba+2].B([O-])([O-])[O-].[Ca+2] CJRWSNPGHPBPPH-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- DXNVUKXMTZHOTP-UHFFFAOYSA-N dialuminum;dimagnesium;barium(2+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Mg+2].[Al+3].[Al+3].[Ba+2].[Ba+2] DXNVUKXMTZHOTP-UHFFFAOYSA-N 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- ABEVUBXCYLEFPJ-UHFFFAOYSA-K dysprosium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Dy+3] ABEVUBXCYLEFPJ-UHFFFAOYSA-K 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- CQQZFSZWNXAJQN-UHFFFAOYSA-K europium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Eu+3] CQQZFSZWNXAJQN-UHFFFAOYSA-K 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
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- ILCLBMDYDXDUJO-UHFFFAOYSA-K gadolinium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Gd+3] ILCLBMDYDXDUJO-UHFFFAOYSA-K 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
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- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical class [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- QVVDHJQBGNVGEB-UHFFFAOYSA-K lutetium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Lu+3] QVVDHJQBGNVGEB-UHFFFAOYSA-K 0.000 description 1
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- 229910000346 scandium sulfate Inorganic materials 0.000 description 1
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 1
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 description 1
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- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- DIRSQPIRPNAECV-UHFFFAOYSA-N terbium;trihydrate Chemical compound O.O.O.[Tb] DIRSQPIRPNAECV-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical class [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は蛍光体及びそれを用いた蛍光ランプに関し、特に液晶表示装置のバックライトに使用される冷陰極蛍光ランプに関する。 The present invention relates to a phosphor and a fluorescent lamp using the same, and more particularly to a cold cathode fluorescent lamp used for a backlight of a liquid crystal display device.
蛍光ランプはガラスバルブ等の透光性気密容器内で放電を起こし、その際に放電媒体から発せられる紫外線が気密容器内壁に形成された蛍光体層中の蛍光体を励起し、その蛍光体が発する光を利用する発光装置である。蛍光体層中の蛍光体の種類、混合比等を変えることにより蛍光ランプの発光スペクトルを制御することができ、これまで照明用など各種用途に使用されている。 A fluorescent lamp causes a discharge in a light-transmitting hermetic container such as a glass bulb, and ultraviolet rays emitted from the discharge medium at that time excite the phosphor in the phosphor layer formed on the inner wall of the hermetic container. It is a light-emitting device that utilizes emitted light. The emission spectrum of the fluorescent lamp can be controlled by changing the type, mixing ratio, etc. of the phosphor in the phosphor layer, and it has been used for various purposes such as illumination.
特に、近年ではカラー液晶表示装置のバックライト用に使用されており、主として細管化しやすい冷陰極蛍光ランプが用いられている。カラー液晶表示装置の構成として例えばバックライトからの発光を導光板等によって液晶パネル背面に面光源として導入し、液晶パネルの各表示画素が液晶層及びカラーフィルターによって特定の波長域の光を特定の強さだけ通過させることで任意の色を再現している。 In particular, in recent years, cold cathode fluorescent lamps, which are used for backlights of color liquid crystal display devices and are mainly easy to be thinned, are used. As a configuration of the color liquid crystal display device, for example, light emitted from the backlight is introduced as a surface light source on the back of the liquid crystal panel by a light guide plate or the like, and each display pixel of the liquid crystal panel specifies light in a specific wavelength range by a liquid crystal layer and a color filter. Arbitrary colors are reproduced by passing only the strength.
バックライト用蛍光ランプにおいては照明用蛍光ランプと異なり次のような問題がある。すなわちバックライトは表示装置の光源として用いられるため、蛍光ランプ全体の光束維持率のみならず各色成分の相対強度の維持率つまり蛍光ランプ全体としての色度の維持率が重要となる。また表示装置の表示面全体が輝度的にも色度的にも均一に照らされる必要があるため、蛍光ランプの輝度及び色度分布は均一であることが求められる。特に色度分布は表示装置の画像品質により強く影響を及ぼす。このため、バックライト用蛍光ランプは両端の色度差（管端色差と呼ぶ）に対する要求が強い。 Unlike the fluorescent lamp for illumination, the backlight fluorescent lamp has the following problems. That is, since the backlight is used as a light source of the display device, not only the luminous flux maintenance factor of the whole fluorescent lamp but also the maintenance factor of the relative intensity of each color component, that is, the chromaticity maintenance factor of the whole fluorescent lamp is important. Further, since the entire display surface of the display device needs to be illuminated uniformly both in terms of luminance and chromaticity, the luminance and chromaticity distribution of the fluorescent lamp are required to be uniform. In particular, the chromaticity distribution strongly affects the image quality of the display device. For this reason, the fluorescent lamp for backlight has a strong demand for a chromaticity difference (referred to as a tube end color difference) at both ends.
また、バックライト用蛍光ランプは一般照明用蛍光ランプに比べて管径が小さいが、このようなランプでは管壁にかかる負荷もより強くなるため、一般照明用蛍光ランプにおいて光束維持率がよいとされてきた蛍光体でもその維持率が低くなる傾向にあり、対策が求められている。 Further, the fluorescent lamp for backlight has a smaller tube diameter than the fluorescent lamp for general illumination. However, since the load on the tube wall becomes stronger in such a lamp, the luminous flux maintenance rate is good in the general fluorescent lamp. Even the phosphors that have been used tend to have a low retention rate, and countermeasures are required.
特許文献１等には、一般照明用蛍光ランプのライフ特性を改善するため、特定の金属酸化物とリンの酸化物からなる複合酸化物による処理が開示されているが、バックライト用蛍光ランプには十分ではなかった。 Patent Document 1 and the like disclose a treatment with a composite oxide composed of a specific metal oxide and phosphorus oxide in order to improve the life characteristics of a fluorescent lamp for general illumination. Was not enough.
このように、バックライト用蛍光ランプにおいて、光束維持率、色度の経時変化、及び管端色差を市場の要求を満たす水準まで改善する手法は確立されていないのが現状であった。 As described above, in the fluorescent lamps for backlights, there is currently no established method for improving the luminous flux maintenance factor, the chromaticity change with time, and the tube end color difference to a level that satisfies the market demand.
さらに、近年では、バックライト用蛍光ランプに対して色再現範囲の拡大要求があり、青色蛍光体として、従来の２価のユーロピウム付活バリウムマグネシウムアルミネート蛍光体（以下ＢＡＭ蛍光体と呼ぶ）に対し、２価のユーロピウム付活ストロンチウムクロロアパタイト蛍光体やこの蛍光体のストロンチウムの一部または全部を他のアルカリ土類金属で置換したアルカリ土類クロロアパタイト蛍光体（両者をまとめて以下ＳＣＡ蛍光体と呼ぶ）が研究されており、特に、ＳＣＡ蛍光体等を用いて色再現範囲を拡大したバックライト用蛍光ランプにおいて、光束維持率、色度の経時変化、及び管端色差の改善が求められている。
本発明は上記問題を解決するためになされたものである。本発明の目的は、バックライト用蛍光ランプにおいて点灯時の光束維持率、色度の経時変化、及び管端色差を改善することであり、さらには、ＳＣＡ蛍光体等を用いて色再現範囲を拡大したバックライト用蛍光ランプにおいてこれらの特性を改善することである。 The present invention has been made to solve the above problems. An object of the present invention is to improve the luminous flux maintenance factor at the time of lighting, the chromaticity change with time, and the tube end color difference in the backlight fluorescent lamp, and further, the color reproduction range can be increased by using an SCA phosphor or the like. It is to improve these characteristics in an expanded backlight fluorescent lamp.
上記目的を達成するために本発明者らは鋭意検討を重ね、本発明を完成するに至った。本発明者らは、特定の希土類リン酸塩と希土類水酸化物を含む表面処理物質で蛍光体を被覆すると、バックライト用蛍光ランプにおいて点灯時の光束維持率、色度の経時変化、及び管端色差が改善されることを見出した。本発明の構成及びその特徴は以下のとおりである。 In order to achieve the above object, the present inventors have conducted intensive studies and have completed the present invention. The present inventors have coated a phosphor with a surface treatment substance containing a specific rare earth phosphate and a rare earth hydroxide, and in a fluorescent lamp for backlight, a luminous flux maintenance factor at the time of lighting, a change with time of chromaticity, and a tube It has been found that the edge color difference is improved. The configuration of the present invention and its features are as follows.
