JPS63308088A - Fluorescent material - Google Patents
Fluorescent materialInfo
- Publication number
- JPS63308088A JPS63308088A JP14317087A JP14317087A JPS63308088A JP S63308088 A JPS63308088 A JP S63308088A JP 14317087 A JP14317087 A JP 14317087A JP 14317087 A JP14317087 A JP 14317087A JP S63308088 A JPS63308088 A JP S63308088A
- Authority
- JP
- Japan
- Prior art keywords
- fluorescent material
- phosphor
- zinc
- aluminum
- compound
- 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
- 239000000463 material Substances 0.000 title abstract 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 12
- -1 aluminum compound Chemical class 0.000 claims abstract description 11
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 239000002344 surface layer Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 47
- BZADFGFBTBPKRI-UHFFFAOYSA-N [O-]B([O-])[O-].OB(O)O.P.[In+3] Chemical compound [O-]B([O-])[O-].OB(O)O.P.[In+3] BZADFGFBTBPKRI-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 8
- JNOXFAKBEFRROH-UHFFFAOYSA-N indium(3+);borate Chemical compound [In+3].[O-]B([O-])[O-] JNOXFAKBEFRROH-UHFFFAOYSA-N 0.000 abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 abstract description 5
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 238000010894 electron beam technology Methods 0.000 abstract description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 abstract description 4
- 229940007718 zinc hydroxide Drugs 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電子線照射による劣化の少ない蛍光体に係り、
特に励起電流密度の高い投写型ブラウン管および端末デ
ィスプレイ・ブラウン管に好適な蛍光体に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a phosphor that exhibits little deterioration due to electron beam irradiation.
In particular, the present invention relates to a phosphor suitable for projection type cathode ray tubes and terminal display cathode ray tubes with high excitation current density.
投写型ブラウン管は２通常のカラー受像管より約２桁高
い電流密度の電子線を用いるため、長時間の使用につれ
て蛍光膜の着色と発光効率の低下（焼け）が生ずる。同
−画偉を長時間表示することの多いディスプレイ管にお
いても同様である０従来このような焼けを軽減させる方
法として、特開昭ＦＩＯ−４９５４４号および特開昭６
０−９４４９１号に記載のようにシリカによる被覆。Since projection type cathode ray tubes use electron beams with a current density about two orders of magnitude higher than that of ordinary color picture tubes, the phosphor film becomes discolored and the luminous efficiency decreases (burnt) over long periods of use. The same applies to display tubes that often display images for long periods of time.As a conventional method for reducing such burnout, Japanese Patent Application Laid-Open Nos. 49544 and 6
Coating with silica as described in No. 0-94491.
あるいは特開昭５９−１４９９８１号に記載のように水
酸化アルミニウムまたは二酸化けい索を含む水酸化アル
ミニウムによる被覆で蛍光粒子表面を保護する方法が知
られている。また特開昭５９−３６１８２号に記載のよ
うに他の目的でシリカアルミニウム化合物および亜鉛化
合物により被覆することも知られている。Alternatively, as described in JP-A-59-149981, a method is known in which the surface of the fluorescent particles is protected by coating with aluminum hydroxide or aluminum hydroxide containing carbon dioxide. It is also known to coat with silica aluminum compounds and zinc compounds for other purposes, as described in JP-A-59-36182.
一方硼酸インジウムを母体とし、希土類イオンを付活剤
とする蛍光体は１９６８年に米国特許第３３９４０８４
号に開示されている。硼酸インジウム蛍光体の応用とし
ては、ユーロピウムおよびテルビウム付活のものが各々
赤色、緑色発光の。On the other hand, a phosphor using indium borate as a matrix and rare earth ions as an activator was published in U.S. Patent No. 3,394,088 in 1968.
Disclosed in the issue. As for the application of indium borate phosphors, those activated with europium and terbium emit red and green light respectively.
