JPH07116425B2 - Method for producing self-activated zinc oxide phosphor - Google Patents
Method for producing self-activated zinc oxide phosphorInfo
- Publication number
- JPH07116425B2 JPH07116425B2 JP5160378A JP16037893A JPH07116425B2 JP H07116425 B2 JPH07116425 B2 JP H07116425B2 JP 5160378 A JP5160378 A JP 5160378A JP 16037893 A JP16037893 A JP 16037893A JP H07116425 B2 JPH07116425 B2 JP H07116425B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- zinc oxide
- activated zinc
- self
- colloidal silica
- 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
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/10—Geothermal energy
Landscapes
- Luminescent Compositions (AREA)
- Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、主として、蛍光表示管
やフライングスポット管に使用される自己付活酸化亜鉛
蛍光体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a method for producing a self-activated zinc oxide phosphor used for a fluorescent display tube or a flying spot tube.
【０００２】[0002]
【従来の技術】自己付活酸化亜鉛蛍光体は、習慣的にＺ
ｎＯ：Ｚｎと書かれている。この蛍光体は、導電性があ
るために、蛍光表示管用として重要である。低速電子線
で刺激されると青緑色に発光し、優れた発光特性を有す
る。2. Description of the Prior Art Self-activated zinc oxide phosphors are customary for Z
It is written as nO: Zn. Since this phosphor has conductivity, it is important for a fluorescent display tube. When stimulated by a low-speed electron beam, it emits blue-green light and has excellent emission characteristics.
【０００３】ＺｎＯ：Ｚｎ蛍光体は、母体構成元素と同
じ亜鉛を付活剤とする。このため、付活剤のＺｎを特定
することが難しい。このことは本蛍光体の特性を改良す
ることを著しく難しくしている。The ZnO: Zn phosphor has the same zinc as the matrix constituent element as the activator. Therefore, it is difficult to specify Zn as the activator. This makes it extremely difficult to improve the properties of the present phosphor.
【０００４】[0004]
【発明が解決しようとする課題】この蛍光体の製造にお
いては、製造者が経験で、焼成雰囲気を調整して付活剤
となるＺｎ量を特定している。すなわち、熟練者の感
が、本蛍光体の性能を左右する重要な要件となってい
る。従って、安定して優れた特性のＺｎＯ：Ｚｎ蛍光体
を製造することは極めて困難を伴っていた。このため、
発光効率が高くて寿命特性の優れた自己付活酸化亜鉛蛍
光体を安定的に製造できる技術開発が切望されていた。In the production of this phosphor, the manufacturer has experienced that the firing atmosphere is adjusted to specify the amount of Zn serving as the activator. That is, the feeling of the expert is an important factor that influences the performance of the present phosphor. Therefore, it has been extremely difficult to stably manufacture a ZnO: Zn phosphor having excellent characteristics. For this reason,
It has been earnestly desired to develop a technology capable of stably producing a self-activated zinc oxide phosphor having high luminous efficiency and excellent life characteristics.
【０００５】本発明はこの要求に答えるために開発され
たものである。この発明の重要な目的は、優れたバーニ
ング特性の自己付活酸化亜鉛蛍光体を製造する方法を提
供することにある。The present invention was developed to meet this need. An important object of the present invention is to provide a method for producing a self-activated zinc oxide phosphor having excellent burning characteristics.
【０００６】[0006]
【課題を解決するための手段】本発明の自己付活酸化亜
鉛蛍光体の製造方法は、前述の目的を達成するために下
記のようにして自己付活酸化亜鉛蛍光体を製造する。本
発明の自己付活酸化亜鉛蛍光体の製造方法は、蛍光体粒
子の表面を、表面処理物質で被覆する。表面処理物質に
は、アルミナ変成型コロイダルシリカ、またはコロイダ
ルシリカおよびアルミナゾルを使用して表面処理する。
このようにして製造された自己付活酸化亜鉛蛍光体は、
アルミナおよびシリカの付着量を０．００１〜０．１重
量％の範囲に調整する。In order to achieve the above-mentioned object, the method for producing a self-activated zinc oxide phosphor of the present invention produces a self-activated zinc oxide phosphor as follows. In the method for producing a self-activated zinc oxide phosphor of the present invention, the surface of the phosphor particles is coated with a surface treatment substance. As the surface treatment material, modified alumina colloidal silica or colloidal silica and alumina sol is used for the surface treatment.
The self-activated zinc oxide phosphor manufactured in this manner is
The adhesion amount of alumina and silica is adjusted within the range of 0.001 to 0.1% by weight.