（１）本発明の蛍光体は、蛍光体粒子表面にスカンジウムのオルトリン酸塩とＬａ、Ｙ、Ｇｄ、Ｅｕ、Ｔｂ、Ｄｙ、及びＬｕからなる群より選ばれた少なくとも１種以上の希土類元素の水酸化物とを含む表面処理物質が被覆されていることを特徴とする。 (1) The phosphor of the present invention comprises at least one rare earth element selected from the group consisting of scandium orthophosphate and La, Y, Gd, Eu, Tb, Dy, and Lu on the phosphor particle surface. A surface treatment substance containing a hydroxide is coated.
（２）本発明の蛍光体は、（1）に記載の蛍光体であって、前記オルトリン酸塩の被覆量は、蛍光体に対しスカンジウムの量に換算して０．０３〜１０ｍｏｌ％の範囲であり、前記水酸化物の被覆量は、蛍光体に対し希土類元素の量に換算して０．３〜５．７ｍｏｌ％の範囲であることを特徴とする。 (2) The phosphor of the present invention is the phosphor according to (1), wherein the orthophosphate coating amount is in the range of 0.03 to 10 mol% in terms of the amount of scandium with respect to the phosphor. The coating amount of the hydroxide is in the range of 0.3 to 5.7 mol% in terms of the amount of rare earth element with respect to the phosphor.
（３）本発明の蛍光ランプは、透光性気密容器と、透光性気密容器内に形成された蛍光体層と、透光性気密容器内に封入された放電媒体と、電極とを具備する蛍光ランプにおいて、前記蛍光体層は（１）又は（２）に記載の蛍光体を含むことを特徴とする。 (3) A fluorescent lamp of the present invention includes a light-transmitting airtight container, a phosphor layer formed in the light-transmitting airtight container, a discharge medium sealed in the light-transmitting airtight container, and an electrode. In the fluorescent lamp, the phosphor layer includes the phosphor described in (1) or (2).
（４）本発明の蛍光ランプは、（３）に記載の蛍光ランプであって、前記蛍光ランプが冷陰極蛍光ランプであることを特徴とする。 (4) The fluorescent lamp of the present invention is the fluorescent lamp described in (3), wherein the fluorescent lamp is a cold cathode fluorescent lamp.
本発明は上記の特徴を備えているため、ランプ点灯時の管端色差が抑えられ、ランプ光束維持率が高く、ランプ色度の経時変化が少ない蛍光ランプが得られる。 Since the present invention has the above features, a fluorescent lamp can be obtained in which the color difference at the tube end when the lamp is turned on is suppressed, the lamp luminous flux maintenance factor is high, and the change in lamp chromaticity with time is small.
以下、本発明に係る蛍光体、蛍光ランプについて実施の形態及び実施例を用いて説明する。但し本発明はこれら実施の形態及び実施例に限定されるものではない。 Hereinafter, a phosphor and a fluorescent lamp according to the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to these embodiments and examples.
ここで、本発明の一実施の形態に係る蛍光体の表面処理方法について詳細に説明する。先ず、通常の方法に従い蛍光体を作製する。次に、この蛍光体を純水、エタノール水溶液等の分散媒に分散し、水溶性のスカンジウム化合物と、オルトリン酸または水溶性のオルトリン酸塩とを添加し攪拌する。この蛍光体懸濁液に酸又は塩基を加えてｐＨを２．０〜６．０の範囲に調整し、スカンジウムのオルトリン酸塩を蛍光体表面に析出させる。その後さらにＬａ、Ｙ、Ｇｄ、Ｅｕ、Ｔｂ、Ｄｙ、及びＬｕからなる群より選ばれた少なくとも１種以上の希土類元素の水溶性化合物を添加し、塩基を加えてｐＨを７．５〜１０．０の範囲に調整し、前記希土類元素の水酸化物を蛍光体表面に析出させる。その後、処理済の蛍光体と分散媒を分離し、乾燥して、本発明の蛍光体を得る。 Here, the phosphor surface treatment method according to the embodiment of the present invention will be described in detail. First, a phosphor is produced according to a normal method. Next, this phosphor is dispersed in a dispersion medium such as pure water or an aqueous ethanol solution, and a water-soluble scandium compound and orthophosphoric acid or a water-soluble orthophosphate are added and stirred. Acid or base is added to this phosphor suspension to adjust the pH to a range of 2.0 to 6.0, and scandium orthophosphate is deposited on the phosphor surface. Thereafter, at least one water-soluble compound of rare earth elements selected from the group consisting of La, Y, Gd, Eu, Tb, Dy, and Lu is added, and a base is added to adjust the pH to 7.5 to 10.2. The rare earth element hydroxide is deposited on the phosphor surface by adjusting the range to 0. Thereafter, the treated phosphor and the dispersion medium are separated and dried to obtain the phosphor of the present invention.
表面処理する蛍光体は紫外線励起で発光する蛍光体が使用できる。例えば、一般式Ｍ１０（ＰＯ４）６Ｘ２：Ｅｕ（但しＭはＳｒ，Ｃａ，Ｂａ，及びＭｇからなる群より選ばれた少なくとも一種以上の元素、ＸはＦ，Ｃｌ，Ｂｒ，及びＩからなる群より選ばれた少なくとも一種以上の元素）で表される２価のユーロピウム付活アルカリ土類ハロリン酸塩、一般式Ｍ２Ｐ２Ｏ７：Ｅｕ（但しＭはＳｒ，Ｃａ，Ｂａ，及びＭｇからなる群より選ばれた少なくとも一種以上の元素）で表される２価のユーロピウム付活アルカリ土類ピロリン酸塩、一般式（Ｂａ，Ｍ）２Ａｌ１０Ｏ１７：Ｅｕ（但しＭはＳｒ，Ｃａ，及びＭｇからなる群より選ばれた少なくとも一種以上の元素）で表される２価のユーロピウム付活アルカリ土類アルミン酸塩、一般式（Ｂａ，Ｍ）２Ａｌ１０Ｏ１７：Ｅｕ，Ｍｎ（但しＭはＳｒ，Ｃａ，及びＭｇからなる群より選ばれた少なくとも一種以上の元素）で表される２価のユーロピウム及び２価のマンガン共付活アルカリ土類アルミン酸塩、一般式Ｃｅ（Ｍｇ，Ｚｎ）ａＡｌ１１Ｏ１９−ａ：Ｍｎ（但し０．４≦ａ≦１．０）で表される３価のセリウム及び２価のマンガン共付活亜鉛マグネシウムアルミン酸塩、一般式Ｚｎ２ＳｉＯ４：Ｍｎで表される２価のマンガン付活亜鉛ケイ酸塩、一般式Ｚｎ２（Ｓｉ，Ｇｅ）Ｏ４：Ｍｎで表される２価のマンガン付活亜鉛ケイ・ゲルマン酸塩、一般式ＬａＰＯ４：Ｃｅ，Ｔｂで表される３価のセリウム及び３価のテルビウム共付活ランタンリン酸塩、一般式ＣｅＭｇＡｌ１１Ｏ１９：Ｔｂで表される３価のセリウム及び３価のテルビウム共付活マグネシウムアルミン酸塩、一般式ＹＶＯ４：Ｅｕで表される３価のユーロピウム付活イットリウムバナジン酸塩、一般式Ｙ（Ｐ，Ｖ）Ｏ４：Ｅｕで表される３価のユーロピウム付活イットリウムリン・バナジン酸塩、一般式ａＭｇＯ・ｂＭｇＦ２・ＧｅＯ２：Ｍｎ（但しａ＋ｂ＝４）で表される４価のマンガン付活マグネシウムフッ化ゲルマン酸塩、一般式Ｒ２Ｏ２Ｓ：Ｅｕ（但しＲはユーロピウムを除く１種または２種以上の希土類元素）で表される３価のユーロピウム付活希土類酸硫化物、及び一般式Ｒ２Ｏ３：Ｅｕ（但しＲはユーロピウムを除く１種または２種以上の希土類元素）で表される３価のユーロピウム付活希土類酸化物等が挙げられる。 As the phosphor to be surface-treated, a phosphor that emits light by ultraviolet excitation can be used. For example, the general formula M 10 (PO 4 ) 6 X 2 : Eu (where M is at least one element selected from the group consisting of Sr, Ca, Ba, and Mg, X is F, Cl, Br, and I) A divalent europium-activated alkaline earth halophosphate represented by the general formula M 2 P 2 O 7 : Eu (where M is Sr, Ca, Ba, And at least one element selected from the group consisting of Mg), a divalent europium-activated alkaline earth pyrophosphate represented by the general formula (Ba, M) 2 Al 10 O 17 : Eu (where M is A divalent europium-activated alkaline earth aluminate represented by the general formula (Ba, M) 2 Al 10 O 17 : Eu, represented by at least one element selected from the group consisting of Sr, Ca, and Mg) , Mn ( M is at least one element selected from the group consisting of Sr, Ca, and Mg) and a divalent europium and divalent manganese co-activated alkaline earth aluminate represented by the general formula Ce (Mg , Zn) a Al 11 O 19-a : trivalent cerium and divalent manganese co-activated zinc magnesium aluminate represented by Mn (where 0.4 ≦ a ≦ 1.0), the general formula Zn 2 Divalent manganese-activated zinc silicate represented by SiO 4 : Mn, general formula Zn 2 (Si, Ge) O 4 : Divalent manganese-activated zinc silicate / germanate represented by Mn, general Formula LaPO 4 : Trivalent cerium and trivalent terbium co-activated lanthanum phosphate represented by Ce, Tb, General formula CeMgAl 11 O 19 : Trivalent cerium and trivalent terbium represented by Tb Activated Magnesium Aluminates, formula YVO 4: 3-valent europium-activated yttrium vanadate represented by Eu, general formula Y (P, V) O 4 : 3 -valent europium activated yttrium Lynn represented by Eu Vanadate, general formula aMgO · bMgF 2 · GeO 2 : tetravalent manganese-activated magnesium fluorinated germanate represented by Mn (where a + b = 4), general formula R 2 O 2 S: Eu (where R Is a trivalent europium activated rare earth oxysulfide represented by one or two or more rare earth elements excluding europium, and a general formula R 2 O 3 : Eu (where R is one or two excluding europium) And trivalent europium activated rare earth oxides represented by the above rare earth elements).