また両者の共付活のものがアンバー色発光の蛍光体とし
てディスプレイ管に用いられた例がある（第２０８回蛍
光体同学会講演予稿、１７頁１９８５年１１月）０
またテレビラム付活蛍光体は投写管用としても有用で１
色調が良く現在用いられている。There is also an example in which a co-activated product of both was used as a phosphor that emits amber color in display tubes (preliminary lecture of the 208th Phosphor Society Conference, p. 17, November 1985). The body is also useful for projection tubes.
It has a good color tone and is currently used.
Ｙ３Ａ１５０□：Ｔｂ系の蛍光体より１０係以上高輝度
の緑色発光が得られる（昭和６１年度電子通信学会総合
全国大会予稿集３２１）。Y3A150□: Green luminescence with high brightness of 10 or more can be obtained from Tb-based phosphors (Proceedings of the 1988 Institute of Electronics and Communication Engineers National Conference 321).
硼酸インジウム系蛍光体は発光効率１色調などの点で優
れた蛍光体ではあるが、高電流密度餉域で励起される場
合にはＹｓ Ａ ／ ５０１□：Ｔｂ系に比べ劣化特性
の点で問題を残しているｏしかし焼けを軽減するための
前記した従来技術を硼酸インジウム系蛍光体に適用した
結果はＹ３Ａ／、０□２：Ｔｂ系を標準とした時なセ不
十分なものであった。Indium borate-based phosphors are excellent in terms of luminous efficiency and one color tone, but when excited in a high current density range, they have problems in terms of deterioration characteristics compared to Ys A / 501□:Tb-based phosphors. However, when the above-mentioned conventional technology for reducing burnout was applied to indium borate-based phosphors, the results were unsatisfactory when Y3A/, 0□2:Tb-based phosphors were used as standard. .
本発明の目的はあらたに硼酸インジウム系蛍光体の焼け
を軽減する方法を見出し、高電流ｑＭ度励起においても
劣化の少ない良好な蛍光体を提供することである。The purpose of the present invention is to find a new method for reducing burnout of indium borate-based phosphors, and to provide a good phosphor that exhibits little deterioration even under high current qM excitation.
投写管の電流密度領域において寿命試験を行ない、下記
の表面処理法の効果を比較した。A lifespan test was conducted in the current density region of the projection tube, and the effects of the following surface treatment methods were compared.
（１） 燐酸カルシウム被櫟：水ガラス溶液中におけ
る沈降塗布において、充填密度の高い平滑度の良い蛍光
体膜が得られる表面処理。(1) Calcium phosphate coating: A surface treatment that allows a phosphor film with high packing density and good smoothness to be obtained by precipitation coating in a water glass solution.
（２）シリカ被榎：前記従来例の−。(2) Silica coating: − of the above-mentioned conventional example.
（３）水酸化アルミニウム被傍：前記従来例の−。(3) Aluminum hydroxide coating: − of the conventional example.
（４）酸化亜鉛または水酸化亜鉛と酸化アルミニウムに
より被轡し、その後加熱処理により蛍光体と、前記化合
物とから生ずる固溶体を蛍光体表面に形成。(4) Covered with zinc oxide or zinc hydroxide and aluminum oxide, and then heated to form a solid solution formed from the phosphor and the compound on the surface of the phosphor.
その結果（４）の方法によってのみ焼けが著しく改善さ
れ、Ｙ３Ａ／、０．２： Ｔｂ系蛍光体と同水準に達す
ることがわかった。As a result, it was found that only method (4) significantly improved the burnout, reaching the same level as the Y3A/, 0.2:Tb-based phosphor.