【０００７】[0007]
【作用】本発明の自己付活酸化亜鉛蛍光体の製造方法
は、アルミナ変成型コロイダルシリカ、またはコロイダ
ルシリカおよびアルミナゾルを使用して蛍光体の粒子表
面を表面処理する。アルミナ変成型コロイダルシリカ、
またはコロイダルシリカおよびアルミナゾルを使用して
表面処理した自己付活酸化亜鉛蛍光体は、蛍光表示管に
使用して寿命特性を著しく改善できる。アルミナ変成型
コロイダルシリカ、または、コロイダルシリカとアルミ
ナゾルとを使用して蛍光体の表面を被覆する表面処理物
質は、結晶表面のＺｎを、電子線の連続刺激から防御
し、電子線照射による蛍光体の温度上昇化と、熱還元に
よる結晶表面の化学変化を抑制する。In the method for producing the self-activating zinc oxide phosphor of the present invention, the particle surface of the phosphor is surface-treated by using modified alumina colloidal silica or colloidal silica and alumina sol. Alumina modified colloidal silica,
Alternatively, the self-activated zinc oxide phosphor surface-treated with colloidal silica and alumina sol can be used in a fluorescent display tube to significantly improve the life characteristics. A surface-modified substance that coats the surface of the phosphor using alumina modified colloidal silica or colloidal silica and alumina sol is a phosphor that protects Zn on the crystal surface from continuous electron beam stimulation and emits phosphor by electron beam irradiation. It suppresses the chemical change of the crystal surface due to the temperature rise and thermal reduction.
【０００８】[0008]
【実施例】以下、実施例について説明するが、本発明は
実施例に限られるものではない。 ［蛍光体１］下記の工程で表面処理する自己付活酸化亜
鉛蛍光体［蛍光体］を製作する。蛍光体原料として、 ＺｎＣＯ3……１ｋｇ ＺｎＳ…………５ｇ 混合する。EXAMPLES Examples will be described below, but the present invention is not limited to the examples. [Phosphor 1] A self-activated zinc oxide phosphor [phosphor] which is surface-treated in the following steps is manufactured. As a phosphor raw material, ZnCO 3 ... 1 kg ZnS ... 5 g are mixed.
【０００９】混合物を石英ルツボに充填し、ルツボを焼
成炉に入れて焼成する。焼成工程においては、焼成炉内
に、体積比で、９８：２の比率で、窒素ガスと水素ガス
とが混合された気体を供給し、この混合ガス雰囲気で、
２時間還元焼成する。焼成温度は、８５０℃とした。A quartz crucible is filled with the mixture, and the crucible is placed in a firing furnace and fired. In the firing step, a gas in which nitrogen gas and hydrogen gas are mixed is supplied into the firing furnace in a volume ratio of 98: 2, and in this mixed gas atmosphere,
Reduce and bake for 2 hours. The firing temperature was 850 ° C.
【００１０】その後、焼成品をルツボから取り出してほ
ぐし、水洗いした後、分離して乾燥する。得られた自己
付活酸化亜鉛蛍光体は、１０ｐｐｍのイオウ（Ｓ）を含
有していた。また。この蛍光体は、ＺｎＳを添加しない
以外、同様にして焼成した従来のＺｎＯ：Ｚｎ蛍光体に
比較して、相対発光輝度が約６０％向上した。相対発光
輝度は、低速電子線ディマンタブル装置にて５０Ｖ、１
ｍＡの条件にて輝度を測定した。Thereafter, the fired product is taken out from the crucible, loosened, washed with water, separated and dried. The obtained self-activated zinc oxide phosphor contained 10 ppm of sulfur (S). Also. This phosphor has a relative emission luminance improved by about 60% as compared with the conventional ZnO: Zn phosphor fired in the same manner except that ZnS is not added. Relative emission brightness is 50V, 1 with a low-speed electron beam demountable device
The brightness was measured under the condition of mA.
【００１１】［実施例１］以上のようにして製作した自
己付活酸化亜鉛蛍光体は、下記の工程で表面処理して、
バーニング特性を改善する。 水洗い後、フルイにかけたＺｎＯ：Ｚｎ蛍光体６０
０ｇを、１．５リットルの水に懸濁させる。 アルミナ変成型コロイダルシリカ（商品名「ルドッ
クスＡＭ」デュポン社製−濃度２０重量％）１．３ｍリ
ットルと、２％のＺｎＳＯ4溶液１．６ｍリットルと
を、の蛍光体懸濁液に滴下し、アルミナ変成型コロイ
ダルシリカを蛍光体の表面に付着した。[Example 1] The self-activated zinc oxide phosphor manufactured as described above was surface-treated in the following steps,
Improves burning characteristics. ZnO: Zn phosphor 60 after rinsing with water and sieving
0 g is suspended in 1.5 l of water. Alumina modified colloidal silica - (trade name "Ludox AM" DuPont concentration 20 wt%) 1.3 m l, and a 2% ZnSO 4 solution 1.6m l was added dropwise to the phosphor suspension, A modified alumina colloidal silica was attached to the surface of the phosphor.
