JPH04270782A - Stimulable phosphor and fluorescent lamp using the same - Google Patents
Stimulable phosphor and fluorescent lamp using the sameInfo
- Publication number
- JPH04270782A JPH04270782A JP3117391A JP3117391A JPH04270782A JP H04270782 A JPH04270782 A JP H04270782A JP 3117391 A JP3117391 A JP 3117391A JP 3117391 A JP3117391 A JP 3117391A JP H04270782 A JPH04270782 A JP H04270782A
- Authority
- JP
- Japan
- Prior art keywords
- fluorescent lamp
- phosphor
- stimulable phosphor
- mol
- fluorescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004020 luminiscence type Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 11
- 150000004645 aluminates Chemical class 0.000 abstract description 10
- 230000007423 decrease Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 229910018404 Al2 O3 Inorganic materials 0.000 description 11
- 229910052693 Europium Inorganic materials 0.000 description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 235000010216 calcium carbonate Nutrition 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 235000012254 magnesium hydroxide Nutrition 0.000 description 6
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002178 europium compounds Chemical class 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
Abstract
Description
【０００１】［発明の目的］[Object of the invention]
【０００２】0002
【産業上の利用分野】この発明は２価のユ−ロピウムで
付活された青色発光の蛍光体および蛍光ランプに関する
。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a blue-emitting phosphor activated with divalent europium and a fluorescent lamp.
【０００３】0003
【従来の技術】近年一般照明用蛍光ランプとして、高演
色性と高効率性を同時に満足する三波長域発光形蛍光ラ
ンプが開発され普及している。この三波長域発光形蛍光
ランプは比較的狭帯域の発光スペクトル分布を有する青
色，緑色，赤色発光蛍光体を任意の割合で混合し蛍光膜
を形成することによって，白色または希望する色の発光
を得る蛍光ランプである。BACKGROUND OF THE INVENTION In recent years, three-wavelength fluorescent lamps that simultaneously satisfy high color rendering properties and high efficiency have been developed and become popular as fluorescent lamps for general illumination. This three-wavelength fluorescent lamp emits white light or a desired color by mixing blue, green, and red light-emitting phosphors with relatively narrow emission spectrum distribution in arbitrary proportions to form a fluorescent film. This is a fluorescent lamp.
【０００４】このため，各蛍光体の発光特性がランプ点
灯中に変化すると，初期のランプ発光色からずれを生じ
ることになる。すなわち，ランプ点灯中の各々の蛍光体
の光出力（発光強度）の低下および発光色の変化の大き
さの違いにより色ずれ現象が起こり，商品価値を低下さ
せている。最近の三波長域発光形蛍光ランプの青色発光
成分として，アルミン酸塩蛍光体が用いられている。[0004] For this reason, if the light emitting characteristics of each phosphor change while the lamp is lit, the color of the light emitted by the lamp will deviate from the initial color. That is, a color shift phenomenon occurs due to a decrease in the light output (emission intensity) of each phosphor and a difference in the magnitude of change in the emitted color while the lamp is on, reducing the commercial value. Aluminate phosphors are used as the blue light-emitting component of recent three-wavelength fluorescent lamps.
【０００５】従来、２価のユ−ロピウムで付活されたア
ルミン酸青色発光蛍光体としては、［（Ｂａ，Ｅｕ）Ｍ
ｇ２ Ａｌ１６Ｏ２７］（特公昭５２−２２８３６）、
［ＡＯ−Ａｌ２ Ｏ３ 、、ＡはＺｎ，Ｃａ，Ｓｒ，Ｂ
ａ，Ｌｉ２，Ｒｂ２，Ｃｓ２ の少なくとも１種からな
る］（特公昭５８−２２４９５）が知られている。Conventionally, as an aluminate blue-emitting phosphor activated with divalent europium, [(Ba,Eu)M
g2 Al16O27] (Special Publication No. 52-22836),
[AO-Al2O3, A is Zn, Ca, Sr, B
a, Li2, Rb2, and Cs2] (Japanese Patent Publication No. 58-22495) is known.