これらの蛍光体のうち、２価のユーロピウム付活アルカリ土類ハロリン酸塩、２価のユーロピウム付活アルカリ土類ピロリン酸塩等のリン酸塩蛍光体の場合、予め蛍光体スラリーをｐＨ２．０〜５．０の範囲に酸処理して、蛍光体表面からリン酸分を溶出させてから、水溶性のスカンジウム化合物を添加してもよく、その分オルトリン酸またはオルトリン酸塩の添加量を調整する。 Among these phosphors, in the case of phosphate phosphors such as divalent europium activated alkaline earth halophosphates and divalent europium activated alkaline earth pyrophosphates, the phosphor slurry is preliminarily adjusted to pH 2.0. After acid treatment in the range of ~ 5.0 to elute the phosphoric acid component from the phosphor surface, a water-soluble scandium compound may be added, and the amount of orthophosphoric acid or orthophosphate added is adjusted accordingly. To do.
水溶性のスカンジウム化合物として、スカンジウムのハロゲン化物、硫酸塩、硝酸塩等が使用できる。例えば、塩化スカンジウム、硫酸スカンジウム、硝酸スカンジウム等が好ましく使用できる。水溶性のオルトリン酸塩として、オルトリン酸ナトリウム、オルトリン酸カリウム、オルトリン酸アンモニウム等が使用できる。Ｌａ、Ｙ、Ｇｄ、Ｅｕ、Ｔｂ、Ｄｙ、及びＬｕからなる群より選ばれた少なくとも１種以上の希土類元素の水溶性化合物として、これらの希土類元素のハロゲン化物、硫酸塩、硝酸塩等が使用できる。例えば、塩化ランタン、硫酸ランタン、硝酸ランタン等が好ましく使用できる。ｐＨ調整に使用する酸として、塩酸、硝酸、硝酸等の水溶液が使用でき、塩基として、アンモニア、アルカリ金属水酸化物等の水溶液が使用できる。 As the water-soluble scandium compound, scandium halides, sulfates, nitrates and the like can be used. For example, scandium chloride, scandium sulfate, scandium nitrate and the like can be preferably used. As the water-soluble orthophosphate, sodium orthophosphate, potassium orthophosphate, ammonium orthophosphate and the like can be used. As a water-soluble compound of at least one rare earth element selected from the group consisting of La, Y, Gd, Eu, Tb, Dy, and Lu, halides, sulfates, nitrates, and the like of these rare earth elements can be used. . For example, lanthanum chloride, lanthanum sulfate, lanthanum nitrate and the like can be preferably used. An aqueous solution such as hydrochloric acid, nitric acid and nitric acid can be used as the acid used for pH adjustment, and an aqueous solution such as ammonia and alkali metal hydroxide can be used as the base.
蛍光体粒子表面に被覆するスカンジウムのオルトリン酸塩の被覆量は、蛍光体に対しスカンジウムの量に換算して０．０３〜１０ｍｏｌ％の範囲が好ましく、０．０３〜８ｍｏｌ％の範囲がより好ましく０．１〜７ｍｏｌ％の範囲がさらに好ましい。 The amount of scandium orthophosphate coated on the phosphor particle surface is preferably in the range of 0.03 to 10 mol%, more preferably in the range of 0.03 to 8 mol% in terms of the amount of scandium with respect to the phosphor. The range of 0.1-7 mol% is more preferable.
蛍光体粒子表面に被覆する希土類元素の水酸化物として、Ｌａ、Ｙ、Ｇｄ、Ｅｕ、Ｔｂ、Ｄｙ、及びＬｕからなる群より選ばれた少なくとも１種以上の希土類元素の水酸化物が好ましく、Ｌａ、Ｙ、及びＧｄからなる群より選ばれた少なくとも１種以上の希土類元素の水酸化物がより好ましく、Ｌａの水酸化物が特に好ましい。スカンジウムのオルトリン酸塩とこれらの希土類元素の水酸化物とを被覆した蛍光体をバックライト用蛍光ランプに用いた場合、点灯時の光束維持率、色度の経時変化、及び管端色差が非常に改善される。 As the rare earth element hydroxide coated on the surface of the phosphor particles, at least one rare earth element hydroxide selected from the group consisting of La, Y, Gd, Eu, Tb, Dy, and Lu is preferable, A hydroxide of at least one rare earth element selected from the group consisting of La, Y, and Gd is more preferable, and a hydroxide of La is particularly preferable. When phosphors coated with scandium orthophosphate and hydroxides of these rare earth elements are used in fluorescent lamps for backlights, the luminous flux maintenance factor during lighting, chronological change in chromaticity, and color difference at the end of the tube are extremely high. To be improved.
蛍光体粒子表面に被覆する希土類元素の水酸化物の被覆量は、蛍光体に対し希土類元素の量に換算して０．３〜５．７ｍｏｌ％の範囲が好ましく、０．４〜４．８ｍｏｌ％の範囲がより好ましく、０．５〜４．４ｍｏｌ％の範囲がさらに好ましい。 The coating amount of the rare earth element hydroxide coated on the surface of the phosphor particles is preferably in the range of 0.3 to 5.7 mol% in terms of the amount of the rare earth element with respect to the phosphor, and 0.4 to 4.8 mol. % Is more preferable, and the range of 0.5 to 4.4 mol% is more preferable.
スカンジウムのオルトリン酸塩を蛍光体表面に析出させる場合、ｐＨ調整はｐＨ２．０〜６．０の範囲に調整するのが好ましく、ｐＨ２．５〜４．０の範囲がより好ましい。ｐＨが２．０より低いとオルトリン酸塩の被覆量が減少し、ｐＨが６．０より高いとスカンジウムの水酸化物の析出により表面処理効果が減少する。 When precipitating scandium orthophosphate onto the phosphor surface, the pH is preferably adjusted to a pH in the range of 2.0 to 6.0, more preferably in the range of pH 2.5 to 4.0. When the pH is lower than 2.0, the coating amount of orthophosphate decreases, and when the pH is higher than 6.0, the surface treatment effect decreases due to precipitation of scandium hydroxide.