【００１２】分離乾燥した蛍光体を分析した結果、この
蛍光体は、０．０３９重量％のシリカ、０．００１重量
％のアルミナを含有し、両者で０．０４重量％の付着量
であった。As a result of analyzing the separated and dried phosphor, this phosphor contained 0.039% by weight of silica and 0.001% by weight of alumina, and the adhering amount of both was 0.04% by weight. .
【００１３】この蛍光体は、１２０時間のバーニング試
験後の発光輝度が９５％もあり、わずか５％の輝度の低
下にすぎなかった。バーニング試験は、低速電子線ディ
マンタブル装置にて５０Ｖ−１ｍＡの条件で電子線刺激
した。This phosphor had an emission brightness of 95% after a 120-hour burning test, which was only a 5% decrease in brightness. In the burning test, electron beam stimulation was performed with a low-speed electron beam demantable device under the condition of 50 V-1 mA.
【００１４】［実施例２〜６］蛍光体に対するアルミナ
変成型コロイダルシリカの混合量を調整する以外、以上
の方法と同様にして、自己付活酸化亜鉛蛍光体の表面を
コーティングした。[Examples 2 to 6] The surface of the self-activated zinc oxide phosphor was coated in the same manner as above except that the mixing amount of the modified alumina colloidal silica with respect to the phosphor was adjusted.
【００１５】得られた蛍光体の、シリカとアルミナの総
量を測定し、また、バーニング試験後の発光輝度を測定
した。測定結果を表１に示す。ただし、バーニング試験
後の輝度は、バーニング試験前の輝度を基準にしてい
る。The total amount of silica and alumina in the obtained phosphor was measured, and the emission brightness after the burning test was measured. The measurement results are shown in Table 1. However, the brightness after the burning test is based on the brightness before the burning test.
【００１６】この表から明かなように、アルミナ変成型
コロイダルシリカを使用して表面コーティングされたＺ
ｎＯ：Ｚｎ蛍光体は、優れたバーニング特性を示す。ア
ルミナ変成型コロイダルシリカの付着量が０．０４重量
％以下の範囲では、付着量が増加するとバーニング特性
も向上する。０．０４重量％以上になると、バーニング
特性は次第に低下する。ちなみに、アルミナ変成型コロ
イダルシリカで表面処理しない蛍光体１は、同一の条件
で１２０時間後の発光輝度が８２％と初期の値から１８
％も低下した。As is clear from this table, Z surface-coated using modified alumina colloidal silica.
The nO: Zn phosphor exhibits excellent burning characteristics. When the amount of the modified alumina colloidal silica deposited is within the range of 0.04% by weight or less, the burning characteristics also improve as the amount of deposition increases. When it is 0.04% by weight or more, the burning property is gradually deteriorated. By the way, the phosphor 1 not surface-treated with modified alumina colloidal silica had an emission luminance of 82% after 120 hours under the same conditions, which was 18% from the initial value.
% Has also dropped.
【００１７】本発明の自己付活酸化亜鉛蛍光体の製造方
法は、コロイダルシリカに加えアルミナゾルを混合し
て、蛍光体の表面をコーティングすることもできる。In the method for producing the self-activating zinc oxide phosphor of the present invention, the surface of the phosphor can be coated by mixing alumina sol in addition to colloidal silica.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】本発明の自己付活酸化亜鉛蛍光体は、粒
子の表面を、アルミナ変成型コロイダルシリカ、また
は、コロイダルシリカとアルミナゾルの混合物を使用し
て、表面処理する。本発明の方法で表面処理した自己付
活酸化亜鉛蛍光体は、表面処理物質でもって、結晶表面
のＺｎを、電子線の連続刺激から防御し、電子線照射に
よる蛍光体の温度上昇化と、熱還元による結晶表面の化
学変化を抑制する。このため、アルミナ変成型コロイダ
ルシリカ、または、コロイダルシリカおよびアルミナゾ
ルを使用して表面処理した自己付活酸化亜鉛蛍光体は、
優れたバーニング特性を示す。たとえば、実施例１で製
作した自己付活酸化亜鉛蛍光体は、低速電子線ディマン
タブル装置を使用して、５０Ｖ−１ｍＡの条件で１２０
時間電子線刺激したときの発光輝度の低下をわずかに５
％とすることができる。実施例１に使用した蛍光体１で
あって、表面処理をしていない自己付活酸化亜鉛蛍光体
は、同じ条件で発光輝度の低下を測定して、初期の輝度
から１８％も低下した。INDUSTRIAL APPLICABILITY The self-activated zinc oxide phosphor of the present invention is surface-treated with a modified alumina colloidal silica or a mixture of colloidal silica and alumina sol. The self-activated zinc oxide phosphor surface-treated by the method of the present invention is a surface-treated substance, which protects the Zn on the crystal surface from continuous stimulation with an electron beam and raises the temperature of the phosphor by electron beam irradiation. Suppresses chemical changes on the crystal surface due to thermal reduction. Therefore, the modified alumina colloidal silica, or the self-activated zinc oxide phosphor surface-treated using colloidal silica and alumina sol,
It shows excellent burning characteristics. For example, the self-activated zinc oxide phosphor manufactured in Example 1 was used under the conditions of 50 V-1 mA using a low-speed electron beam demantable device.