【０００６】また、酸化リンを固溶させたストロンチウ
ムアルミネ−ト蛍光体（特開昭６１−６９８８５），け
い素を固溶させたアルミン酸青色発光蛍光体も知られて
いる（特開昭６２−５７８号、特開昭６２−２４３６８
０）。Also known are strontium aluminate phosphors containing phosphorus oxide as a solid solution (Japanese Patent Application Laid-Open No. 61-69885) and aluminate blue-emitting phosphors containing silicon as a solid solution (Japanese Patent Application Laid-Open No. 62-1999). No.-578, JP-A-62-24368
0).
【０００７】しかし、これらは、ランプ点灯中の蛍光体
の光出力（発光強度）の低下の点で満足いくものとは言
えず，改良すべき点が多い。However, these methods are not satisfactory in terms of a reduction in the light output (emission intensity) of the phosphor during lamp lighting, and there are many points that need to be improved.
【０００８】[0008]
【発明が解決しようとする課題】以上述べたように，三
波長域発光形蛍光ランプはランプ発光強度が高く，色ず
れ現象の小さいものが望まれているが，この色ずれ現象
を最小限にするためには，ランプ点灯中の蛍光体の光出
力（発光強度）の低下の少ないものの出現が必要である
。[Problems to be Solved by the Invention] As mentioned above, it is desired that a three-wavelength fluorescent lamp has a high lamp emission intensity and a small color shift phenomenon, but it is desirable to minimize this color shift phenomenon. In order to achieve this, it is necessary to develop a phosphor whose light output (emission intensity) decreases less during lamp operation.
【０００９】この発明は上記課題を解決するためになさ
れたもので，２５４ｎｍ 水銀輝線励起下で高い発光を
示し，ランプ点灯中の発光強度の低下の少ない蛍光体お
よび蛍光ランプを提供することを目的とする。[0009] This invention was made to solve the above-mentioned problems, and an object thereof is to provide a phosphor and a fluorescent lamp that exhibit high luminescence under 254 nm mercury emission line excitation and exhibit less decrease in luminescence intensity during lamp operation. shall be.
【００１０】［発明の構成］[Configuration of the invention]
【００１１】[0011]
【課題を解決するための手段】この発明は，２価のユ−
ロピウムで付活された青色発光の蛍光体にリンを加える
ことにより三波長域発光形蛍光ランプ点灯中の発光強度
の低下が少なくなることを見いだしたことによる。[Means for Solving the Problems] This invention provides bivalent
This is based on the discovery that the addition of phosphor to a blue-emitting phosphor activated with lopium reduces the drop in luminescence intensity during lighting of a three-wavelength fluorescent lamp.
【００１２】即ち、この発明は，一般式（ＢａＸ Ｍｇ
Ｙ ＣａＺ ＥｕＷ ）Ｏ・ａＡｌ２ Ｏ３ ・ｂＰ２
Ｏ５ （ここで、０．１ ≦Ｘ ≦０．５， ０．
１ ≦Ｙ ≦０．８， ０ ＜ｚ ≦０．２， ０
．０３≦Ｗ ≦０．１０， の範囲の値であり，かつＸ
＋Ｙ＋ｚ＋Ｗ＝１ ，および１．５ ≦ａ ≦４．５，
０．００１ ≦ｂ ≦０．１００ の範囲の値であ
る。）で表される蛍光体である。That is, the present invention is based on the general formula (BaX Mg
Y CaZ EuW )O・aAl2 O3 ・bP2
O5 (where 0.1≦X≦0.5, 0.
1 ≦Y ≦0.8, 0 <z ≦0.2, 0
．． 03≦W≦0.10, and X
+Y+z+W=1, and 1.5≦a≦4.5,
The value is in the range of 0.001≦b≦0.100. ) is a phosphor represented by
【００１３】また，この発明は上記蛍光体を用いた蛍光
ランプである。The present invention also provides a fluorescent lamp using the above-mentioned phosphor.