以下（４）に基づく本発明の詳細な説明する０本発明の
蛍光体はつぎの方法によって製造される０
まず純水中に蛍光体を入れ、充分に懸濁される０次にこ
の懸濁液番こコロイダルアルミナを入れ充分攪拌し更に
亜鉛イオンを含む水溶液を適当量加えしかる後このアル
ミニウムと亜鉛イオンを含む懸濁液にアルカリを加えて
懸濁液のｐＨを７．５乃至１１に調整し、アルミニウム
の水酸化物、亜鉛の水酸化物（以後代表的な組成をＡＪ
（ＯＨ）３、Ｚｎ（ＯＨ）ｇ と略称する）を析出せ
しめる。析出した微粒子のＡｊ（ＯＨ）、、２口（ＯＨ
）ｚ は螢光体表面に吸着される。懸濁液を放置し、
Ａｊ（ＯＨ）ｍとＺｎ（ＯＨ）２微粒子が付着した螢
光体を沈降せしめ、しかる後デガンテーシ璽ンにより上
澄み液を除去する。水洗を数回繰返して残留イオンを除
去した後、脱水、乾燥する。乾燥後、得られる塊状の螢
光体を篩を通してほぐし、その後高温で加熱処理し、目
的とする螢光体を得る。The present invention will be described in detail based on (4) below. The phosphor of the present invention is manufactured by the following method. First, the phosphor is placed in pure water, and the suspension is thoroughly suspended. Add the colloidal alumina, stir thoroughly, add an appropriate amount of an aqueous solution containing zinc ions, and then add an alkali to the suspension containing aluminum and zinc ions to adjust the pH of the suspension to 7.5 to 11. Aluminum hydroxide, zinc hydroxide (hereinafter representative compositions are referred to as AJ)
(OH)3, abbreviated as Zn(OH)g) is precipitated. Aj (OH) of the precipitated fine particles, 2 mouths (OH
)z is adsorbed on the phosphor surface. Leave the suspension
The phosphor to which Aj(OH)m and Zn(OH)2 fine particles are attached is allowed to settle, and then the supernatant liquid is removed using a degantizer. After washing with water several times to remove residual ions, it is dehydrated and dried. After drying, the resulting lumpy phosphor is passed through a sieve to loosen it, and then heat-treated at a high temperature to obtain the desired phosphor.
アルミニウムイオンを含む水溶液としては水溶性アルミ
ニウム化合物、例えば硫酸アルミニウム（ＡＪ２（８０
４）３）、酢酸アルミニウム（Ａｉ（ＣＨｓＣＯＯ）、
）、硝酸アルミニウム（Ａ’（ＮＯ３）ｓ ）を用い、
また亜鉛イオンを含む水溶液としては水溶性亜鉛化合物
１例えば硫酸亜鉛（Ｚ ｎ Ｓ Ｏ４）−酢酸亜鉛（Ｚ
ｎ （ＣＨｓ ＣＯＯ） ２ ）。As the aqueous solution containing aluminum ions, water-soluble aluminum compounds such as aluminum sulfate (AJ2 (80
4) 3), aluminum acetate (Ai(CHsCOO),
), using aluminum nitrate (A'(NO3)s),
In addition, examples of aqueous solutions containing zinc ions include water-soluble zinc compounds 1 such as zinc sulfate (Z n SO4)-zinc acetate (Z
n (CHs COO) 2 ).
硝酸亜鉛（ｚ” （Ｎ Ｏ３） ２ 、 ／Ｎロゲン化
亜鉛（ＺｎＩ２．Ｘは弗素を除くハロゲン）等の水溶液
がか用いられる。才たｐＨ１）Ｊｌ整用のアルカリとし
ては水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（
ＫＯＨ）、水酸化アンモニウム（ＮＨ４０Ｈ）の水溶液
が用いられる。ＮＨ４ＯＨを使用する場合過剰に加える
と可溶性のアンミン錯イオンが生じＺｎ（ＯＨ）、が析
出しないので、ｐＨ値力月Ｏを趙えないようｌご注意す
る必要がある０また前記加熱処理は、蛍光体表面に付着
した前記亜鉛化合物とアルミニウム化合物がその蛍光体
表面層と固溶体を造るような温度と時間で処理される。An aqueous solution such as zinc nitrate (z'' (N O3) 2 , /N zinc halogenide (ZnI2. ), potassium hydroxide (
KOH), ammonium hydroxide (NH40H) aqueous solutions are used. When using NH4OH, if it is added in excess, soluble ammine complex ions will be generated and Zn(OH) will not precipitate, so care must be taken not to lower the pH value. The zinc compound and aluminum compound adhering to the phosphor surface are treated at a temperature and for a time such that they form a solid solution with the phosphor surface layer.
