JPS63196683A - Manufacturing method of zinc silicate powder phosphor - Google Patents
Manufacturing method of zinc silicate powder phosphorInfo
- Publication number
- JPS63196683A JPS63196683A JP2713087A JP2713087A JPS63196683A JP S63196683 A JPS63196683 A JP S63196683A JP 2713087 A JP2713087 A JP 2713087A JP 2713087 A JP2713087 A JP 2713087A JP S63196683 A JPS63196683 A JP S63196683A
- Authority
- JP
- Japan
- Prior art keywords
- silicate powder
- zinc silicate
- zinc
- powder phosphor
- columnar
- 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
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- Luminescent Compositions (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は各種ディスプレー用のブラウン管などの蛍光管
に塗布するケイ酸亜鉛粉末蛍光体およびその製法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a zinc silicate powder phosphor applied to fluorescent tubes such as cathode ray tubes for various displays, and a method for producing the same.
（従来の技術）
従来ケイ酸亜鉛粉末蛍光体は、例えば米国特許第２６５
６３２０号によれば、二段階の方法によって得られてい
る。まず珪酸微粉末、酸化亜鉛や炭酸亜鉛などの亜鉛化
合物および活性剤を所定割合に混合し、１２００〜１３
００℃の温度で焼成してこれら各原料の反応によって活
性剤がドープされたケイ酸亜鉛焼結体を得る。次にこの
焼結体を粉末蛍光体として適した粒径に粉砕する。(Prior Art) Conventional zinc silicate powder phosphors are disclosed in US Pat. No. 265, for example.
According to No. 6320, it is obtained by a two-step method. First, silicic acid fine powder, a zinc compound such as zinc oxide or zinc carbonate, and an activator are mixed in a predetermined ratio,
The zinc silicate sintered body doped with an activator is obtained by firing at a temperature of 0.000C by reaction of these raw materials. Next, this sintered body is pulverized to a particle size suitable for use as a powdered phosphor.
（発明が解決しようとする問題点）
しかし、従来の方法のようにケイ酸亜鉛焼結体を粉砕し
た場合、いわゆるメカノケミカル作用により粉末表面に
欠陥が生じ、粉末蛍光体の発光効率が低下するという問
題が生じる。また粉砕によって得られた粉末蛍光体は粒
子径が一定でなく粒径分布を持つ。このように粒径分布
をもつ粉末蛍光体を蛍光管表面に均一に塗布するために
はどうしても塗布但を多くする必要がある。ざらに塗布
厚さが大きくなると蛍光画面の輝度のむら、鮮明度の低
下などが発生する。(Problems to be Solved by the Invention) However, when zinc silicate sintered bodies are pulverized as in the conventional method, defects occur on the powder surface due to so-called mechanochemical action, reducing the luminous efficiency of the powdered phosphor. A problem arises. Furthermore, the powdered phosphor obtained by pulverization has a particle size distribution rather than a constant particle size. In order to uniformly apply powdered phosphor having such a particle size distribution to the surface of a fluorescent tube, it is necessary to increase the amount of coating. If the coating thickness becomes too large, uneven brightness and a decrease in clarity of the fluorescent screen will occur.
また従来の方法では製造にざいして高温の焼成工程が必
要であるが、活性剤の一部が揮散するためにその賦存量
および賦存状態を正確にコントロールすることが困難で
おり、粉末蛍光体の緒特性に悪影響をおよぼす。また毒
性の高い活性剤の揮散は人体に極めて有害である。In addition, conventional methods require a high-temperature firing process during production, but some of the activator evaporates, making it difficult to accurately control the amount and state of the activator. It has a negative effect on the cord characteristics. Further, volatilization of highly toxic active agents is extremely harmful to the human body.
本発明はこのような従来方法の欠点を解決するものであ
り、水熱反応によって粉砕工程が不要で、閉塞系でかつ
焼成方法よりも大幅に低い温度条件下でケイ酸亜鉛粉末
蛍光体を製造する方法を提供すものである。The present invention solves these drawbacks of the conventional method, and uses a hydrothermal reaction to produce zinc silicate powder phosphor without the need for a pulverization step, in a closed system, and under significantly lower temperature conditions than the firing method. This provides a method to do so.
（問題点を解決するための手段）
本発明は柱状を呈するケイ酸亜鉛粉末蛍光体と珪酸、亜
鉛化合物、活性剤を水性媒体中に分散させた後、攪拌ま
たは静置下において水熱反応させることを特徴とする柱
状を呈するケイ酸亜鉛粉末蛍光体の製法に関する。(Means for Solving the Problems) The present invention involves dispersing a columnar zinc silicate powder phosphor, silicic acid, a zinc compound, and an activator in an aqueous medium, and then subjecting them to a hydrothermal reaction under stirring or standing still. The present invention relates to a method for producing a zinc silicate powder phosphor exhibiting a columnar shape.