【００１４】本発明の蛍光体の原料として，アルカリ土
類金属源にはアルカリ土類金属の酸化物や水酸化物，炭
酸塩等の高温において容易にアルカリ土類金属の酸化物
になる化合物群の中から選ばれた少なくとも一種，ユ−
ロピウム源には酸化ユ−ロピウム，炭酸ユ−ロピウム等
の高温において容易に酸化ユ−ロピウムになるユ−ロピ
ウム化合物群の中から選ばれた少なくとも一種，アルミ
ニウム源には酸化アルミニウム，水酸化アルミニウム等
の高温において容易に酸化アルミニウムになるアルミニ
ウム化合物群の中から選ばれた少なくとも一種，リン源
にはリン酸アンモニウム等の高温において容易に酸化リ
ンになるリン化合物群の中から選ばれた少なくとも一種
が用いられる。As a raw material for the phosphor of the present invention, the alkaline earth metal source includes a group of compounds that easily become alkaline earth metal oxides at high temperatures, such as alkaline earth metal oxides, hydroxides, and carbonates. At least one selected from
The source of europium is at least one selected from the group of europium compounds that easily turn into europium oxide at high temperatures, such as europium oxide and europium carbonate, and the source of aluminum is aluminum oxide, aluminum hydroxide, etc. At least one kind selected from the group of aluminum compounds that easily become aluminum oxide at high temperatures, and at least one selected from the group of phosphorus compounds that easily become phosphorus oxide at high temperatures, such as ammonium phosphate, as the phosphorus source. used.
【００１５】本発明の蛍光体の製造は，まづ，これらの
原料を所定量秤量し，ボ−ルミル等によって充分に粉砕
し，混合する。この充分混合した原料混合物を坩堝等の
耐熱容器に入れ，空気中において１２００℃から１４０
０℃で２ 〜３ 時間焼成する。得られた焼成物を粉砕
し，再び坩堝等の耐熱容器に入れ，還元性雰囲気におい
て１４００℃から１７００℃で４ 〜５ 時間焼成する
。こうしてできた焼成物を粉砕，水洗等の処理を加える
。To manufacture the phosphor of the present invention, first, a predetermined amount of these raw materials is weighed, thoroughly ground using a ball mill, etc., and mixed. This well-mixed raw material mixture was placed in a heat-resistant container such as a crucible, and heated at 1200°C to 140°C in air.
Bake at 0°C for 2-3 hours. The obtained fired product is crushed, placed again in a heat-resistant container such as a crucible, and fired at 1400°C to 1700°C for 4 to 5 hours in a reducing atmosphere. The fired product thus produced is subjected to treatments such as crushing and washing with water.
【００１６】さらに，一般式中のＸ，Ｙ，Ｚ，Ｗ，ａ，
ｂについて範囲を限定した理由を，以下に述べる。Furthermore, in the general formula, X, Y, Z, W, a,
The reason for limiting the range of b is described below.
【００１７】すなわちＷの値が０．０３より小さいと，
蛍光体中の付活剤の濃度が低く，発光強度の点で不十分
であり，０．１０より大きいと濃度消光によって発光強
度が下がる。次に，ａの値が１．５ より小さいと，結
晶構造が不安定になり，蛍光ランプ製造工程中の劣化が
大きく実用性に欠け，４．５ より大きいと，非発光相
の出現により発光強度の点で不十分である。[0017] That is, if the value of W is smaller than 0.03,
The concentration of the activator in the phosphor is low and the emission intensity is insufficient, and if it is greater than 0.10, the emission intensity decreases due to concentration quenching. Next, if the value of a is less than 1.5, the crystal structure becomes unstable and deterioration occurs during the fluorescent lamp manufacturing process, making it impractical. Insufficient strength.
【００１８】また，ｂの値が０．１００ より大きいと
非発光相が現れ，０．００１ より小さいとランプ点灯
中の発光強度の低下に対して効果を示さなくなる。より
好ましいｂの値の範囲は，０．０１〜０．０５である。
Ｘ，Ｙ，Ｚ については，前記範囲以外では発光強度が
下がる。Further, if the value of b is greater than 0.100, a non-luminous phase will appear, and if it is less than 0.001, it will not be effective in reducing the luminous intensity during lamp lighting. A more preferable range of the value of b is 0.01 to 0.05. Regarding X, Y, and Z, the emission intensity decreases outside the above range.
【００１９】[0019]
【作用】この発明によれば，２５４ｎｍ 水銀輝線励起
下で高い発光を示し，ランプ点灯中の発光強度の低下が
著しく改善される。[Operation] According to the present invention, high luminescence is exhibited under excitation of a 254 nm mercury emission line, and the decrease in luminescence intensity during lamp lighting is significantly improved.
