JPH0446988A - Phosphor, its manufacturing method, and cathode ray tube - Google Patents
Phosphor, its manufacturing method, and cathode ray tubeInfo
- Publication number
- JPH0446988A JPH0446988A JP15514090A JP15514090A JPH0446988A JP H0446988 A JPH0446988 A JP H0446988A JP 15514090 A JP15514090 A JP 15514090A JP 15514090 A JP15514090 A JP 15514090A JP H0446988 A JPH0446988 A JP H0446988A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- cathode ray
- ray tube
- manufacturing
- flux
- 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.)
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- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、発光特性の優れた蛍光体組成に係り、特に高
密度電子線照射に好適な緑色蛍光体とその製造方法及び
この蛍光体を用いた陰極線管に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a phosphor composition with excellent luminescent properties, and particularly relates to a green phosphor suitable for high-density electron beam irradiation, a method for producing the same, and a method for producing the phosphor. Regarding the cathode ray tube used.
投射形テレビは３本の単色ブラウン管（投射管）から発
する緑、赤及び青の光から構成される画像をレンズを用
いてスクリーン上に拡大投射よるものである。投射管は
直視形に比へ１００倍以上の電流密度で励起されるため
に、それに用いる蛍光体の特性としては、発光効率が高
いこと、輝度が電流の増加に伴って比例して増す、すな
わち輝度飽和がないこと、蛍光面の温度上昇による輝度
低下がない、すなわち温度特性が良いこと、膜焼けによ
る輝度劣化がないこと等が要求される。投射形テレビに
おいては、白色画面にした場合の輝度の６０％は緑色光
の投射管が受は持つので、特に、緑色蛍光体には優れた
発光特性が望まれる。A projection television uses a lens to enlarge and project an image made up of green, red, and blue light emitted from three monochromatic cathode ray tubes (projection tubes) onto a screen. Since the projection tube is excited with a current density that is more than 100 times that of a direct view type, the characteristics of the phosphor used for it are that it has high luminous efficiency and that the brightness increases in proportion to the increase in current. It is required that there is no brightness saturation, that there is no decrease in brightness due to temperature rise of the phosphor screen, that is, that the temperature characteristics are good, and that there is no brightness deterioration due to film burning. In a projection television, 60% of the brightness of a white screen is received by the projection tube that emits green light, so it is particularly desirable for the green phosphor to have excellent light emitting characteristics.
このような状況のもとて、「第２１７回蛍光体同学会溝
演予稿、Ｐ１９〜２６ （１９８７）；投射管用蛍光体
」に見られるように、各社で蛍光体の改良が行われてお
り、特に緑色蛍光体に関しては色々な材料が検討されて
いる。Under these circumstances, various companies have been making improvements to their phosphors, as seen in ``217th Annual Conference on Phosphors, P19-26 (1987); Phosphors for Projection Tubes.'' In particular, various materials are being considered for green phosphors.
例えば、Ｙ２ＳｉＯ５：Ｔｂとその改良組成に関する技
術として特公昭４８−３７６７０ 、５７−１０５９１
゜米国特許３，７５８，４１３等がある。また。For example, as a technology regarding Y2SiO5:Tb and its improved composition, Japanese Patent Publication No. 48-37670, 57-10591
゜There are U.S. Patent No. 3,758,413, etc. Also.
Ｙ３（ＡＱｌ−Ｇａｘ）ｓＯ−２： Ｔｂに関する技術
は特開昭６０−１０１１７５に記載されている。Y3(AQl-Gax)sO-2: The technology regarding Tb is described in JP-A-60-101175.
上記従来技術において、Ｙ、Ｓ ｉ○じＴｂは高電流密
度下で膜焼けによる輝度劣化があること、Ｙ ３ （Ａ
Ｑ 、−ｚＧ ａ ｚ）ｓＯ，□：Ｔｂは色調が良く
ないこと、またＩｎＢＯ３：Ｔｂ 、Ｚｎ２５ｉＯ，
：Ｍｎは色調は良いが残光が長い（ピークの１／１０に
減衰する時間で各々約１６ｍ５および２６ｒｎｓ）こと
、という問題があった。In the above-mentioned conventional technology, Y, S i○ji Tb suffers from brightness deterioration due to film burning under high current density, and Y 3 (A
Q, -zG az)sO,□:Tb has poor color tone, and InBO3:Tb, Zn25iO,
:Mn has a good color tone, but has a problem in that it has a long afterglow (the time it takes to decay to 1/10 of the peak is about 16 m5 and 26 rns, respectively).