Ｌａ、Ｙ、Ｇｄ、Ｅｕ、Ｔｂ、Ｄｙ、及びＬｕからなる群より選ばれた少なくとも１種以上の希土類元素の水酸化物を蛍光体表面に析出させる場合、ｐＨ調整はｐＨ７．５〜１０．０の範囲に調整するのが好ましく、ｐＨ８．０〜１０．０の範囲がより好ましい。ｐＨが７．５より低いと水酸化物の析出が少なくなるので表面処理効果が減少する。 When the hydroxide of at least one rare earth element selected from the group consisting of La, Y, Gd, Eu, Tb, Dy, and Lu is deposited on the phosphor surface, the pH adjustment is pH 7.5-10. It is preferable to adjust to the range of 0, and the range of pH 8.0 to 10.0 is more preferable. When the pH is lower than 7.5, the precipitation of hydroxide is reduced, so that the surface treatment effect is reduced.
このようにして蛍光体粒子表面にスカンジウムのオルトリン酸塩とＬａ、Ｙ、Ｇｄ、Ｅｕ、Ｔｂ、Ｄｙ、及びＬｕからなる群より選ばれた少なくとも１種以上の希土類元素の水酸化物とを含む表面処理物質が被覆された蛍光体を用いることにより、ランプ点灯時の管端色差が抑えられ、ランプ光束維持率が高く、ランプ色度の経時変化が少ない蛍光ランプが得られる。 In this way, the phosphor particle surface includes scandium orthophosphate and at least one rare earth element hydroxide selected from the group consisting of La, Y, Gd, Eu, Tb, Dy, and Lu. By using a phosphor coated with a surface treatment substance, a fluorescent lamp can be obtained in which the color difference at the tube end when the lamp is turned on is suppressed, the lamp luminous flux maintenance factor is high, and the change in lamp chromaticity with time is small.
次に、本発明の蛍光体を用いて冷陰極蛍光ランプを作製する。先ず、蛍光体とピロリン酸カルシウム、カルシウムバリウムボレート等の結着剤をニトロセルロース／酢酸ブチル溶液に添加し、これらを混合し懸濁させて蛍光体塗布懸濁液を調製する。得られた蛍光体塗布懸濁液をガラス管の内面に流し込み、その後これに温風を通じることで乾燥させ、ベーキング、排気、フィラメントの装着、口金の取り付けを行い、冷陰極蛍光ランプを得る。 Next, a cold cathode fluorescent lamp is produced using the phosphor of the present invention. First, a phosphor and a binder such as calcium pyrophosphate and calcium barium borate are added to a nitrocellulose / butyl acetate solution, and these are mixed and suspended to prepare a phosphor-coated suspension. The obtained phosphor-coated suspension is poured into the inner surface of the glass tube, and then dried by passing warm air through the glass tube, followed by baking, exhausting, attaching a filament, and attaching a base to obtain a cold cathode fluorescent lamp.
図１に、本発明の冷陰極蛍光ランプの一例を示す。ガラス等から成る透光性気密容器11の内壁には一種以上の蛍光体と結着剤から成る蛍光体層12が形成される。透光性気密容器11の内部にはネオン等の希ガス及び水銀蒸気から成る放電媒体13が封入され、透光性気密容器11の両端は一対の電極14a、14bによって封止される。両電極間に電圧をかけて放電媒体13に放電を起こさせ、その際励起された水銀から紫外線が放出され、該紫外線により蛍光体層12の蛍光体が励起されて発光する。
FIG. 1 shows an example of the cold cathode fluorescent lamp of the present invention. A phosphor layer 12 made of one or more phosphors and a binder is formed on the inner wall of the light-transmitting hermetic container 11 made of glass or the like. Inside the translucent airtight container 11, a
本発明の蛍光ランプは白色ランプでも、フィールドシーケンシャル方式液晶表示装置に用いられるような単色ランプであっても、点灯時の光束維持率、色度の経時変化、及び管端色差が改善される。 Whether the fluorescent lamp of the present invention is a white lamp or a monochromatic lamp used in a field sequential type liquid crystal display device, the luminous flux maintenance factor at the time of lighting, chronological change in chromaticity, and tube end color difference are improved.
白色ランプの場合、青色蛍光体（Ｂ：発光ピークが４２０ｎｍ〜４８０ｎｍ付近）、緑色蛍光体（Ｇ：発光ピークが５００ｎｍ〜５６０ｎｍ付近）、赤色蛍光体（Ｒ：発光ピークが６２０ｎｍ〜６８０ｎｍ付近）の混合比が重量比でＢ：２５％〜５５％、Ｇ：１５％〜３５％、Ｒ：２５％〜５５％（但しＢ＋Ｇ＋Ｒ＝１００％）の範囲内で使用される。 In the case of a white lamp, a blue phosphor (B: emission peak around 420 nm to 480 nm), a green phosphor (G: emission peak around 500 nm to 560 nm), a red phosphor (R: emission peak around 620 nm to 680 nm) The mixing ratio is B: 25% to 55%, G: 15% to 35%, R: 25% to 55% (B + G + R = 100%).
青色蛍光体として２価のユーロピウム付活アルカリ土類ハロリン酸塩、２価のユーロピウム付活アルカリ土類ピロリン酸塩、２価のユーロピウム付活アルカリ土類アルミン酸塩からなる群より選ばれた少なくとも１種以上の蛍光体を、緑色蛍光体として２価のユーロピウムおよび２価のマンガン付活アルカリ土類アルミン酸塩、３価のセリウムおよび２価のマンガン付活亜鉛マグネシウムアルミン酸からなる群より選ばれた少なくとも１種以上の蛍光体を、赤色蛍光体として３価のユーロピウム付活イットリウムバナジン酸塩、３価のユーロピウム付活イットリウムリン・バナジン酸塩、４価のマンガン付活マグネシウムフッ化ゲルマン酸塩、３価のユーロピウム付活希土類酸化物からなる群より選ばれた少なくとも１種以上の蛍光体が使用される。 At least selected from the group consisting of a divalent europium activated alkaline earth halophosphate, a divalent europium activated alkaline earth pyrophosphate, and a divalent europium activated alkaline earth aluminate as a blue phosphor One or more phosphors are selected from the group consisting of divalent europium and divalent manganese-activated alkaline earth aluminate, trivalent cerium and divalent manganese-activated zinc magnesium aluminate as the green phosphor. At least one of the phosphors used as a red phosphor is a trivalent europium activated yttrium vanadate, a trivalent europium activated yttrium phosphorus / vanadate, a tetravalent manganese activated magnesium fluorogermanic acid Use at least one phosphor selected from the group consisting of salts, trivalent europium activated rare earth oxides It is.
特に、青色蛍光体として２価のユーロピウム付活アルカリ土類ハロリン酸塩、なかでもＳＣＡ蛍光体（２価のユーロピウム付活ストロンチウムクロロアパタイト蛍光体やこの蛍光体のストロンチウムの一部または全部を他のアルカリ土類金属で置換したアルカリ土類クロロアパタイト蛍光体）を用いて色再現範囲を拡大したバックライト用蛍光ランプにおいて、発光輝度維持率、色度の経時変化、及び管端色差が改善され効果がある。 In particular, divalent europium-activated alkaline earth halophosphates as blue phosphors, especially SCA phosphors (divalent europium-activated strontium chloroapatite phosphors and some or all of the strontium of this phosphor In a fluorescent lamp for backlights that uses an alkaline earth chloroapatite phosphor substituted with an alkaline earth metal), the emission luminance maintenance rate, chromaticity change with time, and tube end color difference are improved. There is.