【００２０】[0020]
【実施例】実施例１
ＢａＣＯ３ ０．４５ モ
ルＭｇ（ＯＨ）２ ０．４０ モル
ＣａＣＯ３ ０．１０ モ
ルＥｕ２ Ｏ３ ０．０２５
モルＡｌ２ Ｏ３ ２．５
モル（ＮＨ４ ）２ ＨＰＯ４ ０．００１
モル上記各原料を秤量し，ボ−ルミルによって十分に
粉砕，混合した。この原料混合物をルツボに入れ，空気
中において１４００℃で３時間焼成した。[Example] Example 1 BaCO3 0.45 mol Mg(OH)2 0.40 mol CaCO3 0.10 mol Eu2 O3 0.025
Mol Al2 O3 2.5
Mol (NH4)2 HPO4 0.001
The moles of each of the above raw materials were weighed, thoroughly ground and mixed using a ball mill. This raw material mixture was placed in a crucible and fired at 1400° C. for 3 hours in air.
【００２１】得られた焼成物を粉砕し再びルツボにいれ
，３％水素，９７％ 窒素の還元性雰囲気において１６
００℃で４ 時間焼成した。[0021] The obtained fired product was pulverized and put into a crucible again, and heated to 16% in a reducing atmosphere of 3% hydrogen and 97% nitrogen.
It was baked at 00°C for 4 hours.
【００２２】こうしてできた焼成物を粉砕，水洗等の処
理を加え
（Ｂａ０．４５Ｍｇ０．４０Ｃａ０．１０Ｅｕ０．０５
）Ｏ・２．５ Ａｌ２ Ｏ３ ・０．００１Ｐ２ Ｏ５
で表される２価のユ−ロピウム付活アルミン酸塩蛍光体
を得た。[0022] The fired product thus produced is subjected to treatments such as pulverization and washing with water (Ba0.45Mg0.40Ca0.10Eu0.05
)O・2.5 Al2 O3 ・0.001P2 O5
A divalent europium-activated aluminate phosphor represented by the following formula was obtained.
【００２３】また，この蛍光体をガラスバルブ内面に塗
布し，蛍光ランプを製造し点灯させたところ，製造直後
の蛍光ランプの発光強度は１３９％で，１０００時間点
灯後の発光強度比も０．９０と，いずれも比較例として
青色発光蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａｌ１６Ｏ２
７を用いたものの１００％および０．７８を上回り，改
善が認められた。Furthermore, when this phosphor was applied to the inner surface of a glass bulb to manufacture a fluorescent lamp and turn it on, the emission intensity of the fluorescent lamp immediately after manufacture was 139%, and the emission intensity ratio after 1000 hours of lighting was also 0. 90 and (Ba,Eu)Mg2Al16O2 for the blue-emitting phosphor as comparative examples.
The improvement was recognized as exceeding 100% and 0.78 of that using 7.
【００２４】実施例２
ＢａＣＯ３ ０．４５ モ
ルＭｇ（ＯＨ）２ ０．３０ モル
ＣａＣＯ３ ０．２０ モ
ルＥｕ２ Ｏ３ ０．０２５
モルＡｌ２ Ｏ３ ２．５
モル（ＮＨ４ ）２ ＨＰＯ４ ０．００１
モル上記各原料を実施例１と同様に処理したところ得
られた２価のユ−ロピウム付活アルミン酸塩蛍光体は（
Ｂａ０．４５Ｍｇ０．３０Ｃａ０．２０Ｅｕ０．０５）
Ｏ・２．５ Ａｌ２ Ｏ３ ・０．００１Ｐ２ Ｏ５
であった。Example 2 BaCO3 0.45 mol Mg(OH)2 0.30 mol CaCO3 0.20 mol Eu2 O3 0.025
Mol Al2 O3 2.5
Mol (NH4)2 HPO4 0.001
Mol The divalent europium-activated aluminate phosphor obtained by treating each of the above raw materials in the same manner as in Example 1 was (
Ba0.45Mg0.30Ca0.20Eu0.05)
O.2.5 Al2 O3 .0.001P2 O5.