Only a slight decrease in emission brightness when stimulated by electron beam for 5 hours
It can be%. The phosphor 1 used in Example 1, which is a self-activated zinc oxide phosphor not surface-treated, measured a decrease in emission brightness under the same conditions, and decreased by 18% from the initial brightness.
【図１】実施例１〜６で試作したアルミナ変成型コロイ
ダルシリカで表面処理した自己付活酸化亜鉛蛍光体のバ
ーニング特性を示すグラフ。この図は低速電子線ディマ
ンタブル装置にて、５０Ｖ−１ｍＡの条件で１２０時間
電子線刺激した後の発光輝度を示している。FIG. 1 is a graph showing burning characteristics of self-activated zinc oxide phosphors surface-treated with modified alumina colloidal silica produced in Examples 1 to 6. This figure shows the emission luminance after electron beam stimulation for 120 hours under the condition of 50 V-1 mA in a low-speed electron beam demantable device.
Claims (2)
己付活酸化亜鉛蛍光体の製造方法において、 蛍光体の粒子表面を被覆する表面処理物質として、アル
ミナ変成型コロイダルシリカを使用し、アルミナおよび
シリカの付着量を０．００１〜０．１重量％とすること
を特徴とする自己付活酸化亜鉛蛍光体の製造方法。1. A method for producing a self-activated zinc oxide phosphor in which a surface of a phosphor is coated with a surface-treating substance, wherein a modified alumina colloidal silica is used as the surface-treating substance for coating the particle surface of the phosphor, and And a method for producing a self-activated zinc oxide phosphor, wherein the amount of silica deposited is 0.001 to 0.1% by weight.
己付活酸化亜鉛蛍光体の製造方法において、 蛍光体の粒子表面を被覆する表面処理物質として、コロ
イダルシリカとアルミナゾルとを使用し、アルミナおよ
びシリカの付着量を０．００１〜０．１重量％とするこ
とを特徴とする自己付活酸化亜鉛蛍光体の製造方法。2. A method for producing a self-activated zinc oxide phosphor in which a surface of a phosphor is coated with a surface-treating substance, wherein colloidal silica and alumina sol are used as the surface-treating substance for coating the particle surface of the phosphor. And a method for producing a self-activated zinc oxide phosphor, wherein the amount of silica deposited is 0.001 to 0.1% by weight.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1050456A JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
| JP5160378A JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1050456A JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
| JP5160378A JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1050456A Division JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0693259A JPH0693259A (en) | 1994-04-05 |
| JPH07116425B2 true JPH07116425B2 (en) | 1995-12-13 |
Family
ID=26390926
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1050456A Expired - Lifetime JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
| JP5160378A Expired - Lifetime JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1050456A Expired - Lifetime JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP2535218B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19626219A1 (en) * | 1996-06-29 | 1998-01-02 | Philips Patentverwaltung | Phosphor preparation with SiO¶2¶ particle coating |
| US7535162B2 (en) | 2003-04-30 | 2009-05-19 | National Institute For Materials Science | Zinc oxide phosphor, process for producing the same and light emitting device |
| CN101775278B (en) * | 2010-01-28 | 2013-10-16 | 海洋王照明科技股份有限公司 | Colloid-coating fluorescent powder and preparation method thereof |
| CN102234512B (en) * | 2010-04-30 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of modified luminescent material |
| WO2018004006A1 (en) | 2016-06-30 | 2018-01-04 | 堺化学工業株式会社 | Zinc oxide phosphor and method for producing same |
-
1989
- 1989-03-01 JP JP1050456A patent/JP2535218B2/en not_active Expired - Lifetime
-
1993
- 1993-06-03 JP JP5160378A patent/JPH07116425B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02228389A (en) | 1990-09-11 |
| JPH0693259A (en) | 1994-04-05 |
| JP2535218B2 (en) | 1996-09-18 |
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