この様な温度とは通常５００〜】０００℃の範囲で行な
われ、その時間は加熱温度でも異なるが３０分〜６時間
程度である。尚１本発明で言う前記固溶体と言う概念は
上述の温度で加熱した時に生じる融着状態を含むもので
あり、またその固溶状態も表面層で均一なものではなく
１表面では亜鉛化合物とアルミニウム化合物が多い状態
であり５表面から蛍光体内部に向って、その量は少くな
るものである。また上記亜鉛化合物とアルミニウム化合
物は通常加熱処理により酸化亜鉛、酸化アルミニウムの
状態で含まれる。Such temperature is usually in the range of 500 to 1,000°C, and the heating time is about 30 minutes to 6 hours, although it varies depending on the heating temperature. Note that the concept of the solid solution referred to in the present invention includes the fused state that occurs when heated at the above-mentioned temperature, and the solid solution state is not uniform on the surface layer, but on one surface, the zinc compound and aluminum are mixed together. There is a large amount of compounds, and the amount decreases from the surface of the phosphor to the inside of the phosphor. Further, the above-mentioned zinc compound and aluminum compound are usually contained in the state of zinc oxide and aluminum oxide by heat treatment.
本発明の蛍光体は、その表面層のみに亜鉛化合物とアル
ミニウム化合物を多幸に含むものであって、蛍光体粒子
全体に亜鉛化合物とアルミニウム化合物が均一にこの様
な量存在するものは１本発明に含まれない。上記蛍光体
表面層−こ含まれる亜鉛化合物およびアルミニウム化合
物Ｃま、亜鉛およびアルミニウムとしてそれぞれ蛍光体
全景に対し１０〜１０００μｇ／ｇの範囲の量で通常含
まれ上記量が１０００μｇ／ｇよりも多い場合には得硼
酸インジウム系蛍光体の表面層を該蛍光体。The phosphor of the present invention contains a zinc compound and an aluminum compound only in its surface layer, and the phosphor in which the zinc compound and aluminum compound are uniformly present in such amounts throughout the phosphor particles is one of the present invention. Not included in The surface layer of the phosphor contains zinc compounds and aluminum compounds C, each of which is normally contained in an amount ranging from 10 to 1000 μg/g relative to the entire surface of the phosphor, and when the above amount is more than 1000 μg/g. The surface layer of the indium borate phosphor is added to the phosphor.
アルミニウム化合物および亜鉛化合物から成る固溶体で
覆うことにより第１図に示す如く劣化を改善する事がで
きた。この図は上記蛍光体を水ガラス溶液中で沈降塗布
して炸裂した単色管について２０００時間寿命試験を行
なった結果を示している。動作条件は３０ｋＶ、５００
μＡでラスターサイズは５インチ対角である。試験終了
後の輝度の初輝度に対する比を実球輝度維持率と呼ぶこ
ととし、これを縦軸に取った。By covering with a solid solution consisting of an aluminum compound and a zinc compound, the deterioration could be improved as shown in FIG. This figure shows the results of a 2000 hour life test on a monochromatic tube in which the above phosphor was applied by precipitation in a water glass solution and exploded. Operating conditions are 30kV, 500
The raster size is 5 inches diagonal in μA. The ratio of the brightness after the end of the test to the initial brightness is called the real sphere brightness maintenance rate, and this is plotted on the vertical axis.