【００２５】また，この蛍光体をガラスバルブ内面に塗
布し，蛍光ランプを製造し点灯させたところ，製造直後
の蛍光ランプの発光強度は１３９％で，１０００時間点
灯後の発光強度比も０．８９と，いずれも比較例として
青色発光蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａｌ１６Ｏ２
７を用いたものの１００％および０．７８を上回り，改
善が認められた。Furthermore, when this phosphor was applied to the inner surface of a glass bulb and a fluorescent lamp was manufactured and turned on, the emission intensity of the fluorescent lamp immediately after manufacture was 139%, and the emission intensity ratio after 1000 hours of lighting was also 0. 89, and (Ba,Eu)Mg2Al16O2 as a blue-emitting phosphor as a comparative example.
The improvement was recognized as exceeding 100% and 0.78 of that using 7.
【００２６】実施例３
ＢａＣＯ３ ０．２５ モ
ルＭｇ（ＯＨ）２ ０．５０ モル
ＣａＣＯ３ ０．２０ モ
ルＥｕ２ Ｏ３ ０．０２５
モルＡｌ２ Ｏ３ ２．５
モル（ＮＨ４ ）２ ＨＰＯ４ ０．００１
モル上記各原料を実施例１と同様に処理したところ得
られた２価のユ−ロピウム付活アルミン酸塩蛍光体は（
Ｂａ０．２５Ｍｇ０．５０Ｃａ０．２０Ｅｕ０．０５）
Ｏ・２．５ Ａｌ２ Ｏ３ ・０．００１Ｐ２ Ｏ５
であった。Example 3 BaCO3 0.25 mol Mg(OH)2 0.50 mol CaCO3 0.20 mol Eu2 O3 0.025
Mol Al2 O3 2.5
Mol (NH4)2 HPO4 0.001
Mol The divalent europium-activated aluminate phosphor obtained by treating each of the above raw materials in the same manner as in Example 1 was (
Ba0.25Mg0.50Ca0.20Eu0.05)
O.2.5 Al2 O3 .0.001P2 O5.
【００２７】また，この蛍光体をガラスバルブ内面に塗
布し，蛍光ランプを製造し点灯させたところ，製造直後
の蛍光ランプの発光強度は１３８％で，１０００時間点
灯後の発光強度比も０．８８と，いずれも比較例として
青色発光蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａｌ１６Ｏ２
７を用いたものの１００％および０．７８を上回り，改
善が認められた。Furthermore, when this phosphor was applied to the inner surface of a glass bulb and a fluorescent lamp was manufactured and turned on, the emission intensity of the fluorescent lamp immediately after manufacture was 138%, and the emission intensity ratio after 1000 hours of lighting was also 0. 88 and (Ba,Eu)Mg2Al16O2 as a comparative example for the blue-emitting phosphor.
The improvement was recognized as exceeding 100% and 0.78 of that using 7.
【００２８】実施例４
ＢａＣＯ３ ０．１８ モ
ルＭｇ（ＯＨ）２ ０．７０ モル
ＣａＣＯ３ ０．０５ モ
ルＥｕ２ Ｏ３ ０．０３５
モルＡｌ２ Ｏ３ ２．５
モル（ＮＨ４ ）２ ＨＰＯ４ ０．００１
モル上記各原料を実施例１と同様に処理したところ得
られた２価のユ−ロピウム付活アルミン酸塩蛍光体は（
Ｂａ０．１８Ｍｇ０．７０Ｃａ０．０５Ｅｕ０．０７）
Ｏ・２．５ Ａｌ２ Ｏ３ ・０．００１Ｐ２ Ｏ５
であった。Example 4 BaCO3 0.18 mol Mg(OH)2 0.70 mol CaCO3 0.05 mol Eu2 O3 0.035
Mol Al2 O3 2.5
Mol (NH4)2 HPO4 0.001
Mol The divalent europium-activated aluminate phosphor obtained by treating each of the above raw materials in the same manner as in Example 1 was (
Ba0.18Mg0.70Ca0.05Eu0.07)
O.2.5 Al2 O3 .0.001P2 O5.