次に、本発明の蛍光体及び蛍光ランプの特性について図を用いて説明する。実施例１において硝酸スカンジウムの添加量を変化させて得られる蛍光体について、実施例１と同様に白色冷陰極蛍光ランプを作製し、蛍光体に被覆した表面処理物質のＳｃ量（ｍｏｌ％）と白色冷陰極蛍光ランプの各特性との関係を図２〜図５に示した。すなわち、白色冷陰極蛍光ランプの初期光束（％）との関係を図２に、光束維持率（％）との関係を図３に、色度ｘの変化量Δｘとの関係を図４に、色度ｙの変化量Δｙとの関係を図５に、それぞれ示した。 Next, characteristics of the phosphor and the fluorescent lamp of the present invention will be described with reference to the drawings. For the phosphor obtained by changing the amount of scandium nitrate added in Example 1, a white cold cathode fluorescent lamp was prepared in the same manner as in Example 1, and the amount of Sc (mol%) of the surface treatment substance coated on the phosphor was determined. The relationship with each characteristic of the white cold cathode fluorescent lamp is shown in FIGS. That is, FIG. 2 shows the relationship with the initial luminous flux (%) of the white cold cathode fluorescent lamp, FIG. 3 shows the relationship with the luminous flux maintenance factor (%), and FIG. 4 shows the relationship with the variation Δx of the chromaticity x. The relationship with the change amount Δy of chromaticity y is shown in FIG.
図２から、白色冷陰極蛍光ランプの初期光束（％）は、蛍光体に被覆した表面処理物質のＳｃ量（ｍｏｌ％）が０．０３〜８ｍｏｌ％の範囲で１０９％以上、０．１〜７ｍｏｌ％の範囲で１０９．５％以上、０．６〜６ｍｏｌ％の範囲で１１０％以上であって、初期光束（％）が高いことがわかる。しかしながら、初期光束（％）が１０８％以上であれば白色冷陰極蛍光ランプとして発光特性は十分であるため、１０ｍｏｌ％未満でも良い。 From FIG. 2, the initial luminous flux (%) of the white cold cathode fluorescent lamp is 109% or more, 0.1 to 0.1% within the range of 0.03 to 8 mol% of the Sc amount (mol%) of the surface treatment material coated on the phosphor. It can be seen that 109.5% or more in the range of 7 mol%, 110% or more in the range of 0.6 to 6 mol%, and the initial luminous flux (%) is high. However, if the initial luminous flux (%) is 108% or more, the light emitting characteristics are sufficient as a white cold cathode fluorescent lamp, and the amount may be less than 10 mol%.
図３から、白色冷陰極蛍光ランプの光束維持率（％）は、蛍光体に被覆した表面処理物質のＳｃ量（ｍｏｌ％）が０．０３〜１０ｍｏｌ％の範囲で９６％以上、０．１〜１０ｍｏｌ％の範囲で９７％以上であって、光束維持率（％）が高いことがわかる。 From FIG. 3, the luminous flux maintenance factor (%) of the white cold cathode fluorescent lamp is 96% or more and 0.1% in the range where the Sc amount (mol%) of the surface treatment material coated on the phosphor is 0.03 to 10 mol%. It can be seen that it is 97% or more in the range of -10 mol% and the luminous flux maintenance factor (%) is high.
図４から、白色冷陰極蛍光ランプの色度ｘの変化量Δｘは、蛍光体に被覆した表面処理物質のＳｃ量（ｍｏｌ％）が０．０３〜１０ｍｏｌ％の範囲で０．００１９以下、０．１〜１０ｍｏｌ％の範囲で０．００１７以下であって、色度ｘの変化量Δｘが小さいことがわかる。 From FIG. 4, the amount of change Δx in the chromaticity x of the white cold cathode fluorescent lamp is 0.0019 or less in the range where the Sc amount (mol%) of the surface treatment material coated on the phosphor is 0.03 to 10 mol%, 0 It can be seen that the amount of change Δx of chromaticity x is small in the range of 0.1 to 10 mol% and 0.0017 or less.
図５から、白色冷陰極蛍光ランプの色度ｙの変化量Δｙは、蛍光体に被覆した表面処理物質のＳｃ量（ｍｏｌ％）が０．０３〜１０ｍｏｌ％の範囲で０．００５５以下、０．１〜１０ｍｏｌ％の範囲で０．００５２５以下であって、色度ｙの変化量Δｙが小さいことがわかる。 From FIG. 5, the amount of change Δy in the chromaticity y of the white cold cathode fluorescent lamp is 0.0055 or less in the range where the Sc amount (mol%) of the surface treatment material coated on the phosphor is 0.03 to 10 mol%, 0 It is 0.00525 or less in the range of 0.1 to 10 mol%, and it can be seen that the change amount Δy of chromaticity y is small.
従って、図２〜図５から、白色冷陰極蛍光ランプの光束と光束維持率が高く、色度変化が少ないＳｃ量の範囲は、蛍光体に対し０．０３〜１０ｍｏｌ％の範囲が好ましく、０．０３〜８ｍｏｌ％の範囲がより好ましく、０．１〜７ｍｏｌ％の範囲がさらに好ましいことがわかる。 Therefore, from FIG. 2 to FIG. 5, the range of Sc amount with a high luminous flux and luminous flux maintenance factor of the white cold cathode fluorescent lamp and little chromaticity change is preferably 0.03 to 10 mol% with respect to the phosphor. The range of 0.03 to 8 mol% is more preferable, and the range of 0.1 to 7 mol% is more preferable.
実施例１において硝酸ランタンの添加量を変化させて得られるＳＣＡ蛍光体について、実施例１と同様にして白色冷陰極蛍光ランプを作製し、蛍光体に被覆した表面処理物質のＬａ量（ｍｏｌ％）と冷陰極蛍光ランプの各特性との関係を図６〜図９に示した。すなわち、白色冷陰極蛍光ランプの初期光束（％）との関係を図６に、光束維持率（％）との関係を図７に、色度ｘの変化量Δｘとの関係を図８に、色度ｙの変化量Δｙとの関係を図９に、それぞれ示した。 For the SCA phosphor obtained by changing the amount of lanthanum nitrate added in Example 1, a white cold cathode fluorescent lamp was prepared in the same manner as in Example 1, and the amount of La (mol%) of the surface treatment substance coated on the phosphor was prepared. ) And the respective characteristics of the cold cathode fluorescent lamp are shown in FIGS. That is, FIG. 6 shows the relationship with the initial luminous flux (%) of the white cold cathode fluorescent lamp, FIG. 7 shows the relationship with the luminous flux maintenance factor (%), and FIG. 8 shows the relationship with the variation Δx of the chromaticity x. The relationship between the change amount Δy of chromaticity y is shown in FIG.
図６から、白色冷陰極蛍光ランプの初期光束（％）は、蛍光体に被覆した表面処理物質のＬａ量（ｍｏｌ％）が０．４〜４．８ｍｏｌ％の範囲で１０９％以上、０．５〜４．４ｍｏｌ％の範囲で１０９．５％以上、０．６５〜３．８５ｍｏｌ％の範囲で１１０％以上であって、初期光束（％）が高いことがわかる。しかしながら、初期光束（％）が１０８％以上であれば白色冷陰極蛍光ランプとして発光特性は十分であるため、０．３〜５．７ｍｏｌ％の範囲でも良い。 From FIG. 6, the initial luminous flux (%) of the white cold cathode fluorescent lamp is 109% or more in the range where the amount of La (mol%) of the surface treatment substance coated on the phosphor is 0.4 to 4.8 mol%, and 0.0%. It can be seen that the initial luminous flux (%) is high with 109.5% or more in the range of 5 to 4.4 mol% and 110% or more in the range of 0.65 to 3.85 mol%. However, if the initial luminous flux (%) is 108% or more, the light emitting characteristics are sufficient as a white cold cathode fluorescent lamp, and the range of 0.3 to 5.7 mol% may be sufficient.
図７から、白色冷陰極蛍光ランプの光束維持率（％）は、蛍光体に被覆した表面処理物質のＬａ量（ｍｏｌ％）が０．１〜９．５ｍｏｌ％の範囲で９６％以上、０．３〜７．３ｍｏｌ％の範囲で９７％以上であって、光束維持率（％）が高いことがわかる。 From FIG. 7, the luminous flux maintenance factor (%) of the white cold cathode fluorescent lamp is 96% or more when the La amount (mol%) of the surface treatment substance coated on the phosphor is 0.1 to 9.5 mol%, 0 It can be seen that it is 97% or more in the range of 0.3 to 7.3 mol%, and the luminous flux maintenance factor (%) is high.
