JPH044287A - Blue luminous fluorescent substance and cathode ray tube - Google Patents
Blue luminous fluorescent substance and cathode ray tubeInfo
- Publication number
- JPH044287A JPH044287A JP10536590A JP10536590A JPH044287A JP H044287 A JPH044287 A JP H044287A JP 10536590 A JP10536590 A JP 10536590A JP 10536590 A JP10536590 A JP 10536590A JP H044287 A JPH044287 A JP H044287A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- barium
- cathode ray
- ray tube
- luminance
- 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.)
- Granted
Links
- 239000000126 substance Substances 0.000 title abstract 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 37
- 229910052788 barium Inorganic materials 0.000 claims abstract description 24
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 68
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- -1 aluminum activated zinc sulfide phosphor Chemical class 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000203 mixture Substances 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 6
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 4
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 30
- 238000007796 conventional method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 4
- 229910001632 barium fluoride Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical group [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的］
（産業上の利用分野）
本発明は青色発光蛍光体及びこの青色発光蛍光体を陰極
線管の蛍光面に用いた陰極線管に係り、特に銀及びアル
ミニウム付活硫化亜鉛蛍光体の改良に関する。Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to a blue-emitting phosphor and a cathode-ray tube using this blue-emitting phosphor in the phosphor screen of the cathode ray tube, and particularly to Related to improvements in activated zinc sulfide phosphors.
（従来の技術）
近年カラーブラウン管の大型化にともない青色、緑色、
赤色発光成分蛍光体は、いずれも従来カラーブラウン管
に用いられていた蛍光体よりも粒子径が大きくなってい
る。これは蛍光体塗布技術の進歩により従来の蛍光体よ
りも粒子径の大きい蛍光体「大粒子蛍光体」の塗布が可
能になったためで、大粒子蛍光体を用いる利点として、
■結晶成長の促進により結晶の均一化を向上させている
ことから機械的強度に優れ、蛍光体塗布工程に先立って
ビーズミル等による輝度劣化が少ない。(Prior technology) In recent years, as color cathode ray tubes have become larger, blue, green,
All of the red light-emitting component phosphors have larger particle diameters than the phosphors conventionally used in color cathode ray tubes. This is because advancements in phosphor coating technology have made it possible to coat ``large-particle phosphors,'' which have larger particle diameters than conventional phosphors.The advantage of using large-particle phosphors is that
■Since crystal uniformity is improved by promoting crystal growth, it has excellent mechanical strength, and there is little brightness deterioration due to bead milling etc. prior to the phosphor coating process.
■蛍光体塗布時、発光の透過性が高く発光を有効に取り
出し蛍光体塗布付着力が向上される。- When applying phosphor, the luminescence is highly transparent and the emitted light is effectively extracted, improving the adhesion of the phosphor coating.
従来、カラーブラウン管の青色成分として実用付
化されていた銀及びアルミニウム不活硫化亜鉛蛍光体（
以下ＺｎＳ：Ａｇ、Ａｊ７蛍光体と記す）は平均粒子径
が４μｍ〜６μｍのものである（この平均粒子径は通気
法に基づくプレイン法によって評価した。）この様な粒
子径を有するＺｎＳ：Ａｇ、／ｌ蛍光体は硫化亜鉛に適
当量の硝酸銀（ＡｇＮＯ３）及び硝酸アルミニウム（Ａ
Ｎ （ＮＯ３）３ ・９Ｈ２０）を添加し、通常はさ
らに適当量のアルカリ金属ノ１０ゲン化物、アルカリ土
類金属ノ１０ゲン化物等を融剤として添加し、硫化水素
還元雰囲気にて９００〜１０３０℃の温度で０．５〜３
時間焼成することによって得られる。Silver and aluminum inactive zinc sulfide phosphors (
ZnS:Ag (hereinafter referred to as ZnS:Ag, Aj7 phosphor) has an average particle size of 4 μm to 6 μm (this average particle size was evaluated by the plain method based on the aeration method). ,/l The phosphor contains zinc sulfide and appropriate amounts of silver nitrate (AgNO3) and aluminum nitrate (AgNO3).