本発明者はケイ酸亜鉛粉末蛍光体の製法について鋭意研
究を重ねた結果、珪酸、亜鉛化合物、活性剤を水性媒体
中に分散させた後、攪拌または静置下において水熱反応
させれば、粉末蛍光体として適した粒径を有する柱状の
ケイ酸亜８Ｂ粉末蛍光体を製造できることを知見した。As a result of intensive research into the manufacturing method of zinc silicate powder phosphor, the present inventor found that if silicic acid, a zinc compound, and an activator are dispersed in an aqueous medium and then subjected to a hydrothermal reaction with stirring or standing still, It has been found that a columnar sub-8B silicate powder phosphor having a particle size suitable as a powder phosphor can be produced.
本発明の製法において使用される珪酸は結晶質、非晶質
のいずれでも良く、結晶質珪酸としては石英砂、ケイ石
粉が用いられ、非晶質珪酸としてはコロイダルシリカ、
水ガラス、シリカゲル、シリカガラスが用いられる。亜
鉛化合物としては酸化亜鉛、水酸化亜鉛の池に、塩化亜
鉛、硫酸亜鉛、硝酸亜鉛、酢酸亜鉛などの可溶性塩、更
には難溶性の水酸化亜鉛が用いられる。また活性剤とし
てはマンガン化合物単独またはマンガン化合物とヒ素化
合物の両方を使用することができ、残光時間の長い蛍光
体を必要とする時には後者が使用される。マンガン化合
物は酸化マンガン、水酸化マンガンの他に、塩化マンガ
ン、硝酸マンガン、硫酸マンガンなどの可溶性塩、更に
は難溶性の水酸化マンガンのいずれでも良い。ヒ素化合
物としては三酸化ニヒ素、五酸化二ヒ素が使用される。The silicic acid used in the production method of the present invention may be either crystalline or amorphous. As the crystalline silicic acid, quartz sand and silica powder are used, and as the amorphous silicic acid, colloidal silica,
Water glass, silica gel, and silica glass are used. As zinc compounds, zinc oxide, zinc hydroxide, soluble salts such as zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, and even sparingly soluble zinc hydroxide are used. Further, as the activator, a manganese compound alone or both a manganese compound and an arsenic compound can be used, and the latter is used when a phosphor with a long afterglow time is required. In addition to manganese oxide and manganese hydroxide, the manganese compound may be any of soluble salts such as manganese chloride, manganese nitrate, and manganese sulfate, as well as sparingly soluble manganese hydroxide. As the arsenic compound, niarsenic trioxide and diarsenic pentoxide are used.
本発明の柱状を呈するケイ酸亜鉛粉末蛍光体は次に説明
される方法によって製造される。The columnar zinc silicate powder phosphor of the present invention is manufactured by the method described below.
まず、水性媒体中に珪酸、亜鉛化合物、活性剤を分散さ
せる。水性媒体としては水以外に、水熱反応の速度を速
めるためにアルカリ性水溶液も使用することができる。First, silicic acid, a zinc compound, and an activator are dispersed in an aqueous medium. In addition to water, an alkaline aqueous solution can also be used as the aqueous medium in order to speed up the hydrothermal reaction.
このアルカリ性水溶液は水酸化ナトリウムや水酸化カリ
ウムなどの塩基性物質を水に溶解させるか、またはアン
モニア水を原液のままもしくは希釈することにより調整
することができる。これら原料の配合割合は、ＳｉＯ２
：ｚｎｏ ：ＭｎＯ：ＡＳのモル比で１：１．５〜２：
０．００１〜０．５二〇−０，０１となるように調整さ
れる。分散量は、余り多すぎると原料の消費に時間を要
するので、その′ｒｉ度は２０重量％以下になるように
分散させるのが好ましい。This alkaline aqueous solution can be prepared by dissolving a basic substance such as sodium hydroxide or potassium hydroxide in water, or by diluting or using aqueous ammonia as a undiluted solution. The blending ratio of these raw materials is SiO2
:zno :MnO:AS molar ratio of 1:1.5 to 2:
It is adjusted to be 0.001 to 0.520-0.01. If the amount of dispersion is too large, it will take time to consume the raw material, so it is preferable to disperse the material so that the degree of oxidation is 20% by weight or less.