【００２９】また，この蛍光体をガラスバルブ内面に塗
布し，蛍光ランプを製造し点灯させたところ，製造直後
の蛍光ランプの発光強度は１３７％で，１０００時間点
灯後の発光強度比も０．８８と，いずれも比較例として
青色発光蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａｌ１６Ｏ２
７を用いたものの１００％および０．７８を上回り，改
善が認められた。Furthermore, when this phosphor was applied to the inner surface of a glass bulb and a fluorescent lamp was manufactured and lit, the luminescence intensity of the fluorescent lamp immediately after manufacture was 137%, and the luminescence intensity ratio after 1000 hours of lighting was also 0. 88 and (Ba,Eu)Mg2Al16O2 as a comparative example for the blue-emitting phosphor.
The improvement was recognized as exceeding 100% and 0.78 of that using 7.
【００３０】実施例５
ＢａＣＯ３ ０．２８ モ
ルＭｇ（ＯＨ）２ ０．６０ モル
ＣａＣＯ３ ０．０５ モ
ルＥｕ２ Ｏ３ ０．０３５
モルＡｌ２ Ｏ３ ２．５
モル（ＮＨ４ ）２ ＨＰＯ４ ０．００１
モル上記各原料を実施例１と同様に処理したところ得
られた２価のユ−ロピウム付活アルミン酸塩蛍光体は（
Ｂａ０．２８Ｍｇ０．６０Ｃａ０．０５Ｅｕ０．０７）
Ｏ・２．５ Ａｌ２ Ｏ３ ・０．００１Ｐ２ Ｏ５
であった。Example 5 BaCO3 0.28 mol Mg(OH)2 0.60 mol CaCO3 0.05 mol Eu2 O3 0.035
Mol Al2 O3 2.5
Mol (NH4)2 HPO4 0.001
Mol The divalent europium-activated aluminate phosphor obtained by treating each of the above raw materials in the same manner as in Example 1 was (
Ba0.28Mg0.60Ca0.05Eu0.07)
O.2.5 Al2 O3 .0.001P2 O5.
【００３１】また，この蛍光体をガラスバルブ内面に塗
布し，蛍光ランプを製造し点灯させたところ，製造直後
の蛍光ランプの発光強度は１３８％で，１０００時間点
灯後の発光強度比も０．８８と，いずれも比較例として
青色発光蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａｌ１６Ｏ２
７を用いたものの１００％および０．７８を上回り，改
善が認められた。Furthermore, when this phosphor was applied to the inner surface of a glass bulb to manufacture a fluorescent lamp and turn it on, the emission intensity of the fluorescent lamp immediately after manufacture was 138%, and the emission intensity ratio after 1000 hours of lighting was also 0. 88 and (Ba,Eu)Mg2Al16O2 as a comparative example for the blue-emitting phosphor.
The improvement was recognized as exceeding 100% and 0.78 of that using 7.
【００３２】実施例６ 〜 実施例８０ＢａＣＯ３
，Ｍｇ（ＯＨ）２ ，ＣａＣＯ３ ，Ｅｕ２ Ｏ３
，Ａｌ２ Ｏ３ ，（ＮＨ４ ）２ ＨＰＯ４ を原料
として用い表１に示す配合で、実施例１と同様に処理し
て得られた２価のユ−ロピウム付活アルミン酸塩蛍光体
をガラスバルブ内面に塗布し，蛍光ランプを製造し点灯
させた。製造直後の蛍光ランプの発光強度および１００
０時間点灯後の発光強度を測定したところ，いずれも比
較例として青色発光蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａ
ｌ１６Ｏ２７を用いたものの１００％および０．７８を
上回り，改善が認められた。その結果を表１から表３に
示す。Examples 6 to 80 BaCO3
, Mg(OH)2 , CaCO3 , Eu2 O3
, Al2O3, (NH4)2HPO4 as raw materials and the composition shown in Table 1, a divalent europium-activated aluminate phosphor obtained by processing in the same manner as in Example 1 was applied to the inner surface of a glass bulb. They applied the material, manufactured fluorescent lamps, and lit them up. Emission intensity of fluorescent lamp immediately after manufacture and 100
When we measured the luminescence intensity after lighting for 0 hours, we found that (Ba, Eu)Mg2A was used as a blue-emitting phosphor as a comparative example.
Improvement was observed, exceeding 100% and 0.78 of that using l16O27. The results are shown in Tables 1 to 3.