本発明における表面処理の効果は蛍光体粒子表面に保蹟
層を形成することではなく、むしろ表面のシリカ付着量
との関連にあると見られる。例えば燐酸カルシウム被願
した従来品とＡ／？２０３゜Ｚｎ（ＯＨ）２を付着後加
熱処理をした本発明品とのＩ ｎ ＨＯｓ蛍光体粒子表
面のＳｉ付着量を調べると、前者の方が多いことが分析
によって判明した（表１）０
水ガラスから形成されるシリカ自身の電子線照射による
着色は微弱であり、蛍光面の焼けを説明できるほどでは
ない。したがって、Ｉｎ８０１表面とシリカとの何らか
の相互作用が焼けを促進するのではないかと考えられる
。シリカを付着する表表１ 表面処理の違いによるＩｎ
ＢＯ： Ｔｂ螢光体粒子表面上のＳｉ付着量
表面処理＊） Ｓｉ付着量 輝度維持率（μｇ／
ｇ） （％）
本発明品 １３００ ８３従来品
１５００ ７９面処理はこの点で好ましい
とは言えない。また燐酸カルシウムは溶解度が高く、Ｃ
ａ２＋イオンの作用によりシリカが凝集しやすくなるの
で、やはり好ましくないと解せられる。水酸化アルミニ
ウムないし酸化アルミニウムあるいは水酸化亜鉛ないし
酸化亜鉛単独の被覆・加熱処理はあまり大きな効果はな
く、両者の併用が効果を発揮している。The effect of the surface treatment in the present invention is not due to the formation of a protective layer on the surface of the phosphor particles, but rather appears to be related to the amount of silica deposited on the surface. For example, the conventional product applied for calcium phosphate and A/? When examining the amount of Si deposited on the surface of In HOs phosphor particles compared to the product of the present invention which was heat-treated after adhering 203゜Zn(OH)2, analysis revealed that the former was larger (Table 1)0 The silica itself, which is formed from water glass, is only slightly colored by electron beam irradiation, and is not strong enough to explain the burnt appearance of the phosphor screen. Therefore, it is thought that some kind of interaction between the In801 surface and silica may promote burning. Table for adhering silica Table 1 In due to differences in surface treatment
BO: Si adhesion amount on the surface of Tb phosphor particles Surface treatment*) Si adhesion amount Brightness maintenance rate (μg/
g) (%) Invention product 1300 83 Conventional product
1500 79 surface processing cannot be said to be preferable in this respect. In addition, calcium phosphate has high solubility and C
Since silica tends to aggregate due to the action of a2+ ions, this is considered to be undesirable. Coating and heat treatment with aluminum hydroxide or aluminum oxide or zinc hydroxide or zinc oxide alone do not have a great effect, but a combination of both is effective.
以下、本発明を実施例により説明する。 The present invention will be explained below with reference to Examples.
実施例１
硼酸インジウム系螢光体ＩｎＢＯ，：Ｔｂｌ ＯＯｇを
３００ ｍ ｊの純水中に懸濁させた。この懸濁液に硫
酸アルミニウムの２０％水溶液０．３５ｍＪ加えで攪拌
した。この懸濁液に硫酸亜鉛の２０％水溶液０．３５
ｍ ｊを加え、その後攪拌しなからＮａＯＨ水溶液で懸
濁液のｐＨ値を１０．０に調整した。Example 1 An indium borate-based phosphor InBO,:Tbl OOg was suspended in 300 mj of pure water. To this suspension, 0.35 mJ of a 20% aqueous solution of aluminum sulfate was added and stirred. Add 0.35% of a 20% aqueous solution of zinc sulfate to this suspension.
m j was added, and then the pH value of the suspension was adjusted to 10.0 with an aqueous NaOH solution without stirring.