次に上記の分散液を攪拌または静置下において水熱反応
させる。水熱反応は１００℃ないし３５０℃１好ましく
は１８０℃ないは３５０℃の範囲で行なわれる。反応時
の圧力は通常飽和水蒸気による自生圧力が用いられるが
、更に加圧してもさしつかえない。反応時間は反応条件
により左右され一定しないが、通常は０．１〜３０時間
が適当である。反応の進行と共に珪酸と亜鉛化合物が反
応して、最終的には活性剤を含有するケイ酸亜Ｇ （Ｚ
ｎ２Ｓ ｉ０４ ）が生成’ｌ。Next, the above dispersion is subjected to a hydrothermal reaction while stirring or standing still. The hydrothermal reaction is carried out at a temperature ranging from 100°C to 350°C, preferably from 180°C to 350°C. Autogenous pressure due to saturated steam is usually used as the pressure during the reaction, but further pressure may be used. Although the reaction time depends on the reaction conditions and is not constant, 0.1 to 30 hours is usually appropriate. As the reaction progresses, silicic acid and zinc compound react, and finally silicate sub-G (Z
n2S i04) is generated'l.
このようにして得られるケイ酸亜鉛粉末蛍光体は、いわ
ゆる自形で粒径が整っている柱状結晶であり、その平均
直径は０．０５〜５ミクロン、平均長さは０．１〜３０
ミクロンである。The zinc silicate powder phosphor obtained in this way is a so-called euhedral columnar crystal with a uniform particle size, the average diameter of which is 0.05 to 5 microns, and the average length of 0.1 to 30 microns.
It is micron.
以下実施例により説明するが、本発明は実施例により限
定されない。The present invention will be explained below with reference to Examples, but the present invention is not limited by the Examples.
（実施例）
実施例１
水６００−に石英砂１．２６６ｇ、酸化亜鉛３．７７１
ｇ、酸化マンガン０．０３０９を分散させた後、圧力容
器中３００″Ｃで５時間攪拌しながら水熱反応を行った
。水熱反応後、生成物をろ集、水洗し、平均直径１ミク
ロン、平均長さ３ミクロンの柱状を呈するケイ酸亜鉛粉
末蛍光体を得た。得られたケイ酸亜鉛粉末蛍光体の走査
型電子顕微鏡写真（，２０００倍）を第１図に示す。本
製法で得られたケイ酸亜鉛粉末蛍光体は微細結晶でおり
、かつ粒径が整っている。(Example) Example 1 1.266 g of quartz sand, 3.771 g of zinc oxide in 600 g of water
After dispersing 0.0309 g of manganese oxide, a hydrothermal reaction was carried out in a pressure vessel at 300"C with stirring for 5 hours. After the hydrothermal reaction, the product was collected by filtration, washed with water, and had an average diameter of 1 micron. A zinc silicate powder phosphor having a columnar shape with an average length of 3 microns was obtained.A scanning electron micrograph (2000x magnification) of the obtained zinc silicate powder phosphor is shown in Figure 1. The obtained zinc silicate powder phosphor has fine crystals and a uniform particle size.
実施例２〜５および比較例１
水６００ｄに珪酸、亜鉛化合物、活性剤を所定量分散さ
せた後、圧力容器中で所定条件で水熱反応を行った。各
側の反応条件および結果を第１表に示す。なあ、比較例
１はは反応温度が８０℃であり、水熱反応を行なわなか
った例でおる。Examples 2 to 5 and Comparative Example 1 After predetermined amounts of silicic acid, zinc compound, and activator were dispersed in 600 d of water, a hydrothermal reaction was performed in a pressure vessel under predetermined conditions. The reaction conditions and results for each side are shown in Table 1. In Comparative Example 1, the reaction temperature was 80° C., and no hydrothermal reaction was performed.
（発明の効果）
本発明は各種ディスプレー用のブラウン管などの蛍光管
に塗布するケイ酸亜鉛粉末蛍光体、とくに特性のすぐれ
たケイ酸亜鉛蛍光体およびその製法を提供するものでお
る。(Effects of the Invention) The present invention provides a zinc silicate powder phosphor to be applied to fluorescent tubes such as cathode ray tubes for various displays, particularly a zinc silicate phosphor with excellent characteristics, and a method for producing the same.
本発明の製法で得られる柱状を呈するケイ酸亜鉛粉末蛍
光体は、粉末蛍光体として適した粒径を有し、しかも分
散性に優れているため、この後に粉砕を行う必要がない
。従って粉砕によって生じる蛍光体表面の欠陥の発生は
なく輝度が高い。また粒径が整っているのでブラウン管
への塗布性に優れ、輝度のむらが少ない。The columnar zinc silicate powder phosphor obtained by the production method of the present invention has a particle size suitable for a powder phosphor and has excellent dispersibility, so there is no need for subsequent pulverization. Therefore, there are no defects on the surface of the phosphor caused by crushing, and the brightness is high. Also, because the particle size is uniform, it has excellent coating properties on cathode ray tubes, and there is little unevenness in brightness.