図８から、白色冷陰極蛍光ランプの色度ｘの変化量Δｘは、蛍光体に被覆した表面処理物質のＬａ量（ｍｏｌ％）が０．３〜９．１ｍｏｌ％の範囲で０．００１９以下、０．４〜８．５ｍｏｌ％の範囲で０．００１７以下であって、色度ｘの変化量Δｘが小さいことがわかる。 From FIG. 8, the amount of change Δx of the chromaticity x of the white cold cathode fluorescent lamp is 0.0019 or less when the La amount (mol%) of the surface treatment substance coated on the phosphor is in the range of 0.3 to 9.1 mol%. In the range of 0.4 to 8.5 mol%, it is 0.0017 or less, and the change amount Δx of the chromaticity x is small.
図９から、白色冷陰極蛍光ランプの色度ｙの変化量Δｙは、蛍光体に被覆した表面処理物質のＬａ量（ｍｏｌ％）が０．３〜１０ｍｏｌ％の範囲で０．００５５以下、０．３５〜１０ｍｏｌ％の範囲で０．００５２５以下であって、色度ｙの変化量Δｙが小さいことがわかる。 From FIG. 9, the amount of change Δy in the chromaticity y of the white cold cathode fluorescent lamp is 0.0055 or less, 0 when the La amount (mol%) of the surface treatment substance coated on the phosphor is 0.3 to 10 mol%. It can be seen that it is 0.00525 or less in the range of 35 to 10 mol%, and the change amount Δy of the chromaticity y is small.
従って、図６〜図９から、白色冷陰極蛍光ランプの光束と光束維持率が高く、色度変化が少ないＬａ量の範囲は、蛍光体に対し０．３〜５．７ｍｏｌ％の範囲が好ましく、０．４〜４．８ｍｏｌ％の範囲がより好ましく、０．５〜４．４ｍｏｌ％の範囲がさらに好ましいことがわかる。 Therefore, from FIG. 6 to FIG. 9, the range of La amount with a high luminous flux and luminous flux maintenance factor of the white cold cathode fluorescent lamp and a small chromaticity change is preferably in the range of 0.3 to 5.7 mol% with respect to the phosphor. The range of 0.4 to 4.8 mol% is more preferable, and the range of 0.5 to 4.4 mol% is more preferable.
以下、本発明の実施例について説明するが、本発明は具体的実施例のみに限定されるものではないことは言うまでもない。 Examples of the present invention will be described below, but it goes without saying that the present invention is not limited to specific examples.
［実施例１］
一般式が（Ｓｒ０．９９Ｅｕ０．０１）１０（ＰＯ４）６Ｃｌ２で表される２価のユーロピウム付活ストロンチウムクロロアパタイト蛍光体（ＳＣＡ蛍光体）１００ｇを純水３００ｍｌに入れ懸濁する。硝酸スカンジウム・ｎ水和物を使用し０．３ｍｏｌ／ｌに調整した硝酸スカンジウム溶液３．７５ｍｌを添加する。さらに、２．０ｗｔ％オルトリン酸溶液１０．６ｍｌを添加し、攪拌する。この蛍光体懸濁液に０．２ｗｔ％硝酸溶液を加えてｐＨを３．０に調整し、スカンジウムのオルトリン酸塩を蛍光体表面に析出させる。その後、硝酸ランタン・六水和物を使用し０．３ｍｏｌ／ｌに調整した硝酸ランタン溶液７．２ｍｌを添加し、２．０ｗｔ％水酸化アンモニウム溶液を加えてｐＨ９．５に調整し、ランタンの水酸化物を蛍光体表面に析出させる。ｐＨ調整後、十分に洗浄、脱液、乾燥、篩を行い、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 1]
100 g of divalent europium activated strontium chloroapatite phosphor (SCA phosphor) represented by the general formula (Sr 0.99 Eu 0.01 ) 10 (PO 4 ) 6 Cl 2 is suspended in 300 ml of pure water. To do. Add 3.75 ml of scandium nitrate solution adjusted to 0.3 mol / l using scandium nitrate n-hydrate. Further, 10.6 ml of 2.0 wt% orthophosphoric acid solution is added and stirred. A 0.2 wt% nitric acid solution is added to the phosphor suspension to adjust the pH to 3.0, and scandium orthophosphate is deposited on the phosphor surface. Thereafter, 7.2 ml of lanthanum nitrate solution adjusted to 0.3 mol / l using lanthanum nitrate hexahydrate was added, and adjusted to pH 9.5 by adding 2.0 wt% ammonium hydroxide solution. A hydroxide is deposited on the phosphor surface. After adjusting the pH, washing, draining, drying and sieving are performed sufficiently to obtain an SCA phosphor coated with scandium orthophosphate and lanthanum hydroxide.
こうして得られる青色発光の上記ＳＣＡ蛍光体と、（Ｂａ０．９Ｅｕ０．１）（Ｍｇ０．９Ｍｎ０．１）Ａｌ１０Ｏ１７緑色発光蛍光体と、（Ｙ０．９Ｅｕ０．１）２Ｏ３赤色発光蛍光体を重量比で青色：緑色：赤色＝５０：２０：３０の割合で混合する。この混合蛍光体と結着剤をニトロセルロース／酢酸ブチル溶液に添加し、混合して蛍光体塗布スラリーを調製する。これを管径３ｍｍ、長さ４００ｍｍのガラス管に流し込み、その内面に塗布し、温風を通じて乾燥し、５６０℃で３分間塗布バルブをベーキングして、蛍光膜を形成する。その後、通常の方法に従い、排気、電極のマウント、口金の取り付けを行い、白色冷陰極蛍光ランプを得る。 The blue light-emitting SCA phosphor thus obtained, (Ba 0.9 Eu 0.1 ) (Mg 0.9 Mn 0.1 ) Al 10 O 17 green light-emitting phosphor, and (Y 0.9 Eu 0. 1 ) 2 O 3 red light emitting phosphors are mixed at a weight ratio of blue: green: red = 50: 20: 30. This mixed phosphor and binder are added to a nitrocellulose / butyl acetate solution and mixed to prepare a phosphor-coated slurry. This is poured into a glass tube having a tube diameter of 3 mm and a length of 400 mm, applied to the inner surface thereof, dried through warm air, and baked at 560 ° C. for 3 minutes to form a fluorescent film. Then, according to a normal method, exhaust, electrode mounting, and attachment of a base are performed to obtain a white cold cathode fluorescent lamp.
［実施例２］
０．３ｍｏｌ／ｌに調整した硝酸スカンジウム溶液を０．７５ｍｌ添加する以外は実施例１と同様の方法で作製し、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 2]
A SCA phosphor coated with scandium orthophosphate and lanthanum hydroxide was prepared in the same manner as in Example 1 except that 0.75 ml of scandium nitrate solution adjusted to 0.3 mol / l was added. .
［実施例３］
０．３ｍｏｌ／ｌに調整した硝酸スカンジウム溶液を７．５ｍｌ添加する以外は実施例１と同様の方法で作製し、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 3]
A SCA phosphor coated with scandium orthophosphate and lanthanum hydroxide was prepared in the same manner as in Example 1 except that 7.5 ml of scandium nitrate solution adjusted to 0.3 mol / l was added. .
［実施例４］
０．３ｍｏｌ／ｌに調整した硝酸ランタン溶液を３．６ｍｌ添加する以外は実施例１と同様の方法で作製し、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 4]
An SCA phosphor coated with scandium orthophosphate and lanthanum hydroxide was prepared in the same manner as in Example 1 except that 3.6 ml of a lanthanum nitrate solution adjusted to 0.3 mol / l was added. .
［実施例５］
０．３ｍｏｌ／ｌに調整した硝酸ランタン溶液を１１．２８ｍｌ添加する以外は実施例１と同様の方法で作製し、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 5]
An SCA phosphor coated with scandium orthophosphate and lanthanum hydroxide was prepared in the same manner as in Example 1 except that 11.28 ml of lanthanum nitrate solution adjusted to 0.3 mol / l was added. .
［実施例６］
０．３ｍｏｌ／ｌに調整した硝酸イットリウム溶液を７．５ｍｌ添加する以外は実施例３と同様の方法で作製し、スカンジウムのオルトリン酸塩とイットリウムの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 6]
A SCA phosphor coated with scandium orthophosphate and yttrium hydroxide was prepared in the same manner as in Example 3 except that 7.5 ml of an yttrium nitrate solution adjusted to 0.3 mol / l was added. .