【００３３】実施例８１
この発明の蛍光ランプの赤色発光蛍光体として（Ｙ，Ｅ
ｕ）２ Ｏ３ ，緑色発光蛍光体として（Ｌａ，Ｃｅ，
Ｔｂ）ＰＯ４ ，青色発光蛍光体として上記実施例１の
（Ｂａ０．４５Ｍｇ０．４０Ｃａ０．１０Ｅｕ０．０５
）Ｏ・２．５ Ａｌ２ Ｏ３ ・０．００１ Ｐ２ Ｏ
５ を用い，これら３蛍光体の総重量を１００％とした
時，それぞれ４２重量％ ，４５重量％ ，１３重量％
の割合で含有するように充分混合し，これをガラスバ
ルブ内面に塗布して蛍光膜を形成して，昼白色蛍光ラン
プを得た。Example 81 As a red-emitting phosphor of the fluorescent lamp of the present invention (Y, E
u) 2 O3, as a green-emitting phosphor (La, Ce,
Tb)PO4, (Ba0.45Mg0.40Ca0.10Eu0.05 of Example 1 above) as a blue-emitting phosphor
)O・2.5 Al2 O3 ・0.001 P2 O
5, and when the total weight of these three phosphors is taken as 100%, they are 42% by weight, 45% by weight, and 13% by weight, respectively.
A daylight white fluorescent lamp was obtained by coating the inner surface of a glass bulb to form a fluorescent film.
【００３４】この蛍光ランプを点灯させたところ，製造
直後の蛍光ランプの発光強度は，比較例として青色発光
蛍光体に（Ｂａ，Ｅｕ）Ｍｇ２ Ａｌ１６Ｏ２７を用い
たものを１００ としたときに１１８ ，また１０００
時間点灯後の発光強度の比も比較例の０．８３に対して
０．９２と，特性の向上が認められた。When this fluorescent lamp was turned on, the luminescence intensity of the fluorescent lamp immediately after manufacture was 118 when compared to 100 for a comparative example using (Ba,Eu)Mg2Al16O27 as a blue-emitting phosphor, and 1000
The ratio of luminescence intensity after lighting for a certain period of time was also 0.92 compared to 0.83 in the comparative example, indicating an improvement in characteristics.
【００３５】実施例８２ 〜 実施例９０表４に示
す配合で、実施例８１と同様に処理して昼白色蛍光ラン
プを得た。製造直後の蛍光ランプの発光強度および１０
００時間点灯後の発光強度を測定したところ，いずれも
特性の向上が認められた。その結果を表４に示す。Examples 82 to 90 Daylight white fluorescent lamps were obtained using the formulations shown in Table 4 and treated in the same manner as in Example 81. Emission intensity of fluorescent lamp immediately after manufacture and 10
When the luminescence intensity was measured after lighting for 00 hours, improvement in characteristics was observed in all cases. The results are shown in Table 4.
【００３６】次に，上述した蛍光体からなる蛍光膜を備
えた蛍光ランプの例を図１に示す。蛍光ランプは図に示
すように，バルブ（１） の内面に被着された蛍光膜（
２） を備え，さらにバルブ（１） 内に所定圧の放電
用ガスを封入しており，バルブ（１） の両端部に取り
付けられた電極（３）に所定電圧を印加し，励起源によ
って蛍光膜（２） が発光するものである。Next, FIG. 1 shows an example of a fluorescent lamp equipped with a fluorescent film made of the above-mentioned fluorescent material. As shown in the figure, a fluorescent lamp consists of a fluorescent film (1) coated on the inner surface of a bulb (1).
2), and a discharge gas of a predetermined pressure is sealed in the bulb (1), and a predetermined voltage is applied to the electrodes (3) attached to both ends of the bulb (1), and the excitation source generates fluorescence. The film (2) emits light.
【００３７】もちろん，この蛍光膜（２） はこの発明
による蛍光体からなっている。Of course, this phosphor film (2) is made of the phosphor according to the present invention.
【００３８】この発明は，上記のこの発明に係る蛍光体
からなる蛍光膜を具備する蛍光ランプを含むものである
。The present invention includes a fluorescent lamp provided with a fluorescent film made of the above-mentioned phosphor according to the present invention.
