JPH0559358A - Production of blue pigment for fluorescent substance and pigmented blue light-emitting fluorescent substance - Google Patents
Production of blue pigment for fluorescent substance and pigmented blue light-emitting fluorescent substanceInfo
- Publication number
- JPH0559358A JPH0559358A JP24023791A JP24023791A JPH0559358A JP H0559358 A JPH0559358 A JP H0559358A JP 24023791 A JP24023791 A JP 24023791A JP 24023791 A JP24023791 A JP 24023791A JP H0559358 A JPH0559358 A JP H0559358A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- blue
- zinc
- blue pigment
- aqueous solution
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カラーブラウン管等の
蛍光体膜に適した顔料付青色発光蛍光体及びその青色発
光蛍光体に適した青色顔料の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigmented blue light emitting phosphor suitable for a phosphor film such as a color cathode ray tube and a method for producing a blue pigment suitable for the blue light emitting phosphor.
【０００２】[0002]
【従来の技術】カラーブラウン管や蛍光表示管等の画像
のコントラストを向上させるために蛍光面における外光
の反射を吸収するフィルターを蛍光体表面に付着するこ
とは知られている。青色発光蛍光体においては、その発
光ピークである４５０ｎｍ付近における吸収ができるだ
け少なく、それ以外の波長領域における吸収ができるだ
け多い顔料を使用することが要求される。2. Description of the Related Art It is known to attach a filter, which absorbs reflection of external light on a fluorescent screen, to the surface of a fluorescent material in order to improve the contrast of an image of a color cathode ray tube or a fluorescent display tube. In the blue light emitting phosphor, it is required to use a pigment that absorbs as little as possible near the emission peak of 450 nm and has as much absorption as possible in other wavelength regions.
【０００３】この種の青色顔料として、特開昭５４─２
８７８４号公報に群青（３ＮａＡｌ・ＳｉＯ2 ・Ｎａ2
Ｓ2 ）、紺青（Ｆｅ4 Ｆｅ( ＣＮ) 6 3 ・ｎＨ
2Ｏ）、アルミン酸コバルト（ＣｏＯ・ｎＡｌ2 Ｏ3 )
、セルリアンブルー（ＣｏＯ・ｎＳｎＯ2 ) 、硫化銅
（ＣｕＳ）等が提案されている。As a blue pigment of this type, JP-A-54-2
Ultramarine (3NaAl ・ SiO 2・ Na 2
S 2 ), dark blue (Fe 4 Fe (CN) 6 3・ nH
2 O), cobalt aluminate (CoO ・ nAl 2 O 3 ).
, Cerulean blue (CoO.nSnO 2 ), copper sulfide (CuS), etc. have been proposed.
【０００４】しかし、一般に実用されているアルミン酸
コバルトは、体色が青色蛍光体の発光スペクトルと一致
せず、特に、４９０ｎｍ付近の反射率が高いためにコン
トラストの向上を目的とするときには有効でない。ま
た、一部に実用されている群青は、アルミン酸コバルト
に比べて優れた特性を有するものの、化学的安定性が極
めて乏しいために、蛍光体への付着工程やブラウン管へ
の塗布工程において退色する欠点を有している。特に、
ブラウン管を作製した後、電子線照射によって顕著にそ
の体色を変化させ、蛍光面の発光スペクトルのピークを
シフトさせるという欠点がある。However, the commonly used cobalt aluminate is not effective for the purpose of improving the contrast because its body color does not match the emission spectrum of the blue phosphor, and in particular, its reflectance near 490 nm is high. .. In addition, although some of the ultramarine blues that are in practical use have superior properties compared to cobalt aluminate, they have very poor chemical stability, and therefore discolor in the process of attaching to phosphors and the process of applying to cathode ray tubes. It has drawbacks. In particular,
After producing a cathode ray tube, there is a drawback that the body color is remarkably changed by electron beam irradiation and the peak of the emission spectrum of the phosphor screen is shifted.
【０００５】一方、先に提案した特願平３─１４８６３
６号出願のＣｏＯ・ＺｎＯ・ＳｉＯ2 系青色顔料は、顔
料付蛍光体における色調、堅牢性の点でアルミン酸コバ
ルトや群青より優れている。しかし、この種の無機酸化
物顔料は、従来、酸化物或いは炭酸塩、塩化物などの原
料を乾式で混合し、９００℃以上の温度で焼成し、冷却
後粉砕する方法で製造されていたが、ＣｏＯ・ＺｎＯ・
ＳｉＯ2 系青色顔料をこの方法で製造すると、十分な色
調を保持したまま１ミクロン以下の粒子径の顔料を得る
ことは困難であった。そして、これらの比較的粒子径の
大きなＣｏＯ・ＺｎＯ・ＳｉＯ2 系青色顔料は、蛍光体
に対する付着力及び着色力が必ずしも十分でなく、これ
を補うためには多量の顔料を付着する必要があった。し
かし、顔料を多量に付着すると、輝度が低下するという
問題があった。On the other hand, the previously proposed Japanese Patent Application No. 3-14863.