［実施例７］
０．３ｍｏｌ／ｌに調整した硝酸ガドリニウム溶液を７．５ｍｌ添加する以外は実施例３と同様の方法で作製し、スカンジウムのオルトリン酸塩とガドリニウムの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 7]
A SCA phosphor coated with scandium orthophosphate and gadolinium hydroxide was prepared in the same manner as in Example 3 except that 7.5 ml of gadolinium nitrate solution adjusted to 0.3 mol / l was added. .
［実施例８］
０．３ｍｏｌ／ｌに調整した硝酸ユーロピウム溶液を７．５ｍｌ添加する以外は実施例３と同様の方法で作製し、スカンジウムのオルトリン酸塩とユーロピウムの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 8]
An SCA phosphor coated with scandium orthophosphate and europium hydroxide was prepared in the same manner as in Example 3 except that 7.5 ml of europium nitrate solution adjusted to 0.3 mol / l was added. .
［実施例９］
０．３ｍｏｌ／ｌに調整した硝酸テルビウム溶液を７．５ｍｌ添加する以外は実施例１と同様の方法で作製し、スカンジウムのオルトリン酸塩とテルビウムの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 9]
An SCA phosphor coated with scandium orthophosphate and terbium hydroxide was prepared in the same manner as in Example 1 except that 7.5 ml of a terbium nitrate solution adjusted to 0.3 mol / l was added. .
［実施例１０］
０．３ｍｏｌ／ｌに調整した硝酸ディスプロシウム溶液を７．５ｍｌ添加する以外は実施例１と同様の方法で作製し、スカンジウムのオルトリン酸塩とディスプロシウムの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 10]
An SCA prepared in the same manner as in Example 1 except that 7.5 ml of a dysprosium nitrate solution adjusted to 0.3 mol / l was added and coated with scandium orthophosphate and dysprosium hydroxide A phosphor is obtained.
［実施例１１］
０．３ｍｏｌ／ｌに調整した硝酸ルテチウム溶液を７．５ｍｌ添加する以外は実施例３と同様の方法で作製し、スカンジウムのオルトリン酸塩とルテチウムの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Example 11]
A SCA phosphor coated with scandium orthophosphate and lutetium hydroxide was prepared in the same manner as in Example 3 except that 7.5 ml of a lutetium nitrate solution adjusted to 0.3 mol / l was added. .
［比較例１］
表面処理物質が被覆されていないＳＣＡ蛍光体を用意する。
[Comparative Example 1]
An SCA phosphor that is not coated with a surface treatment substance is prepared.
［比較例２］
ＳＣＡ蛍光体１００ｇを純水３００ｍｌに入れ懸濁する。硝酸スカンジウム・ｎ水和物を使用し０．３ｍｏｌ／ｌに調整した硝酸スカンジウム溶液３．７５ｍｌを添加する。さらに、２．０ｗｔ％オルトリン酸溶液１０．６ｍｌを添加し、攪拌する。この蛍光体懸濁液に０．２ｗｔ％硝酸溶液を加えてｐＨを３．０に調整し、スカンジウムのオルトリン酸塩を蛍光体表面に析出させる。ｐＨ調整後、十分に洗浄、脱液、乾燥、篩を行い、スカンジウムのオルトリン酸塩で被覆されたＳＣＡ蛍光体を得る。
[Comparative Example 2]
100 g of SCA phosphor is suspended in 300 ml of pure water. Add 3.75 ml of scandium nitrate solution adjusted to 0.3 mol / l using scandium nitrate n-hydrate. Further, 10.6 ml of 2.0 wt% orthophosphoric acid solution is added and stirred. A 0.2 wt% nitric acid solution is added to the phosphor suspension to adjust the pH to 3.0, and scandium orthophosphate is deposited on the phosphor surface. After adjusting the pH, washing, draining, drying and sieving are performed sufficiently to obtain an SCA phosphor coated with scandium orthophosphate.
［比較例３］
ＳＣＡ蛍光体１００ｇを純水３００ｍｌに入れ懸濁する。硝酸ランタン・六水和物を使用し０．３ｍｏｌ／ｌに調整した硝酸ランタン溶液７．２ｍｌを添加し、２．０ｗｔ％水酸化アンモニウム溶液を加えてｐＨ９．５に調整し、ランタンの水酸化物を蛍光体表面に析出させる。ｐＨ調整後、十分に洗浄、脱液、乾燥、篩を行い、ランタンの水酸化物で被覆されたＳＣＡ蛍光体を得る。
[Comparative Example 3]
100 g of SCA phosphor is suspended in 300 ml of pure water. Add 7.2 ml of lanthanum nitrate solution adjusted to 0.3 mol / l using lanthanum nitrate hexahydrate, adjust to pH 9.5 by adding 2.0 wt% ammonium hydroxide solution, and hydrate the lanthanum hydroxide. Deposits on the phosphor surface. After pH adjustment, washing, draining, drying and sieving are performed sufficiently to obtain an SCA phosphor coated with lanthanum hydroxide.
実施例１〜１１及び比較例１〜３で得られるＳＣＡ蛍光体について、表面処理物質の被覆量をＩＣＰ発光分光分析法により測定した結果を表１に示す。この表から、本発明の実施例の蛍光体は、スカンジウムのオルトリン酸塩の被覆量が蛍光体に対しスカンジウムの量に換算して０．０３〜１０ｍｏｌ％の範囲であり、希土類元素の水酸化物の被覆量が蛍光体に対し希土類元素の量に換算して０．４〜５．７ｍｏｌ％の範囲であることがわかる。また、これらの蛍光体を用いて、実施例１と同様にして白色冷陰極蛍光ランプを作製する。 Table 1 shows the results of measuring the coating amount of the surface treatment substance by ICP emission spectroscopic analysis for the SCA phosphors obtained in Examples 1 to 11 and Comparative Examples 1 to 3. From this table, the phosphor of the example of the present invention has a scandium orthophosphate coating amount in the range of 0.03 to 10 mol% in terms of the amount of scandium with respect to the phosphor, and the hydroxylation of rare earth elements. It can be seen that the coating amount of the product is in the range of 0.4 to 5.7 mol% in terms of the amount of rare earth element with respect to the phosphor. Also, using these phosphors, a white cold cathode fluorescent lamp is produced in the same manner as in Example 1.
こうして得られる白色冷陰極蛍光ランプについて、初期光束（％）（相対値）と、１００時間点灯したときの光束維持率（％）、色度ｘの変化量Δｘ、及び色度ｙの変化量Δｙを求め、表１に示す。この表から、本発明の実施例の蛍光ランプはいずれも１００時間点灯したときの光束維持率が９６％以上であり、比較例の蛍光ランプに比べて光束維持率が高いことがわかる。また、本発明の実施例の蛍光ランプは、Δｘ及びΔｙがそれぞれΔｘ≦＋０．００１９、Δｙ≦＋０．０５５の範囲にあり、比較例の蛍光ランプに比べて小さく、色度の経時変化が少ないことがわかる。 For the white cold cathode fluorescent lamp thus obtained, the initial luminous flux (%) (relative value), the luminous flux maintenance factor (%) when lit for 100 hours, the change amount Δx of chromaticity x, and the change amount Δy of chromaticity y. Is shown in Table 1. From this table, it can be seen that all of the fluorescent lamps of the examples of the present invention have a luminous flux maintenance factor of 96% or more when lit for 100 hours, which is higher than that of the fluorescent lamp of the comparative example. Further, in the fluorescent lamp of the example of the present invention, Δx and Δy are in the ranges of Δx ≦ + 0.0019 and Δy ≦ + 0.055, respectively, which is smaller than the fluorescent lamp of the comparative example and has little change with time in chromaticity. I understand that.
次に、実施例１と比較例１〜３の白色冷陰極蛍光ランプについて、点灯直後の管端色差を次のように測定する。すなわち、蛍光ランプの一端から３０ｍｍ、２００ｍｍ、３７０ｍｍの位置で発光色を測定し、管端部（３０ｍｍ、３７０ｍｍ）と中央部（２００ｍｍ）における発光色の差を求め、表２に示した。この表から、本発明の実施例１の蛍光ランプは、比較例１〜３の蛍光ランプに比べ、管端色差が少ないことがわかる。 Next, for the white cold cathode fluorescent lamps of Example 1 and Comparative Examples 1 to 3, the tube end color difference immediately after lighting is measured as follows. That is, the emission color was measured at positions of 30 mm, 200 mm, and 370 mm from one end of the fluorescent lamp, and the difference in emission color between the tube end portion (30 mm, 370 mm) and the central portion (200 mm) was determined. From this table, it can be seen that the fluorescent lamp of Example 1 of the present invention has less tube end color difference than the fluorescent lamps of Comparative Examples 1 to 3.