ｐＪＩ４整後更に５分間攪拌を続けた。攪拌を止め螢光
体を沈降させた後、上澄みをデカンテーシ冒ンにて除去
し、さらに螢光体をＩＪの純水で３回水洗した。その後
螢光体を吸引脱水し、１００℃で８時間乾燥した。After pJI4, stirring was continued for an additional 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant was removed by decanting, and the phosphor was washed three times with IJ pure water. Thereafter, the phosphor was dehydrated by suction and dried at 100° C. for 8 hours.
更に上記螢光体８００℃、１時間加熱処理して酸化アル
ミニウム、酸化亜鉛と螢光体から成る固溶体層を螢光体
表面層に生成後、出来上った螢光体を篩い、劣化に強い
螢光体を得ることができた。Further, the above phosphor is heat-treated at 800°C for 1 hour to form a solid solution layer consisting of aluminum oxide, zinc oxide and phosphor on the surface layer of the phosphor, and the resulting phosphor is sieved to make it resistant to deterioration. I was able to obtain a phosphor.
上述のようにして得られた螢光体はＡｊ、０．ｉびＺｎ
Ｏが螢光体表面層に含まれており、その含有量はＡ ｔ
ｔ Ｚ ｎ換算で各々５０μｇ／ｇ１１５０μｇ／ｇ
てありた。The phosphor obtained as described above has Aj, 0. IbiZn
O is contained in the surface layer of the phosphor, and its content is A t
50μg/g1150μg/g each in terms of tZn
There was.
劣化特許（輝度給持率で表現〕は第１図に示す如く、処
理なしに比し３０％アップした。As shown in FIG. 1, the deterioration rate (expressed as brightness retention rate) increased by 30% compared to the case without treatment.
実施例２
ＩｎＢＯ，： Ｔｂ （０，１ｍｏｉｆｂ ）、 Ｅ
ｕ （０，３ｍｏ／％）１００ｇを３００ｍ／の純水中
に懸濁させた０この懸濁液にコロイダルアルミナ（Ａ／
２０３ として２０９６含有）を１ ｍ ／加えて攪
拌した。Example 2 InBO,: Tb (0,1moifb), E
u (0.3 mo/%) 100 g was suspended in 300 m/p of pure water. Colloidal alumina (A/%) was added to this suspension.
203 (containing 2096) was added at 1 m/m and stirred.
これにさらに硫酸亜鉛の２０係水溶液０．０３ｍ／を加
え、その後攪拌しなからＮａＯＨ水溶液で懸濁液のｐＨ
値を１０．０に１１整した。以後実施例】桁値で各々１
００μｇ／ｇ、１２μｇ／ｇである試料を得た。この試
料の劣化特性を実施例】と同様の方法で測定し、処理な
しの試料と比較したところ輝度維持率は２０％アップし
た。To this, 0.03 m/20% aqueous solution of zinc sulfate was added, and after stirring, the pH of the suspension was adjusted with NaOH aqueous solution.
The value was adjusted to 10.0. Examples below] Each digit value is 1
Samples with concentrations of 00 μg/g and 12 μg/g were obtained. The deterioration characteristics of this sample were measured in the same manner as in Example], and compared with the untreated sample, the brightness maintenance rate was increased by 20%.
本発明によってＩｎＢＯ３： Ｔｂ蛍光体の焼けも著し
く改善した結果１色調が良好で輝度の高い緑色投写管を
実用化できた。またＩ ｎ Ｂ Ｏｓ系蛍光体を用いた
単色ディスプレイ管についても焼けを著しく改善できた
。According to the present invention, burnout of the InBO3:Tb phosphor has been significantly improved, and as a result, a green projection tube with good color tone and high brightness has been put into practical use. Furthermore, burnout was significantly improved in monochrome display tubes using InBOs-based phosphors.
