JPH0745656B2 - Phosphor - Google Patents
PhosphorInfo
- Publication number
- JPH0745656B2 JPH0745656B2 JP8618386A JP8618386A JPH0745656B2 JP H0745656 B2 JPH0745656 B2 JP H0745656B2 JP 8618386 A JP8618386 A JP 8618386A JP 8618386 A JP8618386 A JP 8618386A JP H0745656 B2 JPH0745656 B2 JP H0745656B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- emission intensity
- hours
- emission
- present
- 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.)
- Expired - Lifetime
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Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は青色発光アルミン酸塩蛍光体に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a blue light emitting aluminate phosphor.
（従来の技術） 近年、一般照明用蛍光ランプは高演色化、高出力化の要
求が高く、この要求を満足する一手段として比較的狭帯
域の発光スペクトル分布をもつ青色、緑色、赤色発光蛍
光体を適当な割合で混合して使用する三波長域発光形蛍
光ランプがある。この方式の蛍光ランプは各々の蛍光体
の発光色が大幅に異なっているためにランプ点灯中の各
々の蛍光体の光出力（発光強度）の低下の違いによって
生じる色ずれ現象がおこる。また、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系の蛍
光体が用いられている。よく知られている青色発光蛍光
体であるユーロピウム不活アルミン酸塩蛍光体〔（Ba1E
u）Mg2Al16O27〕（特公昭52−22836号公報）は働程中の
発光強度低下の点で改良の余地がある。また同じユーロ
ピウム付活アルミン酸塩蛍光体〔（Ba,Eu）Ｏ・xAl2O3
・yY2O3〕（特開昭60−139784号公報）は発光強度や働
程中の発光強度低下の点で改良の余地がある。同様にユ
ーロピウム付活アルミン酸蛍光体 （特開昭56−86982号公報）は発光強度や働程中の発光
強度低下の点で改良の余地がある。(Prior Art) In recent years, fluorescent lamps for general lighting have been required to have high color rendering and high output, and as one means for satisfying these requirements, blue, green, and red emitting fluorescent light having a relatively narrow band emission spectrum distribution. There is a three-wavelength band emission type fluorescent lamp which is used by mixing the body in an appropriate ratio. In this type of fluorescent lamp, since the emission colors of the respective phosphors are significantly different, a color shift phenomenon occurs due to a difference in reduction in light output (emission intensity) of the respective phosphors during lighting of the lamp. Further, an aluminate-based phosphor is used as a blue light emitting component of a recent three-wavelength band fluorescent lamp. Europium inactive aluminate phosphor [(Ba 1 E
u) Mg 2 Al 16 O 27 ] (Japanese Patent Publication No. 52-22836) has room for improvement in terms of reduction in emission intensity during working. The same europium-activated aluminate phosphor [(Ba, Eu) O.xAl 2 O 3
Yy 2 O 3 ] (Japanese Patent Laid-Open No. 60-139784) has room for improvement in terms of emission intensity and reduction in emission intensity during working. Similarly, europium-activated aluminate phosphor (JP-A-56-86982) has room for improvement in terms of emission intensity and reduction in emission intensity during working.
（発明が解決しようとする問題点） 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
光出力が高く色ずれ現象が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発光強度低
下の少ない蛍光体の出現が望まれている。(Problems to be Solved by the Invention) As described above, it is desired that the three-wavelength band emission type fluorescent lamp has a high lamp emission output and a small color shift phenomenon, but the color shift phenomenon is minimized. Therefore, the emergence of a phosphor with a small decrease in emission intensity is desired.
そこで本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、働程中の
発光強度低下の少ない青色発光アルミン酸塩蛍光体を提
供することを目的とする。Therefore, the present invention has been made to solve the above-described problems, and an object thereof is to provide a blue light emitting aluminate phosphor that exhibits high light emission under the excitation of a 254 nm mercury emission line and has a small decrease in emission intensity during working. To do.
（問題を解決するための手段） 本発明は青色発光アルミン酸塩蛍光体として、一般式
（BawCaxMgyEuz）Ｏ・aAl2O3・bSiO2で表わされること
を特徴とするものである。ただし0.1≦ｗ≦0.5,0.0004
≦ｘ≦0.0020,0.1≦ｙ≦0.8,0.03≦ｚ≦0.10,w＋ｘ＋ｙ
＋ｚ＝1,1.5≦ａ≦4.5,0.0005≦ｂ≦0.0030である。(Means for Solving the Problems) The present invention is a blue light-emitting aluminate phosphor, characterized in that it is represented by the general formula (Ba w Ca x Mg y Eu z) O · aAl 2 O 3 · bSiO 2 It is a thing. However, 0.1 ≦ w ≦ 0.5, 0.0004
≤ x ≤ 0.0020, 0.1 ≤ y ≤ 0.8, 0.03 ≤ z ≤ 0.10, w + x + y
+ Z = 1,1.5 ≦ a ≦ 4.5, 0.0005 ≦ b ≦ 0.0030.