更に、本発明の製法では密閉された容器内、しかも溶液
中で反応が進行するのでヒ素が大気中に揮散する懸念は
なく、所定量を正確にドープすることができる。Furthermore, in the production method of the present invention, the reaction proceeds in a sealed container and in a solution, so there is no concern that arsenic will volatilize into the atmosphere, and a predetermined amount of arsenic can be doped accurately.
第１図は、実例１で得たケイ酸亜鉛粉末蛍光体の電子顕
微鏡写真である。
特許出願人 宇部興産株式会社
第１図
（２０００倍）FIG. 1 is an electron micrograph of the zinc silicate powder phosphor obtained in Example 1. Patent applicant: Ube Industries, Ltd. Figure 1 (2000x)
Claims (5)
均長さが０．１〜３０ミクロンであることを特徴とする
特許請求範囲第（１）項記載のケイ酸亜鉛粉末蛍光体。(2) The zinc silicate powder phosphor according to claim (1), wherein the columnar crystals have an average diameter of 0.05 to 5 microns and an average length of 0.1 to 30 microns.
せた後、攪拌または静置下において水熱反応させること
を特徴とする柱状を呈するケイ酸亜鉛粉末蛍光体の製法
。(3) A method for producing a columnar zinc silicate powder phosphor, which comprises dispersing silicic acid, a zinc compound, and an activator in an aqueous medium, and then subjecting the dispersion to a hydrothermal reaction while stirring or standing still.
許請求範囲第（３）項記載の柱状を呈するケイ酸亜鉛粉
末蛍光体の製法。(4) A method for producing a columnar zinc silicate powder phosphor according to claim (3), in which the hydrothermal reaction is carried out at a temperature of 180°C to 350°C.
化合物とヒ素化合物の両方を使用することを特徴とする
特許請求範囲第（３）項記載の柱状を呈するケイ酸亜鉛
粉末蛍光体の製法。(5) A method for producing a columnar zinc silicate powder phosphor according to claim (3), characterized in that a manganese compound alone or both a manganese compound and an arsenic compound are used as the activator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027130A JPH0765038B2 (en) | 1987-02-10 | 1987-02-10 | Manufacturing method of zinc silicate powder phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027130A JPH0765038B2 (en) | 1987-02-10 | 1987-02-10 | Manufacturing method of zinc silicate powder phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63196683A true JPS63196683A (en) | 1988-08-15 |
| JPH0765038B2 JPH0765038B2 (en) | 1995-07-12 |
Family
ID=12212470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62027130A Expired - Fee Related JPH0765038B2 (en) | 1987-02-10 | 1987-02-10 | Manufacturing method of zinc silicate powder phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0765038B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087289B (en) * | 2014-06-30 | 2016-01-20 | 中国石油大学(华东) | A kind of method utilizing waste silicon powder water heat transfer nanometer zinc silicate luminescent material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50142482A (en) * | 1974-04-01 | 1975-11-17 | ||
| JPS5221289A (en) * | 1975-08-13 | 1977-02-17 | Toyo Ink Mfg Co Ltd | Element of hot fluorescent dosagemeter and its manufacturing process |
| JPS54145386A (en) * | 1978-05-02 | 1979-11-13 | Matsushita Electric Ind Co Ltd | Production of zinc silicate phosphor |
| JPS587478A (en) * | 1981-06-30 | 1983-01-17 | インタ−ナシヨナル・ビジネス・マシ−ンズ・コ−ポレ−シヨン | Fluorescent body and manufacture |
| JPS58151322A (en) * | 1982-03-05 | 1983-09-08 | Kasei Optonix Co Ltd | Zinc silicate phosphor |
-
1987
- 1987-02-10 JP JP62027130A patent/JPH0765038B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50142482A (en) * | 1974-04-01 | 1975-11-17 | ||
| JPS5221289A (en) * | 1975-08-13 | 1977-02-17 | Toyo Ink Mfg Co Ltd | Element of hot fluorescent dosagemeter and its manufacturing process |
| JPS54145386A (en) * | 1978-05-02 | 1979-11-13 | Matsushita Electric Ind Co Ltd | Production of zinc silicate phosphor |
| JPS587478A (en) * | 1981-06-30 | 1983-01-17 | インタ−ナシヨナル・ビジネス・マシ−ンズ・コ−ポレ−シヨン | Fluorescent body and manufacture |
| JPS58151322A (en) * | 1982-03-05 | 1983-09-08 | Kasei Optonix Co Ltd | Zinc silicate phosphor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0765038B2 (en) | 1995-07-12 |
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| LAPS | Cancellation because of no payment of annual fees |