第１図はＡ／及びＺｎ含有黛と実球寿命試験を２０００
時間行った後の輝度維持率（試験後の実球輝度の初輝度
に対する比）の関係を示す図である０
１・・・Ａ／換算含有量５０μｇ／ｇ、２・・・Ａ／換
算含有量１００μＭ７ｇ、３・・・Ａ／なし。
代理人 弁理士 小 川 勝 男
【 １、
（檜Figure 1 shows the A/ and Zn-containing powder and real ball life test at 2000
This is a diagram showing the relationship between the brightness maintenance rate (ratio of actual bulb brightness to initial brightness after the test) after the test is performed for a certain period of time. Amount 100μM 7g, 3...A/none. Agent: Patent Attorney Katsuo Ogawa [1, (Hinoki
Claims (1)
層が硼酸インジウム系蛍光体、亜鉛化合物およびアルミ
ニウム化合物の固溶体から成ることを特徴とする蛍光体
。 ２）上記固溶体に含有される亜鉛化合物およびアルミニ
ウム化合物は亜鉛およびアルミニウムとしてそれぞれ該
蛍光体全量に対し１０〜１０００μｇ／ｇの範囲の量で
該表面層に含むことを特徴とする特許請求の範囲第１項
記載の蛍光体。[Scope of Claims] 1) An indium borate phosphor, wherein the surface layer of the phosphor is composed of a solid solution of an indium borate phosphor, a zinc compound, and an aluminum compound. 2) The zinc compound and aluminum compound contained in the solid solution are contained in the surface layer in an amount ranging from 10 to 1000 μg/g based on the total amount of the phosphor as zinc and aluminum, respectively. The phosphor according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14317087A JPS63308088A (en) | 1987-06-10 | 1987-06-10 | Fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14317087A JPS63308088A (en) | 1987-06-10 | 1987-06-10 | Fluorescent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63308088A true JPS63308088A (en) | 1988-12-15 |
Family
ID=15332543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14317087A Pending JPS63308088A (en) | 1987-06-10 | 1987-06-10 | Fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63308088A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02261891A (en) * | 1989-03-31 | 1990-10-24 | Nichia Chem Ind Ltd | Indium borate phosphor and cathode ray tube |
| EP0457337A2 (en) * | 1990-05-18 | 1991-11-21 | Kasei Optonix, Ltd. | Color cathode-ray tube, and surface-treated phosphor and method for its production |
| EP0516193A2 (en) * | 1988-04-25 | 1992-12-02 | Gte Products Corporation | Process for imparting stir-in capabilities to a silver activated zinc sulfide phosphor |
| CN103025848A (en) * | 2010-08-19 | 2013-04-03 | 海洋王照明科技股份有限公司 | Borate luminescent materials, preparation methods and uses thereof |
-
1987
- 1987-06-10 JP JP14317087A patent/JPS63308088A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0516193A2 (en) * | 1988-04-25 | 1992-12-02 | Gte Products Corporation | Process for imparting stir-in capabilities to a silver activated zinc sulfide phosphor |
| JPH02261891A (en) * | 1989-03-31 | 1990-10-24 | Nichia Chem Ind Ltd | Indium borate phosphor and cathode ray tube |
| EP0457337A2 (en) * | 1990-05-18 | 1991-11-21 | Kasei Optonix, Ltd. | Color cathode-ray tube, and surface-treated phosphor and method for its production |
| US5304889A (en) * | 1990-05-18 | 1994-04-19 | Kasei Optonix Ltd. | Color cathode-ray tube, and surface-treated phosphor and method for its production |
| KR100221261B1 (en) * | 1990-05-18 | 1999-09-15 | 이시즈까 가즈오 | Color cathode-ray tube, and surface-treated phosphor and method for its manufacture |
| CN103025848A (en) * | 2010-08-19 | 2013-04-03 | 海洋王照明科技股份有限公司 | Borate luminescent materials, preparation methods and uses thereof |
| CN103025848B (en) * | 2010-08-19 | 2014-04-30 | 海洋王照明科技股份有限公司 | Borate luminescent materials, preparation methods and uses thereof |
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