N (NO3)3 ・9H20) is added, and usually an appropriate amount of an alkali metal 10-genide, an alkaline earth metal 10-genide, etc. is added as a flux, and the temperature is reduced to 900 to 1030 in a hydrogen sulfide reducing atmosphere. 0.5-3 at temperature of °C
Obtained by firing for hours.
しかしながら、上述の従来の製造方法によってカラーブ
ラウン管の青色発光蛍光面に適した大粒子蛍光体を得る
ことは困難である。However, it is difficult to obtain a large particle phosphor suitable for a blue-emitting phosphor screen of a color cathode ray tube using the conventional manufacturing method described above.
たとえば融剤を多量に用いることによって、Ｚ ／ Ａ
ｇ、 Ａｌｌ蛍光体の平均粒径を大きくすることは可
能であるが、この場合発光輝度の低下。For example, by using a large amount of flux, Z/A
g. It is possible to increase the average particle size of the All phosphor, but in this case the luminance will decrease.
粒度分布の広がり等により粒子径の揃った明るい蛍光体
を得られない。また、より高い温度や焼成時間の延長に
よっても平均粒径の大きいＺｎＳ：Ａｇ、 Ａｌｌ蛍光
体は得られるが、やはり発光輝度。Due to the broadening of the particle size distribution, bright phosphors with uniform particle sizes cannot be obtained. Additionally, ZnS:Ag, All phosphors with larger average particle sizes can be obtained by using higher temperatures and longer firing times, but the luminance still remains.
発光色の低下や粒度分布の広がり等を生じ好ましくない
。This is undesirable because it causes a decrease in the luminescent color and a broadening of the particle size distribution.
（発明が解決しようとする課題）
本発明は上述した課題を解決するものであり、ＺｎＳ
：Ａｇ、Ａｌｌ蛍光体に比べて粒子径が太きく、しかも
発光輝度の高いＺｎＳ：Ａｇ、Ａｊ７蛍光体を提供する
ことを目的とする。(Problems to be solved by the invention) The present invention solves the above-mentioned problems, and
An object of the present invention is to provide a ZnS:Ag, Aj7 phosphor which has a larger particle diameter and higher emission brightness than a :Ag, All phosphor.
［発明の構成］
（課題を解決するための手段と作用）
本発明は、従来の方法によって得られるＺｎＳ：Ａｇ、
Ａｊ７蛍光体よりも粒子径の大きいＺｎＳ：Ａｇ、ＡΩ
蛍光体を得ることを目的として数々の実験を行いその結
果、従来の方法によってＺｎＳ：Ａｇ、Ａ、Ｑ蛍光体を
製造する際、さらに別の添加物を用いることにより上記
目的が達成されることを見いだした。つまり添加物とし
て適当量のバリウムを添加することにより、従来の方法
によってつくられるＺｎＳ ：Ａｇ、Ａｌｌ蛍光体より
も大粒子でかつ、発光輝度も高くその他の諸特性をも満
足されるＺｎＳ：Ａｇ、Ａｌｌ蛍光体が得られることを
見いだした。[Structure of the invention] (Means and effects for solving the problem) The present invention provides ZnS:Ag obtained by a conventional method,
ZnS with larger particle size than Aj7 phosphor: Ag, AΩ
A number of experiments have been carried out with the aim of obtaining a phosphor, and the results show that the above objective can be achieved by using additional additives when producing ZnS:Ag,A,Q phosphors by conventional methods. I found it. In other words, by adding an appropriate amount of barium as an additive, ZnS:Ag can be produced which has larger particles, higher luminance, and satisfies other characteristics than ZnS:Ag, All phosphor produced by conventional methods. , it has been found that an All phosphor can be obtained.
即ち本発明は、従来のＺｎＳ：Ａｇ、Ａρ蛍光体組成に
バ１功ムが加えられ添加量が付備量と共に規制されるこ
とにより、大粒子でかつ発光輝度の高いＺｎＳ：Ａｇ、
Ａｌｌ蛍光体を得るものである。That is, the present invention adds a barrier effect to the conventional ZnS:Ag, Aρ phosphor composition and regulates the amount of addition as well as the amount of addition, thereby producing ZnS:Ag, which has large particles and high luminance.
This is to obtain an All phosphor.
第１図は、銀及びアルミニウムを硫化亜鉛１００ｇに対
して、いずれも０．０６重量％で付活したＺｎＳ：Ａｇ
、Ａｌｌ蛍光体の製造時におけるバリウム添加量と得ら
れる蛍光体の平均粒径との関係を示したものである。こ
のときの平均粒子径は、通気法に基づくプレイン法によ
って測定した。Figure 1 shows ZnS:Ag activated with silver and aluminum at 0.06% by weight per 100g of zinc sulfide.
, which shows the relationship between the amount of barium added during the production of All-I phosphor and the average particle size of the obtained phosphor. The average particle diameter at this time was measured by the plain method based on the aeration method.
第１図から明らかなように、バリウム添加量が０．１５
重量％付近までは得られる蛍光体の平均粒子径は、バリ
ウム添加量が増加するに従って増大するか、それ以上で
は平均粒子径の増大は余りなく、次第に飽和する。As is clear from Figure 1, the amount of barium added is 0.15
The average particle size of the obtained phosphor increases as the amount of barium added increases up to about % by weight, and beyond that, the average particle size does not increase much and gradually becomes saturated.
また、このときのバリウムは臭化バリウム（ＢａＢｒ２
）、塩化バリウム（ＢａＣｆｆｓ＋）。In addition, barium at this time is barium bromide (BaBr2
), barium chloride (BaCffs+).
弗化バリウム（ＢａＦ２）、沃化バリウム（Ｂａ＃２）
、硝酸バリウム（Ｂ ａ （ＮＯ３） ２ ）等のバリ
ウム化合物の形で添加される。Barium fluoride (BaF2), barium iodide (Ba#2)
, barium nitrate (B a (NO3) 2 ) and other barium compounds.
第２図は、銀及びアルミニウムの付活量が第１図と同じ
ＺｎＳ：Ａｇ、Ａ、Ｑ蛍光体について、製造時における
バリウム添加量と発光輝度との関係を示したものである
。発光輝度は１０ｋｖ、 １μＡ／ｃｊの電子線を照
射し、このときの発光強度をフォトセルによって受光し
測定したものである。FIG. 2 shows the relationship between the amount of barium added during manufacture and the luminance for ZnS:Ag, A, Q phosphors in which the activation amounts of silver and aluminum are the same as in FIG. 1. Emission brightness was measured by irradiating an electron beam of 10 kV and 1 μA/cj and receiving the emitted light intensity by a photocell.
第２図から明らかなように、発光輝度はバリウム添加量
の増加にともない上昇し、バリウム添加量が０．０７重
量％でピークに達するが、バリウム添加量をさらに増加
していくにしたがって低下しはじめるバリウム添加量が
０．１５重量％を越えるとバリウム無添加蛍光体より低
くなる。これは、バリウム添加量が０，１５重量％を越
える付近より、蛍光体のボディーカラーが茶色に着色し
始め、次第に濃くなるためと考えられる。As is clear from Figure 2, the luminance increases as the amount of barium added increases, reaching a peak when the amount of barium added is 0.07% by weight, but decreases as the amount of barium added is further increased. If the initial amount of barium added exceeds 0.15% by weight, it will be lower than that of the barium-free phosphor. This is considered to be because the body color of the phosphor begins to turn brown and gradually becomes darker when the amount of barium added exceeds 0.15% by weight.
上述のバリウム添加量と平均粒子径及び発光輝度との関
係から、本発明の青色発光蛍光体の添加物として用いら
れるバリウム添加量は硫化亜鉛１００ ｇに対して０．
１５重量％以下が好ましい。From the above-mentioned relationship between the amount of barium added and the average particle diameter and luminance, the amount of barium used as an additive in the blue-emitting phosphor of the present invention is 0.000 g per 100 g of zinc sulfide.
It is preferably 15% by weight or less.
以上述べたように、本発明によれば、従来の技術によっ
て得ることのできなかった、大粒子でかつ発光輝度の高
いＺｎＳ：Ａｇ、Ａｌｌ蛍光体を得ることができる。更
に本発明のＺｎＳ：Ａｇ。As described above, according to the present invention, it is possible to obtain a ZnS:Ag, All phosphor having large particles and high luminance, which could not be obtained by conventional techniques. Furthermore, ZnS:Ag of the present invention.
Ａｎ）蛍光体を陰極線管の蛍光面に用いた陰極線管は、
従来の陰極線管に比較して５〜２０％明るい。An) A cathode ray tube that uses phosphor for the fluorescent screen of the cathode ray tube is
5-20% brighter than conventional cathode ray tubes.
以下、本発明のＺｎＳ：Ａｇ、Ａｆｆ蛍光体及びこの蛍
光体を用いた陰極線管について具体的実施例により詳細
に説明する。Hereinafter, the ZnS:Ag, Aff phosphor of the present invention and a cathode ray tube using this phosphor will be described in detail with reference to specific examples.
（実施例−１）
まず、硫化亜鉛１００ ｇに対して硝酸銀（ＡｇＮＣｈ
）を０．１ ｇ、硝酸アルミニウム溶剤、例えば塩化ア
ンモニウム（ＮＨ４Ｃｊ７ ）を０．１ｇ加えスラリー
状にして混合、乾燥した後、この混合物にイオウ（Ｓ）
を３ｇ添加し硫化水素性還元雰囲気中にて９８０℃、３
時間焼成し脱イオン水で数回洗浄、粉砕、処理等を行い
濾過、乾燥した後、篩別した。こうして０．０６重量％
の銀、０．０６重量％のアルミニウム、更に０．０７重
量％のバリウムを含有したＺｎＳ：Ａｇ、Ａｌｌ蛍光体
が得られる。(Example-1) First, silver nitrate (AgNCh
) and 0.1 g of an aluminum nitrate solvent, such as ammonium chloride (NH4Cj7), are mixed into a slurry, dried, and then sulfur (S) is added to the mixture.
3g was added and heated at 980℃ in a hydrogen sulfide reducing atmosphere
The product was calcined for a period of time, washed several times with deionized water, pulverized, treated, etc., filtered, dried, and then sieved. Thus 0.06% by weight
A ZnS:Ag,All phosphor containing 0.06% by weight of aluminum, and further 0.07% by weight of barium is obtained.
この粒子の平均粒子径は通気法に基づくプレイン法によ
って測定した結果、９．０μｍであった。The average particle diameter of these particles was 9.0 μm as measured by the plain method based on the aeration method.
また、このときの発光輝度はバリウムを、添加されてい
ない従来蛍光体の発光輝度を１００％として測定した結
果、１０４％であった。Further, the luminance at this time was 104% when measured with the luminance of a conventional phosphor to which no barium was added as 100%.
更にこの蛍光体を陰極線管の蛍光面に用いたとき蛍光体
結晶が十分に成長していること等から機械的強度に優れ
、蛍光面塗布に先立つビーズミル等の蛍光体分散工程で
の輝度劣化を少なくし充分な分散処理を施すことができ
る。また、この結晶形状の均一化によりの大粒子蛍光体
であるにもかかわらず緻密な蛍光面を得ることができ、
従来方法で製造した同程度の大きさのＺｎＳ：Ａｇ。Furthermore, when this phosphor is used in the phosphor screen of a cathode ray tube, it has excellent mechanical strength due to the sufficient growth of phosphor crystals, and reduces brightness deterioration during the phosphor dispersion process using bead mills etc. prior to coating the phosphor screen. It is possible to perform sufficient dispersion treatment with a small amount. In addition, by making the crystal shape uniform, it is possible to obtain a dense phosphor screen even though it is a large particle phosphor.
Comparably sized ZnS:Ag produced by conventional methods.
Ａｆｉ蛍光体に比較し、明るさが約２０％高い陰極線管
が得られた。A cathode ray tube with approximately 20% higher brightness than the Afi phosphor was obtained.
第３図はこの陰極線管を示す図で、パネル１にファンネ
ル２およびネック３が封着されて外囲器４を構成し、ネ
ック３から電子銃５が挿入されている。そして、パネル
１の内面に蛍光膜６が形成され、電子銃５によって放出
された電子ビームが蛍光膜６に射突して励起発光するよ
うになっている。FIG. 3 shows this cathode ray tube, in which a funnel 2 and a neck 3 are sealed to a panel 1 to form an envelope 4, and an electron gun 5 is inserted through the neck 3. A fluorescent film 6 is formed on the inner surface of the panel 1, and the electron beam emitted by the electron gun 5 impinges on the fluorescent film 6 to excite it and emit light.
（実施例−２）
硫化亜鉛１００ ｇに対して硝酸銀（ＡｇＮ０３）を０
．１ ｇ、硝酸アルミニウム（Ａｇ （ＮＯ３）３・９
Ｈ２０）を０．８ｇ、塩化バリウム（ＢａＣｊ！２）を
０．０７ｇ、沃化アンモニウム（ＮＨ４ｔ ） ０．１
ｇ加えスラリー状にして混合、乾燥した後、この混合
物にイオウ（Ｓ）を３ｇ添加し硫化水素性還元雰囲気中
にて９８０℃、３時間焼成し脱イオン水で数回洗浄、粉
砕、処理等を行い濾過、乾燥した後、篩別した。こうし
て０．０６重量％の銀、ｏ、ｏｅ重量％のアルミニウム
、更に０．０３重量％のバリウムを含有したＺｎＳ：Ａ
ｇ、ＡＮ蛍光体が得られる。この蛍光体の平均粒子径は
７．８μｍであり、このときの発光輝度はバリウムを添
加していない従来の蛍光体の発光輝度を１００％として
測定した結果、１０２％であった。(Example-2) 0 silver nitrate (AgN03) was added to 100 g of zinc sulfide.
．． 1 g, aluminum nitrate (Ag (NO3) 3.9
H20) 0.8g, barium chloride (BaCj!2) 0.07g, ammonium iodide (NH4t) 0.1
After adding g and mixing to form a slurry and drying, 3 g of sulfur (S) was added to this mixture, and the mixture was calcined at 980°C for 3 hours in a hydrogen sulfide reducing atmosphere, washed several times with deionized water, pulverized, treated, etc. After filtering and drying, the mixture was sieved. Thus ZnS:A containing 0.06% by weight of silver, o, oe% by weight of aluminum, and further 0.03% by weight of barium.
g. AN phosphor is obtained. The average particle diameter of this phosphor was 7.8 μm, and the luminance was 102% when measured with the luminance of a conventional phosphor to which no barium was added as 100%.
この蛍光体を陰極線管の蛍光面に用いたとき、従来方法
で製造した同程度の大きさのＺｎＳ：Ａｇ、Ａｌｌ蛍光
体に比較し、明るさが約ｌＯ％高い陰極線管が得られた
。When this phosphor was used in the phosphor screen of a cathode ray tube, a cathode ray tube with approximately 10% higher brightness was obtained compared to a ZnS:Ag, All phosphor of similar size manufactured by a conventional method.
（実施例−３）
硫化亜鉛ｔｏｏ ｇに対して硝酸銀（ＡｇＮＯ３）を０
．１ ｇ、硝酸アルミニウム（／ｌ （ＮＯ３）３・
９Ｈ２０）を０．８ ｇ、弗化バリウム（ＢａＦ２）を
０．２ ｇ、塩化アンモニウム（ＮＨ４ＣＤ ） ０．
１ｇ加えスラリー状にして混合、乾燥した後、この混合
物にイオウ（Ｓ）を３ｇ添加し硫化水素性還元雰囲気中
にて９８０℃、３時間焼成し脱イオン水で数回洗浄、粉
砕、処理等を行い濾過、乾燥した後、篩別した。こうし
て０．０６重量％の銀、０．０６重量％のアルミニウム
、更に０．１０重量％のバリウムを含有したＺｎＳ：Ａ
ｇ、Ａｊ７蛍光体が得られた。(Example-3) 0 silver nitrate (AgNO3) for too much zinc sulfide
．． 1 g, aluminum nitrate (/l (NO3)3.
9H20), 0.2 g of barium fluoride (BaF2), and 0.8 g of ammonium chloride (NH4CD).
Add 1g of sulfur (S) to the mixture, mix it into a slurry, and dry. 3g of sulfur (S) is added to this mixture, and it is calcined at 980°C for 3 hours in a hydrogen sulfide reducing atmosphere, washed several times with deionized water, pulverized, treated, etc. After filtering and drying, the mixture was sieved. Thus, ZnS:A contained 0.06% by weight of silver, 0.06% by weight of aluminum, and further 0.10% by weight of barium.
g, Aj7 phosphor was obtained.
この蛍光体の平均粒子径は９．８μｍであり、このとき
の発光輝度はバリウムを添加していない従来の蛍光体の
発光輝度を１００％して測定した結果、１０３％であっ
た。The average particle diameter of this phosphor was 9.8 μm, and the luminance was 103%, as measured by setting the luminance of a conventional phosphor to which no barium was added as 100%.
この蛍光体を陰極線管の蛍光面に用いたとき、従来方法
で製造した同程度の大きさのＺｎＳ：Ａｇ、Ａｇ蛍光体
に比較し、明るさが約１５％高い陰極線管が得られた。When this phosphor was used in the phosphor screen of a cathode ray tube, a cathode ray tube with approximately 15% higher brightness was obtained compared to ZnS:Ag, Ag phosphors of similar size manufactured by conventional methods.
（実施例−４）
硫化亜鉛１００ ｇに対して硝酸銀（ＡｇＮＯ３）を０
．１ ｇ、硝酸アルミニウムＣＡＤ （ＮＯ３）３・
９Ｈ２０）を０．８ ｇ、臭化バリウム（ＢａＢｒ２）
を０．４７ｇ、塩化カリウム（ＫＣｊｌｌ）０．１ｇ加
えスラリー状にして混合、乾燥した後、この混合物にイ
オウ（Ｓ）を３ｇ添加し硫化水素性還元雰囲気中にて９
８０℃、３時間焼成し脱イオン水で数回洗浄、粉砕、処
理等を行い濾過、乾燥した後、篩別した。こうして０．
０６重量％の銀、０゜０６重量％のアルミニウム、更に
０．１５重量％のバリウムを含有したＺｎＳ：Ａｇ、Ａ
ｌ蛍光体が得られた。この蛍光体の平均粒子径は１００
０μｍであり、このときの発光輝度はバリウムを添加し
ていない従来の蛍光体の発光輝度を１００％としたとき
の測定値と同じであった。(Example-4) Silver nitrate (AgNO3) was added to 100 g of zinc sulfide.
．． 1 g, aluminum nitrate CAD (NO3)3.
9H20), 0.8 g of barium bromide (BaBr2)
After adding 0.47 g of potassium chloride (KCjll) and 0.1 g of potassium chloride (KCjll) to form a slurry, mixing and drying, 3 g of sulfur (S) was added to this mixture, and 9 g of sulfur was added in a hydrogen sulfide reducing atmosphere.
The product was calcined at 80° C. for 3 hours, washed several times with deionized water, pulverized, treated, etc., filtered, dried, and then sieved. Thus 0.
ZnS:Ag,A
1 phosphor was obtained. The average particle diameter of this phosphor is 100
0 μm, and the luminance at this time was the same as the measured value when the luminance of a conventional phosphor not added with barium was taken as 100%.
この蛍光体を陰極線管の蛍光面に用いたとき、従来方法
で製造した同程度の大きさのＺｎＳ：Ａｇ、Ａｌ蛍光体
に比較し、明るさが約１５％高い陰極線管が得られた。When this phosphor was used in the phosphor screen of a cathode ray tube, a cathode ray tube with approximately 15% higher brightness was obtained compared to a ZnS:Ag, Al phosphor of similar size manufactured by a conventional method.
［発明の効果コ
本発明によれば、結晶が均一化し、かつ充分に成長し機
械的強度に優れている。従って蛍光面塗布に先立ってビ
ーズミル等の蛍光体分散工程での輝度劣化を少なくする
とともに、発光輝度の高い大粒子蛍光体を得ることがで
きる。[Effects of the Invention] According to the present invention, the crystals are uniform and grow sufficiently, and have excellent mechanical strength. Therefore, it is possible to reduce luminance deterioration in a phosphor dispersion process using a bead mill or the like prior to coating on a phosphor screen, and to obtain a large particle phosphor with high luminance.
第１図は本発明の青色発光蛍光体における硫化亜鉛１０
０ｇに対するバリウム添加量と得られるＺｎＳ：Ａｇ、
ＡＩＩ蛍光体の平均粒子径との関係を示す図、第２図は
バリウムを添加していない従来の蛍光体の発光輝度を１
００％として本発明の青色発光蛍光体の硫化亜鉛１００
ｇに対するバリウムト・・パネル ２・・・ファンネル
３・・・ネック４・・・外囲器 ５・・・電子銃
６・・・蛍光膜代理人 弁理士 則 近 憲 佑
同 竹 花 喜久男
第１図
第３図
第２図Figure 1 shows zinc sulfide 10 in the blue-emitting phosphor of the present invention.
Barium addition amount to 0g and obtained ZnS:Ag,
Figure 2 shows the relationship between the average particle diameter of AII phosphor and the luminance of conventional phosphor without barium added.
Zinc sulfide of the blue-emitting phosphor of the present invention as 00%
Bariumt for g...Panel 2...Funnel 3...Neck 4...Envelope 5...Electron gun
6... Fluorescent membrane agent Patent attorney Nori Chika Yudo Kikuo Takehana Figure 1 Figure 3 Figure 2
Claims (2)
鉛蛍光体において、前記蛍光体全量に対して０．１５重
量％以下（０を除く）バリウムを含有してなることを特
徴とする青色発光蛍光体。(1) A blue-emitting phosphor comprising a silver and aluminum activated zinc sulfide phosphor using zinc sulfide as a matrix and containing 0.15% by weight or less (excluding 0) of barium based on the total amount of the phosphor. body.
るパネル内面に形成した蛍光膜を有することを特徴とす
る陰極線管。(2) A cathode ray tube comprising a phosphor film formed of the blue-emitting phosphor according to claim 1 on the inner surface of a panel constituting an envelope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10536590A JP2807311B2 (en) | 1990-04-23 | 1990-04-23 | Blue light emitting phosphor and cathode ray tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10536590A JP2807311B2 (en) | 1990-04-23 | 1990-04-23 | Blue light emitting phosphor and cathode ray tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH044287A true JPH044287A (en) | 1992-01-08 |
| JP2807311B2 JP2807311B2 (en) | 1998-10-08 |
Family
ID=14405696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10536590A Expired - Fee Related JP2807311B2 (en) | 1990-04-23 | 1990-04-23 | Blue light emitting phosphor and cathode ray tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2807311B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002061014A1 (en) * | 2001-01-30 | 2002-08-08 | Hitachi, Ltd. | Image display device |
| JP2002241193A (en) * | 2001-02-14 | 2002-08-28 | Sumitomo Electric Ind Ltd | Window material, optical window and method for producing the window material |
-
1990
- 1990-04-23 JP JP10536590A patent/JP2807311B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002061014A1 (en) * | 2001-01-30 | 2002-08-08 | Hitachi, Ltd. | Image display device |
| US6808829B2 (en) | 2001-01-30 | 2004-10-26 | Hitachi, Ltd. | Image-display device |
| JP2002241193A (en) * | 2001-02-14 | 2002-08-28 | Sumitomo Electric Ind Ltd | Window material, optical window and method for producing the window material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2807311B2 (en) | 1998-10-08 |
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