なお、Euはその一部をMnで置換してもよい。Mnの置換割
合はモル比でEuの２倍以下である。その場合、ＺはEuと
Mnとの総量に係る係数となる。Note that Eu may partially replace Mn. The substitution ratio of Mn is not more than twice the molar ratio of Eu. In that case, Z is Eu
It is a coefficient related to the total amount with Mn.
一般式におけるａは2.0≦ａ≦3.0の範囲の値がより好ま
しく、また、ｘは0.0006≦ｘ≦0.0015の範囲の値がより
好ましい。The value of a in the general formula is more preferably 2.0 ≦ a ≦ 3.0, and the value of x is more preferably 0.0006 ≦ x ≦ 0.0015.
以上の通り本発明においては母体を構成するBa,Ca,Mg,A
l2O3,SiO2はいずれも必要な要素であり例えばCaやSiO2
等いずれが欠けても効果を奏することができない。As described above, in the present invention, Ba, Ca, Mg, A constituting the matrix
l 2 O 3 and SiO 2 are both necessary elements, such as Ca and SiO 2
If any of these is missing, the effect cannot be obtained.
（作用） 第１表は本発明の作用効果を説明するためのものであ
る。本発明における蛍光体と従来の青色発光アルミン酸
塩蛍光体とを比較した場合、本発明の一般式（BawCaxMg
yEuz）Ｏ・aAl2O3・bSiO2で表わされる蛍光体の方が発
光強度および1000時間後の発光強度において向上が認め
られた。さらに指数a,xが2.0≦ａ≦3.0,0.0006≦ｘ≦0.
0015の場合により好ましい向上が認められた。(Operation) Table 1 is for explaining the operation and effect of the present invention. When the phosphor of the present invention is compared with the conventional blue light emitting aluminate phosphor, the general formula (Ba w Ca x Mg) of the present invention is used.
y Eu z) O · aAl increase in the emission intensity after the light-emitting intensity and 1000 hours towards the phosphor represented by 2 O 3 · bSiO 2 was observed. Furthermore, the indices a and x are 2.0 ≦ a ≦ 3.0, 0.0006 ≦ x ≦ 0.
In the case of 0015, a preferable improvement was observed.
また、ｂの範囲は0.0005≦ｂ≦0.0030の範囲が好まし
い。第２図は、組成式（Ba0.449Ca0.0010Mg0.5Eu0.05）
Ｏ・2.5Al2O3・bSiO2における1000時間後の発光強度のS
iO2濃度依存性を示している。同図から明らかなよう
に、ｂの値が0.005より小さいと本発明の課題である100
0時間後の発光強度に対して十分な効果が得られない。
一方、ｂの値が0.0030より大きいと、目的とする物質以
外の相が現われ、蛍光体として安定なものが得られな
い。このことは、指数x,y,z,w,aについても同様のこと
がいえる。The range of b is preferably 0.0005 ≦ b ≦ 0.0030. Fig. 2 shows the composition formula (Ba 0.449 Ca 0.0010 Mg 0.5 Eu 0.05 ).
S of emission intensity after 1000 hours in O ・ 2.5Al 2 O 3・ bSiO 2
It shows the iO 2 concentration dependence. As is clear from the figure, if the value of b is smaller than 0.005, the problem of the present invention is 100.
A sufficient effect cannot be obtained with respect to the emission intensity after 0 hours.
On the other hand, if the value of b is greater than 0.0030, a phase other than the target substance appears, and a stable phosphor cannot be obtained. The same can be said for the indices x, y, z, w, a.
（実施例） 本発明の蛍光体（BawCaxMgyEuz）Ｏ・aAl2O3・bSiO2は
以下のようにして合成することができる。蛍光体原料に
はバリウム源として酸化バリウム、水酸化バリウム、炭
酸バリウム等のバリウム化合物群の中より選ばれる化合
物の少なくとも一種、カルシウム源として酸化カルシウ
ム、水酸化カルシウム、炭酸カルシウム等のカルシウム
化合物群の中より選ばれる化合物の少なくとも一種、マ
グネシウム源として酸化マグネシウム、水酸化マグネシ
ウム、炭酸マグネシウム等のマグネシウム化合物群の中
より選ばれる化合物の少なくとも一種、ユーロピウム源
として酸化ユーロピウム、弗化ユーロピウム等のユーロ
ピウム化合物群の中より選ばれる化合物の少なくとも一
種、アルミニウム源として酸化アルミニウム、水酸化ア
ルミニウム等のアルミニウム化合物群の中より選ばれる
化合物の少なくとも一種、珪素源として二酸化珪素等の
珪素化合物群の中より選ばれる化合物の少なくとも一種
を用いる。これらの原料を所定量秤量し原料混合物を十
分に混合する。前記混合物をルツボ等の耐熱性容器に入
れて空気中において1200℃から1600℃で３〜４時間焼成
する。得られた焼成物を粉砕、水洗等の処理を行ない、
乾燥後再びルツボ等に入れ還元性雰囲気において1400℃
から1600℃で３〜４時間焼成する。焼成物を粉砕、水洗
等の処理を行ない本発明の青色発光アルミン酸塩蛍光体
を得ることができる。(Example) The phosphor of the present invention (Ba w Ca x Mg y Eu z) O · aAl 2 O 3 · bSiO 2 can be synthesized as follows. At least one compound selected from the barium compound group such as barium oxide, barium hydroxide and barium carbonate as a barium source for the phosphor raw material, and calcium oxide, calcium hydroxide, a calcium compound group such as calcium carbonate as a calcium source. At least one compound selected from among, at least one compound selected from the group of magnesium compounds such as magnesium oxide, magnesium hydroxide, magnesium carbonate as a magnesium source, europium oxide as a europium source, europium compound group such as europium fluoride At least one compound selected from the group, at least one compound selected from the group of aluminum compounds such as aluminum oxide and aluminum hydroxide as the aluminum source, and silicon such as silicon dioxide as the silicon source. Using at least one compound selected from among compounds group. A predetermined amount of these raw materials is weighed and the raw material mixture is sufficiently mixed. The mixture is placed in a heat-resistant container such as a crucible and baked in air at 1200 ° C to 1600 ° C for 3 to 4 hours. The obtained baked product is crushed, washed with water, etc.,
After drying, put it again in a crucible etc. in a reducing atmosphere at 1400 ℃
To 1600 ° C for 3-4 hours. The fired product is pulverized and washed with water to obtain the blue light emitting aluminate phosphor of the present invention.
（実施例−１） 酸化バリウム BaO 68.85g 水酸化カルシウム Ca（OH）２ 0.07 水酸化マグネシウム Mg（OH）２ 29.17 酸化ユーロピウム Eu2O3 8.80 酸化アルミニウム Al2O3 254.90 二酸化珪素 SiO2 0.06 上記原料を十分に混合し空気中において1350℃で４時間
焼成する。得られた焼成物を粉砕、水洗、乾燥後還元性
雰囲気において1400℃で４時間焼成し、粉砕、水洗、乾
燥後蛍光体を得た。得られた蛍光体の組成は（Ba0.449C
a0.0010Mg0.5Fu0.05）Ｏ・2.5Al2O3・0.0010SiO2であ
る。この蛍光体の254nm励起発光強度は従来の青色発光
アルミン酸塩蛍光体である（Ba1Eu）Mg2Al16O27に比べ
て110％であった。また（Ba,Eu）Ｏ・xAl2O3・yY2O3に
比べて254nm励起発光強度は120％であり、1000時間点灯
後の発光強度は180％であった。(Example-1) Barium oxide BaO 68.85 g Calcium hydroxide Ca (OH) 2 0.07 Magnesium hydroxide Mg (OH) 2 29.17 Europium oxide Eu 2 O 3 8.80 Aluminum oxide Al 2 O 3 254.90 Silicon dioxide SiO 2 0.06 The above raw materials Are thoroughly mixed and calcined in air at 1350 ° C. for 4 hours. The obtained fired product was crushed, washed with water and dried, and then fired at 1400 ° C. for 4 hours in a reducing atmosphere to obtain a phosphor after crushing, washing with water and drying. The composition of the obtained phosphor is (Ba 0.449 C
a 0.0010 Mg 0.5 Fu 0.05 ) O · 2.5Al 2 O 3 · 0.0010SiO 2 . The emission intensity at 254 nm of this phosphor was 110% as compared with the conventional blue-emitting aluminate phosphor (Ba 1 Eu) Mg 2 Al 16 O 27 . Further, the emission intensity at 254 nm excitation was 120%, and the emission intensity after lighting for 1000 hours was 180%, as compared with (Ba, Eu) O.xAl 2 O 3 .yY 2 O 3 .
上記原料を実施例−１と同様に処理する。得られた蛍光
体の組成は（Ba0.198Ca0.0020Mg0.7Eu0.1）Ｏ・3.5Al2O
3・0.0020SiO2である。この蛍光体は（Ba,Eu）Ｏ・xAl2
O3・yY2O3に比べて254nm励起発光強度は114％であり、1
000時間点灯後の発光強度は135％であった。 The above raw material is treated as in Example 1. The composition of the obtained phosphor is (Ba 0.198 Ca 0.0020 Mg 0.7 Eu 0.1 ) O.3.5Al 2 O
3 · 0.0020 SiO 2 . This phosphor is (Ba, Eu) O.xAl 2
The emission intensity at 254 nm excitation is 114%, which is higher than that of O 3 · yY 2 O 3.
The emission intensity after lighting for 000 hours was 135%.
上記原料を実施例−１と同様に処理する。得られた蛍光
体の組成は（Ba0.2Ca0.0015Mg0.7385Eu0.06）Ｏ・2.0Al
2O3・0.0030SiO2である。この蛍光体は（Ba,Eu）Ｏ・xA
l2O3・yY2O3に比べて254nm励起発光強度は118％であ
り、1000時間点灯後の発光強度は155％であった。 The above raw material is treated as in Example 1. The composition of the obtained phosphor is (Ba 0.2 Ca 0.0015 Mg 0.7385 Eu 0.06 ) O.2.0Al
2 O 3 · 0.0030SiO 2 . This phosphor is (Ba, Eu) O.xA
The emission intensity at 254 nm excitation was 118%, and the emission intensity after lighting for 1000 hours was 155%, as compared with l 2 O 3 · yY 2 O 3 .
第１表は実施例１〜３の結果および同様な方法で製作し
た実施例４〜16の結果ならびに比較例の結果を示す。Table 1 shows the results of Examples 1 to 3, the results of Examples 4 to 16 produced by the same method, and the results of Comparative Examples.
〔発明の効果〕 以上説明した通り、本発明により発光強度が高く、発光
強度低下の少ない蛍光体を実現することができる。 [Effects of the Invention] As described above, according to the present invention, it is possible to realize a phosphor having high emission intensity and less reduction in emission intensity.
【図面の簡単な説明】 第１図は本発明に係る蛍光体の発光スペクトルを示す
図、第２図はSiO2の濃度と1000時間後の発光強度との関
係を示す図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the emission spectrum of the phosphor according to the present invention, and FIG. 2 is a diagram showing the relationship between the SiO 2 concentration and the emission intensity after 1000 hours.
Claims (2)
2（ただしｗは0.1≦ｗ≦0.5,xは0.0004≦ｘ≦0.0020,y
は0.1≦ｙ≦0.8,zは0.03≦ｚ≦0.10,w＋ｘ＋ｙ＋ｚ＝1,
aは1.5≦ａ≦4.5,bは0.0005≦ｂ≦0.0030の範囲の値で
ある）で表わされることを特徴とする蛍光体。1. A general formula (Ba w Ca x Mg y Eu z ) O.aAl 2 O 3 .bSiO
2 (however, w is 0.1 ≦ w ≦ 0.5, x is 0.0004 ≦ x ≦ 0.0020, y
Is 0.1 ≦ y ≦ 0.8, z is 0.03 ≦ z ≦ 0.10, w + x + y + z = 1,
a is a value in the range of 1.5 ≦ a ≦ 4.5 and b is a value in the range of 0.0005 ≦ b ≦ 0.0030).
が0.0006≦ｘ≦0.0015の範囲の値である特許請求の範囲
第１項記載の蛍光体。2. In the general formula, a is 2.0 ≦ a ≦ 3.0 or x
Is a value in the range of 0.0006 ≦ x ≦ 0.0015, The phosphor according to claim 1.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8618386A JPH0745656B2 (en) | 1986-04-16 | 1986-04-16 | Phosphor |
| DE8787105145T DE3761906D1 (en) | 1986-04-16 | 1987-04-07 | PHOSPHORUS AND FLUORESCENT LAMP USING THE SAME. |
| EP87105145A EP0241848B1 (en) | 1986-04-16 | 1987-04-07 | Phosphor and fluorescent lamp using the same |
| US07/036,452 US4733126A (en) | 1986-04-16 | 1987-04-09 | Phosphor and fluorescent lamp using the same |
| KR1019870003650A KR900002447B1 (en) | 1986-04-16 | 1987-04-16 | Fluorescent substance and fluorescent lamp using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8618386A JPH0745656B2 (en) | 1986-04-16 | 1986-04-16 | Phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62243680A JPS62243680A (en) | 1987-10-24 |
| JPH0745656B2 true JPH0745656B2 (en) | 1995-05-17 |
Family
ID=13879650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8618386A Expired - Lifetime JPH0745656B2 (en) | 1986-04-16 | 1986-04-16 | Phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745656B2 (en) |
-
1986
- 1986-04-16 JP JP8618386A patent/JPH0745656B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62243680A (en) | 1987-10-24 |
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