本発明の目的は、投射管用蛍光体として必要な発光特性
を満たし、かつ色調の良い緑色蛍光体を提供することに
ある。An object of the present invention is to provide a green phosphor that satisfies the emission characteristics necessary for a phosphor for a projection tube and has a good color tone.
上記目的は、（１）一般式 ％式％ で表わされる蛍光体を用いることによって達成される。 The above purpose is (1) General formula %formula% This is achieved by using a phosphor represented by
また、上記蛍光体を製造する際に、フラックスとしてア
ルカリ金属の硫酸塩を用いることが好ましい。Further, when manufacturing the above-mentioned phosphor, it is preferable to use an alkali metal sulfate as the flux.
本発明の蛍光体は通常、Ｇｄ２Ｏ，、Ｔｂ４Ｏ７および
Ａｆ１２０．を一般式に合うように混合して焼成するこ
とによって得られるが、その他の方法としては、加熱に
よって分解して酸化物になるガドリウム化合物、テルビ
ウム化合物およびアルミニウム化合物を用いて合成する
こともできる。The phosphors of the present invention typically include Gd2O,, Tb4O7 and Af120. It can be obtained by mixing and firing the mixture according to the general formula, but it can also be synthesized using gadolinium compounds, terbium compounds, and aluminum compounds that decompose into oxides by heating.
Ｇｄ２Ｏ３，Ｔｂ４Ｏ７およびＡＱ２０３をＧｄ４（、
−ｚ＞Ｔ ｂ 、ｚＡ Ｑ ２０ｇの組成になるように
配合して１５００’で合成する場合、フラックスとして
、Ｋ２ＳＯ４，Ｎａ２ＳＯ４，Ｒｂ２５０．４およびＣ
８２ＳＯ４を用いることが有効である。フラックスを用
いることによりＧｄ４ＡＱ２０．の単一相が容易に得ら
れる。フラックスを用いないとＧｄ４ＡＱ３０ｇへのＴ
ｂの導入が不十分になり試料は褐色に着色する。フラッ
クスの添加量は、Ｇｄ４（□−Ｚ、Ｔｂ４ｚＡＱ２０ｇ
１モルに対して０．６モル以上が適当である。Gd2O3, Tb4O7 and AQ203 with Gd4(,
-z>T b , zA When synthesizing at 1500' with a composition of 20 g, K2SO4, Na2SO4, Rb250.4 and C
It is effective to use 82SO4. By using flux, Gd4AQ20. A single phase of can be easily obtained. T to Gd4AQ30g without flux
The introduction of b becomes insufficient and the sample turns brown. The amount of flux added is Gd4 (□-Z, Tb4zAQ20g
A suitable amount is 0.6 mole or more per mole.
Ｇ ｄ ４（１−Ｚ＋Ｔ ｂ ４ＺＡ Ｑ Ｊ○３の組
成においてＴｂ濃度（Ｚ）と輝度および色度座標の関係
を実施例１〜５に示した。これから明らかなように、２
が０．０１ 以上ではＹ、ＡＱ、０１□：Ｔｂよりも色
度座標のＸ値が小さく、より緑味の強い蛍光体であるこ
とがわかる。Ｔｂ濃度の範囲は、
Ｙ、ＡＱ、、○、２：ＴｂよりもＸ値が小さく、かつ実
用上必要な輝度を有するという条件で、２は０．０１＜
Ｚ＜０．１の範囲に限定した。Examples 1 to 5 show the relationship between the Tb concentration (Z) and the brightness and chromaticity coordinates in the composition of G d 4(1-Z+T b 4ZA Q J○3. As is clear from this, 2
is 0.01 or more, the X value of the chromaticity coordinate is smaller than that of Y, AQ, 01□:Tb, indicating that the phosphor has a stronger green tint. The range of Tb concentration is Y, AQ, ○, 2: 2 is 0.01<, provided that the X value is smaller than Tb and the luminance is practically necessary.
The range was limited to Z<0.1.
実施例３の蛍光体（Ｇ ｄ、、、Ｔ ｂ。、２Ａ Ｑ２
０ｇ）の発光スペクトルを第１図に、比較のためにＹ、
ＡＱ、、○Ｘ２：Ｔｂの発光スペクトルを第２図に示し
た。図から明らかなように、本発明の蛍光体はＹ３ＡＱ
、○、２：Ｔｂに比へ４９０ｎｍ付近および５８０ｎｍ
より長波長の発光が小さいのが特徴である。また、本発
明の蛍光体の残光時間（ピークの１／１０に減衰する時
間）は５．４ｍｓ であった。Ｇｄ、、、Ｔｂｏ、２
ＡＱ２０３の組成においてＧｄの一部をＹ、Ｌａ、Ｌｕ
、ＳｃおよびＩｎで、ＡＱの一部をＧａで置換すること
ができる。Phosphor of Example 3 (G d, , T b., 2A Q2
0g) is shown in Figure 1, and for comparison, Y,
AQ, ○X2: The emission spectrum of Tb is shown in FIG. As is clear from the figure, the phosphor of the present invention is Y3AQ
, ○, 2: around 490 nm and 580 nm relative to Tb
It is characterized by the fact that the emission of longer wavelengths is smaller. Further, the afterglow time (time for decay to 1/10 of the peak) of the phosphor of the present invention was 5.4 ms. Gd, , Tbo, 2
In the composition of AQ203, a part of Gd is replaced by Y, La, Lu.
, Sc and In, part of AQ can be replaced by Ga.
なお、公知の蛍光体としてＹ４Ａ Ｑ２０．、 ： Ｔ
ｂが、フィリップス リサーチ レポート、２２巻（
１９６７年）４８１頁（Ｐｈｉｌｉｐｓ Ｒｅｓ、Ｒｅ
ｐｏｒｔ２２ （１９６７）Ｐ２Ｓ５）に記載されてい
るが、この蛍光体の輝度はＧｄ４ＡＱ２０３：Ｔｂ に
比へ３５％低かった。Incidentally, Y4A Q20. , : T
b is Philips Research Report, Volume 22 (
1967) p. 481 (Philips Res, Re
port22 (1967) P2S5), the luminance of this phosphor was 35% lower than that of Gd4AQ203:Tb.
以下、本発明の一実施例を説明する。 An embodiment of the present invention will be described below.
実施例１〜５
Ｇｄ２０． ０．０２Ｘ（１−ｚ）モルＴｂ４ｏ７０．
０１ｘｚモル
ＡＱ、Ｏ，０，０１モル
に２Ｓｏ４０．０１モル
をメノウの乳鉢で良く混合したのち、空気中において１
５００℃で２時間焼成した。フラックスを除去するため
に焼成物を水洗し、ついで１２０°Ｃで乾燥した。こう
して得られた蛍光体の組成はＧ ｄ ４＜１−ｚ＞Ｔ
ｂ嗜ｚＡＱ２０．であり、これらの蛍光体の発光特性を
第１表に示す。Examples 1-5 Gd20. 0.02X(1-z)mol Tb4o70.
After thoroughly mixing 0.01 mole of 2So with 0.01 mole of AQ, O, in an agate mortar, 1
It was baked at 500°C for 2 hours. The fired product was washed with water to remove flux, and then dried at 120°C. The composition of the phosphor thus obtained is G d 4<1-z>T
b zAQ20. Table 1 shows the emission characteristics of these phosphors.
第 １ 表
以上のように本実施例で得られた蛍光体組成物は、Ｙ３
ＡＱ、○、２：Ｔｂに比べ色度座標のＸ値が小さく、緑
色成分として好ましいものであることがわかる。Table 1 As shown above, the phosphor composition obtained in this example was Y3
AQ, ○, 2: It can be seen that the X value of the chromaticity coordinate is smaller than that of Tb, and it is preferable as a green component.
実施例６〜９
Ｇｄ２０． ０．０１９モル
Ｔｂ４Ｏ７０，０００５−１＝ル
Ａｎ２０． ０．０１モル
Ｍ２Ｓ０． ０．０１モル
をメノウの乳鉢で良く混合し、あとは実施例１と同様に
処理した。こうして得られた蛍光体の組成はＧ ｄ、、
ｓＴ’ｂｏ、２Ａ Ｑ２０．であり、色度座標はＸ＝０
．３４３．Ｙ＝０．６０７である。第２表に各種フラッ
クス（Ｍ２ＳＯ，）を用いた場合の輝度を示す。Examples 6-9 Gd20. 0.019 mol Tb4O70,0005-1=An20. 0.01 mol M2S0. 0.01 mol was mixed well in an agate mortar, and the rest was treated in the same manner as in Example 1. The composition of the phosphor thus obtained is G d,
sT'bo, 2A Q20. and the chromaticity coordinate is X=0
．． 343. Y=0.607. Table 2 shows the brightness when using various fluxes (M2SO,).
第 ２ 表
＊ Ｙ、Ａ Ｑ５０□２ ： Ｔ ｂ （７）輝度を１
０ｏとした。Table 2 * Y, A Q50□2: T b (7) Brightness 1
It was set to 0o.
以上のようなフラックスを用いることにより本発明の蛍
光体の輝度を大幅に向上することができる。By using the above flux, the brightness of the phosphor of the present invention can be significantly improved.
本発明の蛍光体を用いることにより、色調の良い投射管
を提供することができる。By using the phosphor of the present invention, a projection tube with good color tone can be provided.
第１図は本発明の一実施例になる
Ｇｃｌ、、！ｌＴｂ、、２ＡＱ２０．の発光スペクトル
を示す図、第２図は従来例のＹ、ＡＱ；○、２：Ｔｂの
発光スペクトルを示す図である。
（〜
■
図
第
え
／膚雀（ル垢ジFIG. 1 shows Gcl, which is an embodiment of the present invention. lTb,,2AQ20. FIG. 2 is a diagram showing the emission spectra of conventional examples of Y, AQ;○, and 2:Tb. (~ ■ Figure number / skin sparrow)
Claims (3)
＿５但し、０．０１≦Ｚ≦０．１ で表わされることを特徴とする蛍光体。1. General formula Gd_4_(_1_-_Z_)Tb_4_ZAl_2O
_5 However, a phosphor characterized by 0.01≦Z≦0.1.
ＺＡｌ＿２Ｏ＿５（但し、０．０１≦Ｚ≦０．１）で表
わされる蛍光体を製造する際に、フラックスとして、ア
ルカリ金属の硫酸塩を用いることを特徴とする蛍光体の
製造方法。2. General formula Gd_4_(_1_-_Z_)Tb_4_
A method for producing a phosphor, characterized in that an alkali metal sulfate is used as a flux when producing a phosphor represented by ZAl_2O_5 (0.01≦Z≦0.1).
極線管。3. A cathode ray tube characterized by using the phosphor according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15514090A JPH0446988A (en) | 1990-06-15 | 1990-06-15 | Phosphor, its manufacturing method, and cathode ray tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15514090A JPH0446988A (en) | 1990-06-15 | 1990-06-15 | Phosphor, its manufacturing method, and cathode ray tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0446988A true JPH0446988A (en) | 1992-02-17 |
Family
ID=15599425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15514090A Pending JPH0446988A (en) | 1990-06-15 | 1990-06-15 | Phosphor, its manufacturing method, and cathode ray tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0446988A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6676853B1 (en) * | 1999-10-27 | 2004-01-13 | Sumitomo Chemical Company, Limited | Phosphor for vacuum ultraviolet excitation material |
| US6696782B2 (en) * | 2000-10-12 | 2004-02-24 | Hitachi, Ltd. | Green-emitting phosphor and image display device using the same |
| KR100447947B1 (en) * | 2001-11-30 | 2004-09-08 | 한국화학연구원 | The composition of Tb-activated green phosphors in ternary system CaO-Gd2O3-Al2O3 for VUV excitation |
-
1990
- 1990-06-15 JP JP15514090A patent/JPH0446988A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6676853B1 (en) * | 1999-10-27 | 2004-01-13 | Sumitomo Chemical Company, Limited | Phosphor for vacuum ultraviolet excitation material |
| US6696782B2 (en) * | 2000-10-12 | 2004-02-24 | Hitachi, Ltd. | Green-emitting phosphor and image display device using the same |
| KR100447947B1 (en) * | 2001-11-30 | 2004-09-08 | 한국화학연구원 | The composition of Tb-activated green phosphors in ternary system CaO-Gd2O3-Al2O3 for VUV excitation |
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