【００３９】[0039]
【表１】[Table 1]
【００４０】[0040]
【表２】[Table 2]
【００４１】[0041]
【表３】[Table 3]
【００４２】[0042]
【表４】[Table 4]
【００４３】[0043]
【発明の効果】以上の実施例から明らかなように、この
発明によればランプ点灯中の発光強度の低下の少ない青
色蛍光体およびこの蛍光体からなる蛍光膜を備えた蛍光
ランプを実現することができる。[Effects of the Invention] As is clear from the above embodiments, according to the present invention, it is possible to realize a fluorescent lamp equipped with a blue phosphor and a fluorescent film made of this phosphor, in which the luminescence intensity decreases little during lamp lighting. Can be done.
【図１】この発明の蛍光体からなる蛍光膜を備えた蛍光
ランプの一実施例を一部断面にして示す正面図である。FIG. 1 is a partially cross-sectional front view of an embodiment of a fluorescent lamp equipped with a fluorescent film made of the phosphor of the present invention.
１ ガラスバルブ ２ 蛍光膜 ３ 電極 1 Glass bulb 2. Fluorescent film 3 Electrode
Claims (2)
ｕＷ ）Ｏ・ａＡｌ２ Ｏ３ ・ｂＰ２ Ｏ５ （ここ
で、 ０．１ ≦Ｘ ≦０．５，０．１ ≦Ｙ ≦０
．８，０ ＜ｚ ≦０．２，０．０３≦Ｗ ≦０．１０
， の範囲の値であり，かつ、Ｘ＋Ｙ＋ｚ＋Ｗ＝１ ，
および、１．５ ≦ａ ≦４．５， ０．００１ ≦
ｂ ≦０．１００ の範囲の値である。）で表されるこ
とを特徴とする蛍光体。[Claim 1] General formula (BaX MgY CaZ E
uW ) O・aAl2 O3 ・bP2 O5 (where, 0.1 ≦X ≦0.5, 0.1 ≦Y ≦0
．． 8,0 <z ≦0.2, 0.03≦W ≦0.10
, and X+Y+z+W=1 ,
and 1.5≦a≦4.5, 0.001≦
It is a value in the range of b≦0.100. ) A phosphor characterized by being represented by:
を特徴とする蛍光ランプ。2. A fluorescent lamp characterized by using the phosphor according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3117391A JPH04270782A (en) | 1991-02-27 | 1991-02-27 | Stimulable phosphor and fluorescent lamp using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3117391A JPH04270782A (en) | 1991-02-27 | 1991-02-27 | Stimulable phosphor and fluorescent lamp using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04270782A true JPH04270782A (en) | 1992-09-28 |
Family
ID=12324054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3117391A Withdrawn JPH04270782A (en) | 1991-02-27 | 1991-02-27 | Stimulable phosphor and fluorescent lamp using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04270782A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0921172A1 (en) * | 1997-11-06 | 1999-06-09 | Matsushita Electric Industrial Co., Ltd. | Method for producing a divalent europium-activated phosphor |
| WO2003097769A1 (en) * | 2002-05-17 | 2003-11-27 | Matsushita Electric Industrial Co., Ltd. | Plasma display unit, phosphor and process for producing phosphor |
| KR100589734B1 (en) * | 2003-08-29 | 2006-06-19 | 마쯔시다덴기산교 가부시키가이샤 | Plasma display device |
-
1991
- 1991-02-27 JP JP3117391A patent/JPH04270782A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0921172A1 (en) * | 1997-11-06 | 1999-06-09 | Matsushita Electric Industrial Co., Ltd. | Method for producing a divalent europium-activated phosphor |
| US6096243A (en) * | 1997-11-06 | 2000-08-01 | Matsushita Electric Industrial Co., Ltd. | Method for producing a divalent europium-activated phosphor |
| WO2003097769A1 (en) * | 2002-05-17 | 2003-11-27 | Matsushita Electric Industrial Co., Ltd. | Plasma display unit, phosphor and process for producing phosphor |
| US7208102B2 (en) | 2002-05-17 | 2007-04-24 | Matsushita Electric Industrial Co., Ltd. | Plasma display unit, phosphor and process for producing phosphor |
| CN100396753C (en) * | 2002-05-17 | 2008-06-25 | 松下电器产业株式会社 | Plasma display unit, phosphor and process for producing phosphor |
| KR100589734B1 (en) * | 2003-08-29 | 2006-06-19 | 마쯔시다덴기산교 가부시키가이샤 | Plasma display device |
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