［実施例１２］
一般式が（Ｚｎ０．９４Ｍｎ０．０６）２ＳｉＯ４で表される２価のマンガン付活亜鉛ケイ酸塩蛍光体（ＺＳＭ蛍光体）１００ｇを純水３００ｍｌに入れ懸濁する。硝酸スカンジウム・ｎ水和物を使用し０．３ｍｏｌ／ｌに調整した硝酸スカンジウム溶液７．４ｍｌを添加する。さらに、２．０ｗｔ％オルトリン酸溶液１０．６ｍｌを添加し、攪拌する。この蛍光体懸濁液に０．２ｗｔ％硝酸溶液を加えてｐＨを３．０に調整し、スカンジウムのオルトリン酸塩を蛍光体表面に析出させる。その後、硝酸ランタン・六水和物を使用し０．３ｍｏｌ／ｌに調整した硝酸ランタン溶液７．２ｍｌを添加し、２．０ｗｔ％水酸化アンモニウム溶液を加えてｐＨ９．５に調整し、ランタンの水酸化物を蛍光体表面に析出させる。ｐＨ調整後、十分に洗浄、脱液、乾燥、篩を行い、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＺＳＭ蛍光体を得る。
[Example 12]
100 g of divalent manganese-activated zinc silicate phosphor (ZSM phosphor) represented by the general formula (Zn 0.94 Mn 0.06 ) 2 SiO 4 is suspended in 300 ml of pure water. 7.4 ml of a scandium nitrate solution adjusted to 0.3 mol / l using scandium nitrate.n hydrate is added. Further, 10.6 ml of 2.0 wt% orthophosphoric acid solution is added and stirred. A 0.2 wt% nitric acid solution is added to the phosphor suspension to adjust the pH to 3.0, and scandium orthophosphate is deposited on the phosphor surface. Thereafter, 7.2 ml of lanthanum nitrate solution adjusted to 0.3 mol / l using lanthanum nitrate hexahydrate was added, and adjusted to pH 9.5 by adding 2.0 wt% ammonium hydroxide solution. A hydroxide is deposited on the phosphor surface. After pH adjustment, washing, draining, drying and sieving are performed sufficiently to obtain a ZSM phosphor coated with scandium orthophosphate and lanthanum hydroxide.
こうして得られる緑色発光の上記ＺＳＭ蛍光体と結着剤をニトロセルロース／酢酸ブチル溶液に添加し、混合して蛍光体塗布スラリーを調製する。これを管径３ｍｍ、長さ４００ｍｍのガラス管に流し込み、その内面に塗布し、温風を通じて乾燥し、５６０℃で３分間塗布バルブをベーキングして、蛍光膜を形成する。その後、通常の方法に従い、排気、電極のマウント、口金の取り付けを行い、単色冷陰極蛍光ランプを得る。 The green light emitting ZSM phosphor thus obtained and a binder are added to a nitrocellulose / butyl acetate solution and mixed to prepare a phosphor coating slurry. This is poured into a glass tube having a tube diameter of 3 mm and a length of 400 mm, applied to the inner surface thereof, dried through warm air, and baked at 560 ° C. for 3 minutes to form a fluorescent film. Then, according to a normal method, exhaust, electrode mounting, and attachment of a base are performed, and a monochromatic cold cathode fluorescent lamp is obtained.
［比較例４］
表面処理物質が被覆されていないＺＳＭ蛍光体を用意する。
[Comparative Example 4]
A ZSM phosphor that is not coated with a surface treatment material is prepared.
［実施例１３］
ＺＳＭ蛍光体の代わりに一般式が（Ｙ０．９４Ｅｕ０．０６）２Ｏ２Ｓで表される３価のユーロピウム付活希土類酸硫化物蛍光体（ＹＯＳ蛍光体）を使用する以外は実施例１２と同様の方法で作製し、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＹＯＳ蛍光体を得る。
[Example 13]
Implemented except that a trivalent europium activated rare earth oxysulfide phosphor (YOS phosphor) represented by the general formula (Y 0.94 Eu 0.06 ) 2 O 2 S is used instead of the ZSM phosphor. A YOS phosphor coated with scandium orthophosphate and lanthanum hydroxide is obtained in the same manner as in Example 12.
［比較例５］
表面処理物質が被覆されていないＹＯＳ蛍光体を用意する。
[Comparative Example 5]
A YOS phosphor that is not coated with a surface treatment substance is prepared.
［実施例１４］
ＺＳＭ蛍光体の代わりに一般式が（Ｂａ０．９Ｅｕ０．１）ＭｇＡｌ１０Ｏ１７で表される３価のユーロピウム付活希土類酸硫化物蛍光体（ＢＡＭ蛍光体）を使用する以外は実施例１２と同様の方法で作製し、スカンジウムのオルトリン酸塩とランタンの水酸化物で被覆されたＢＡＭ蛍光体を得る。
[Example 14]
Implemented except that a trivalent europium activated rare earth oxysulfide phosphor (BAM phosphor) represented by the general formula (Ba 0.9 Eu 0.1 ) MgAl 10 O 17 is used instead of the ZSM phosphor. A BAM phosphor coated with scandium orthophosphate and lanthanum hydroxide is prepared in the same manner as in Example 12.
［比較例６］
表面処理物質が被覆されていないＢＡＭ蛍光体を用意する。
[Comparative Example 6]
A BAM phosphor that is not coated with a surface treatment substance is prepared.
実施例１２〜１４及び比較例４〜６で得られる蛍光体について、表面処理物質の被覆量を表３に示す。この表から、本発明の実施例の蛍光体は、スカンジウムのオルトリン酸塩の被覆量が蛍光体に対しスカンジウムの量に換算して０．０３〜１０ｍｏｌ％の範囲であり、希土類元素の水酸化物の被覆量が蛍光体に対し希土類元素の量に換算して０．４〜５．７ｍｏｌ％の範囲であることがわかる。また、これらの蛍光体を用いて、実施例１２と同様にして単色冷陰極蛍光ランプを作製する。 Table 3 shows the coating amounts of the surface treatment substances for the phosphors obtained in Examples 12 to 14 and Comparative Examples 4 to 6. From this table, the phosphor of the example of the present invention has a scandium orthophosphate coating amount in the range of 0.03 to 10 mol% in terms of the amount of scandium with respect to the phosphor, and the hydroxylation of rare earth elements. It can be seen that the coating amount of the product is in the range of 0.4 to 5.7 mol% in terms of the amount of rare earth element with respect to the phosphor. In addition, using these phosphors, a monochromatic cold cathode fluorescent lamp is manufactured in the same manner as in Example 12.
こうして得られる単色冷陰極蛍光ランプについて、３００時間点灯したときの光束維持率（％）を求め、表３に示す。この表から、本発明の実施例の蛍光ランプは、表面処理物質が被覆されていない比較例の蛍光ランプに比べて、光束維持率が高いことがわかる。 For the monochromatic cold cathode fluorescent lamp thus obtained, the luminous flux maintenance factor (%) when lit for 300 hours was determined and shown in Table 3. From this table, it can be seen that the fluorescent lamp of the example of the present invention has a higher luminous flux maintenance factor than the fluorescent lamp of the comparative example not coated with the surface treatment substance.
以上に述べたように、本発明によって、ランプ点灯時の管端色差が抑えられ、ランプ光束維持率が高く、ランプ色度の経時変化が少ない蛍光ランプが得られることから、カラー液晶表示装置のバックライト等の光源用として好適に利用することができる。 As described above, according to the present invention, it is possible to obtain a fluorescent lamp that suppresses the color difference at the tube end when the lamp is turned on, has a high lamp luminous flux maintenance factor, and has little change over time in lamp chromaticity. It can be suitably used for a light source such as a backlight.
11 透光性気密容器
12 蛍光体層
13 放電媒体
14a、14b 電極
11 Translucent airtight container
12 Phosphor layer
13 Discharge medium
14a, 14b electrode
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |