JPS63128094A - Production of fluorescent material - Google Patents
Production of fluorescent materialInfo
- Publication number
- JPS63128094A JPS63128094A JP27581486A JP27581486A JPS63128094A JP S63128094 A JPS63128094 A JP S63128094A JP 27581486 A JP27581486 A JP 27581486A JP 27581486 A JP27581486 A JP 27581486A JP S63128094 A JPS63128094 A JP S63128094A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- mixture
- mixed
- phosphor
- europium
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 title abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 229910052788 barium Inorganic materials 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 3
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- 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 3
- 238000000034 method Methods 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、赤色発光の蛍光体、特にユーロピウムで付
活したイツトリウム・ランタンすキサイド蛍光体の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a red-emitting phosphor, particularly a yttrium lanthanum oxide phosphor activated with europium.
〔従来の技ｖＲ）
従来、ユーロピウムで付活したイツトリウム・ランタン
オキシサイド蛍光体の製造方法は、公開特許公報昭６０
−１６６３８１号に示されている。その第１の従来例と
して、酸化イツトリウム、酸化ランタン及び酸化ユーロ
ピウムの所定量を塩酸に溶解し、その溶液を加熱し、蒸
発乾固してから塩化物を得る。この塩化物をメタノール
に溶解した後、それにナトリオムメチラートのメタノー
ル溶液を加える。析出する塩化ナトリウムを除去して、
アンモニア水を加え、水酸化物を生成させる。この水酸
化物を乾燥し、１５００℃程度で焼成してユーロピウム
で付活したイツトリウム・ランタンオキサイド蛍光体を
得ていた。[Conventional Technique vR] Conventionally, a method for manufacturing a yttrium lanthanum oxide phosphor activated with europium is disclosed in Japanese Patent Application Publication No. 1983.
-166381. As a first conventional example, predetermined amounts of yttrium oxide, lanthanum oxide, and europium oxide are dissolved in hydrochloric acid, and the solution is heated and evaporated to dryness to obtain chloride. After dissolving the chloride in methanol, a methanol solution of sodium methylate is added to it. Remove precipitated sodium chloride,
Add ammonia water to generate hydroxide. This hydroxide was dried and fired at about 1500° C. to obtain a europium-activated yttrium lanthanum oxide phosphor.
次に、第２の従来例として、酸化イツトリウム、酸化ラ
ンタン及び酸化ユーロピウムを塩酸に溶解し、その溶液
を加熱し蒸発乾固した後、生成した塩化物に修酸アンモ
ニウム水溶液を加え、修酸塩を生成させる。その生成物
を空気中において、８００℃〜１０００℃で、１次焼成
し、酸化物とした後、この酸化物にホウ酸バリウムの粉
末を混合し、再度１２５０℃〜１３００℃で２次焼成し
て、ユーロピウムで付活したイツトリウム・ランタンオ
キサイド蛍光体を得ていた。Next, as a second conventional example, yttrium oxide, lanthanum oxide, and europium oxide were dissolved in hydrochloric acid, the solution was heated and evaporated to dryness, and then an ammonium oxalate aqueous solution was added to the generated chloride. to be generated. The product is first fired in the air at 800°C to 1000°C to form an oxide, then barium borate powder is mixed with this oxide and secondarily fired again at 1250°C to 1300°C. As a result, a yttrium lanthanum oxide phosphor activated with europium was obtained.
しかしながら、上記のような製造方法では、蛍光体に含
まれるナトリウムの含有量が多いので、蛍光ランプに使
用した場合、水銀との反応が顕著であって、光束維持率
が極めて低く実用的ではなく、更に蛍光体の平均粒径が
１〜３μｍと小さいので、発光輝度も不十分なものであ
フた。However, with the above manufacturing method, the phosphor contains a large amount of sodium, so when used in a fluorescent lamp, the reaction with mercury is significant and the luminous flux maintenance rate is extremely low, making it impractical. Furthermore, since the average particle size of the phosphor was small, 1 to 3 μm, the luminance of the light was insufficient.
また、錯酸塩を焼成し、分解して得られた酸化物にホウ
酸バリウムを混合し、再度焼成する方法では、ホウ酸バ
リウムを溶液として混合せずに、物理的または機械的に
混合するため、均一な混合が困難であり、更に、２次焼
成した固形物の性状が固く、その機械的粉砕処理が必要
であって、この粉砕処理により微細粒子が発生し、粒度
分布がシャープさを欠き、平均粒径が大きいにもかかわ
らず、発光輝度が上昇しないなどの欠点がありた。In addition, in the method of calcining the complex salt, mixing barium borate with the oxide obtained by decomposition, and calcining it again, barium borate is not mixed as a solution, but mixed physically or mechanically. Therefore, it is difficult to mix uniformly, and furthermore, the properties of the secondary fired solid are hard and require mechanical pulverization, and this pulverization generates fine particles and the particle size distribution becomes sharp. There were drawbacks such as lack of improvement in luminance despite the large average particle size.
そこで、この発明は、かかる欠点を解消するためになさ
れたもので、ナトリウム含有量が少なく、かつ粒度分布
が良好で発光輝度が高い蛍光体の製造方法を得ることを
目的とする。Therefore, the present invention was made to eliminate such drawbacks, and an object of the present invention is to provide a method for producing a phosphor that has a low sodium content, a good particle size distribution, and high luminance.
この発明に係る蛍光体の製造方法は、イツトリウム、ラ
ンタン及びユーロピウムの酸性混合水溶液に修酸水溶液
を混合して、生成した沈殿物を含むスラリーにアルカリ
土類金属の炭酸塩とホウ酸を加えて混合物とした後、該
混合物を乾燥して。The method for producing a phosphor according to the present invention includes mixing an acidic mixed aqueous solution of yttrium, lanthanum, and europium with an oxalic acid aqueous solution, and adding an alkaline earth metal carbonate and boric acid to the slurry containing the generated precipitate. After forming a mixture, the mixture is dried.
焼成し、ユーロピウムて付活したイツトリウム・ランタ
ンオキサイド蛍光体を得る方法としたものである。This is a method for obtaining a yttrium lanthanum oxide phosphor that is fired and activated with europium.
この発明における蛍光体の製造方法はイツトリウム、ラ
ンタン及びユーロピウムの酸性混合水溶液に修酸水溶液
を加え、それから得られたスラリーにアルカリ土類金属
の炭酸塩とホウ酸を加えて混合し、その混合物を乾燥し
焼成することとしたので、蛍光体へのナトリウムの混入
量が抑制され、また、１回の焼成で所望の蛍光体を得る
ことが可能となる。The method for producing a phosphor in this invention is to add an oxalic acid aqueous solution to an acidic mixed aqueous solution of yttrium, lanthanum, and europium, and then add and mix an alkaline earth metal carbonate and boric acid to the resulting slurry. Since the phosphor is dried and fired, the amount of sodium mixed into the phosphor is suppressed, and the desired phosphor can be obtained in one firing.
酸化イツトリウム８７ｇ、酸化ランタン５ｇ及び酸化ユ
ーロピウム８ｇを硝酸に溶解し、これから得られた酸性
混合水溶液に修酸２４０ｇを溶解した水溶液を加え、錯
酸塩として共沈させる。その生成した錯酸塩を水で洗浄
し、濾過した後、この錯酸塩の沈殿に純水１．５ｆＬを
加えスラリーとする。そのスラリーに炭酸バリウム０．
２７９ｇとホウ酸０．４７４ｇを加え、十分に混合した
後、乾燥する。これをアルミナの素材からなるルツボに
入れ、１２５０℃で２時間焼成する。これを粉砕し、３
５０メツシユの篩を通過させ、所望のユーロピウムで付
活したイツトリウム・ランタンオキサイド蛍光体が得ら
れた。この蛍光体は、従来の蛍光体に比較し、シャープ
な粒度分布を示し、発光輝度が３〜５％向上したもので
ある。87 g of yttrium oxide, 5 g of lanthanum oxide, and 8 g of europium oxide are dissolved in nitric acid, and an aqueous solution in which 240 g of oxalic acid is dissolved is added to the resulting acidic mixed aqueous solution to co-precipitate as a complex acid salt. The generated complex salt is washed with water and filtered, and then 1.5 fL of pure water is added to the precipitate of the complex salt to form a slurry. The slurry contains 0.0% barium carbonate.
Add 279 g and 0.474 g of boric acid, mix thoroughly, and then dry. This was placed in a crucible made of alumina material and fired at 1250°C for 2 hours. Crush this, 3
The desired europium-activated yttrium lanthanum oxide phosphor was obtained by passing through a 50 mesh sieve. This phosphor exhibits a sharp particle size distribution and has improved luminance by 3 to 5% compared to conventional phosphors.
上記の実施例では、出発原料の各成分の酸化物をｆｌＮ
＆に溶解し、酸性混合水溶液を得ているが、硝酸に特定
するものではなく、塩酸などに各成分の酸化物を溶解し
て、酸性混合水溶液を得ても差支えない。また、酸性混
合水溶液に修酸水溶液を加え、錯酸塩として共沈させ、
それから得たスラリーに炭酸バリウムとホウ酸を加えて
混合し、乾燥しているが、ここで、炭酸バリウムに特定
するものではなく、炭酸カルシウムなどのアルカリ土類
金属の炭酸塩とホウ酸を加えても差支えない。In the above example, the oxide of each component of the starting material was flN
& to obtain an acidic mixed aqueous solution, but this is not limited to nitric acid, and an acidic mixed aqueous solution may be obtained by dissolving the oxides of each component in hydrochloric acid or the like. In addition, an oxalic acid aqueous solution is added to an acidic mixed aqueous solution to co-precipitate as a complex acid salt,
Barium carbonate and boric acid are then added to the resulting slurry, mixed, and dried. There is no problem.
この発明は、以上説明したように、イツトリウム、ラン
タン及びユーロピウムの錯酸塩を含むスラリーにアルカ
リ土類金属の炭酸塩とホウ酸を加え、湿式混合すること
としたので粒度分布が良好で、発光輝度の向上した赤色
発光の蛍光体を得ることができる。また、蛍光体の製造
工程において、１回の焼成で所望の蛍光体が得られ、顕
著なコスト低減を図ることができる。As explained above, this invention adds alkaline earth metal carbonate and boric acid to a slurry containing complex salts of yttrium, lanthanum, and europium and wet-mixes the slurry, resulting in good particle size distribution and luminescence. A red-emitting phosphor with improved brightness can be obtained. Further, in the phosphor manufacturing process, a desired phosphor can be obtained by one firing, and a significant cost reduction can be achieved.
Claims (1)
サイド蛍光体の製造方法において、イツトリウム，ラン
タン及びユーロピウムの酸性混合水溶液と修酸水溶液と
を混合して、生成した沈殿物を含むスラリーにアルカリ
土類金属の炭酸塩とホウ酸を加えて混合物とした後、該
混合物を乾燥して、焼成することを特徴とする蛍光体の
製造方法。In a method for producing a europium-activated yztrium-lanthanum oxide phosphor, an acidic mixed aqueous solution of yztrium, lanthanum, and europium is mixed with an oxalic acid aqueous solution, and an alkaline earth metal carbonate is added to the slurry containing the generated precipitate. and boric acid to form a mixture, and then drying and firing the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27581486A JPS63128094A (en) | 1986-11-19 | 1986-11-19 | Production of fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27581486A JPS63128094A (en) | 1986-11-19 | 1986-11-19 | Production of fluorescent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63128094A true JPS63128094A (en) | 1988-05-31 |
Family
ID=17560790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27581486A Pending JPS63128094A (en) | 1986-11-19 | 1986-11-19 | Production of fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63128094A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994019422A1 (en) * | 1993-02-26 | 1994-09-01 | Kabushiki Kaisha Toshiba | Phospor and fluorescent lamp made by using the same |
-
1986
- 1986-11-19 JP JP27581486A patent/JPS63128094A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994019422A1 (en) * | 1993-02-26 | 1994-09-01 | Kabushiki Kaisha Toshiba | Phospor and fluorescent lamp made by using the same |
| US5585692A (en) * | 1993-02-26 | 1996-12-17 | Kabushiki Kaisha Toshiba | Fluorescent material and fluorescent lamp using same |
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