The CoO / ZnO / SiO 2 based blue pigment of the No. 6 application is superior to cobalt aluminate and ultramarine in terms of color tone and fastness of the pigmented phosphor. However, this type of inorganic oxide pigment has hitherto been manufactured by a method in which raw materials such as oxides, carbonates, and chlorides are dry-mixed, baked at a temperature of 900 ° C. or higher, cooled, and then ground. , CoO / ZnO /
When the SiO 2 blue pigment is produced by this method, it is difficult to obtain a pigment having a particle size of 1 micron or less while maintaining a sufficient color tone. Further, these CoO.ZnO.SiO 2 blue pigments having a relatively large particle size do not necessarily have sufficient adhesiveness and coloring power to the phosphor, and in order to compensate for this, it is necessary to attach a large amount of pigment. It was However, when a large amount of pigment is attached, there is a problem that the brightness is lowered.
【０００６】[0006]
【発明が解決しようとする課題】そこで、本発明は、上
記の問題を解消し、蛍光体への付着力及び着色力に優
れ、輝度低下を招くことのないＣｏＯ・ＺｎＯ・ＳｉＯ
2 系青色顔料の製造方法並びにその顔料を付着した青色
発光蛍光体を提供しようとするものである。SUMMARY OF THE INVENTION Therefore, the present invention solves the above-mentioned problems, is excellent in the adhesive force to the phosphor and the coloring power, and does not cause a decrease in brightness. CoO.ZnO.SiO.
A method for producing a 2 type blue pigment and a blue light emitting phosphor having the pigment attached thereto.
【０００７】[0007]
【課題を解決するための手段】本発明は、青色発光蛍光
体の表面に付着するための、ＣｏＯ・ＺｎＯ・ＳｉＯ2
系青色顔料の製造方法において、コバルトと亜鉛を含む
水溶液にアルカリ水溶液を添加し、コバルトと亜鉛を水
酸化物として共沈させ、有機溶媒で水を置換した後、加
水分解により酸化珪素を沈殿の表面に沈着し、焼成する
ことを特徴とする蛍光体用青色顔料の製造方法である。The present invention is directed to CoO.ZnO.SiO 2 for adhering to the surface of a blue-emitting phosphor.
In the method for producing a blue pigment, an alkaline aqueous solution is added to an aqueous solution containing cobalt and zinc to coprecipitate cobalt and zinc as hydroxides, and water is replaced with an organic solvent, followed by hydrolysis to precipitate silicon oxide. A method for producing a blue pigment for a phosphor, which comprises depositing on a surface and firing.
【０００８】ここで、コバルトと亜鉛を含む水溶液とし
ては、塩化物、フッ化物、ヨウ化物、臭化物、硫酸塩、
硝酸塩等を使用することができ、水置換用の有機溶媒と
しては、エタノール、メタノール等を使用することがで
き、珪素原料としては、珪酸アルコキシド等を使用する
ことができる。As the aqueous solution containing cobalt and zinc, chloride, fluoride, iodide, bromide, sulfate,
Nitrate or the like can be used, ethanol, methanol or the like can be used as the organic solvent for water replacement, and silicic acid alkoxide or the like can be used as the silicon raw material.
【０００９】なお、上記の顔料の焼成時に必要に応じて
各種の融剤やその他の元素を含有させることができる。
具体的には、Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｍｇ，Ｂａ，Ｆ
ｅ，Ｎｉ，Ｃｕ，Ｍｎ，Ｔｉ，Ｖ，Ａｌ，Ｓｎ，Ｓｂ，
Ｃｒ，Ｐｒ等を含有させてもよい。これらの元素は約５
重量％以下の範囲で添加することができる。これを超え
ると、青色顔料として好ましい色調を得ることができな
くなる。When the above pigment is fired, various fluxes and other elements can be added as required.
Specifically, Li, Na, K, Ca, Mg, Ba, F
e, Ni, Cu, Mn, Ti, V, Al, Sn, Sb,
You may contain Cr, Pr, etc. These elements are about 5
It can be added in the range of not more than wt%. When it exceeds this, it becomes impossible to obtain a preferable color tone as a blue pigment.
【００１０】また、加水分解に際してはアンモニア水を
適量加えて攪拌しながら３０〜４０℃に加温することが
好ましく、さらに、沈殿は、遠心分離した後、空気中で
８００〜９００℃で焼成することが好ましい。この方法
により、平均粒子径が０．５ミクロン以下のＣｏＯ・Ｚ
ｎＯ・ＳｉＯ2 系青色顔料を容易に製造することができ
る。In addition, upon hydrolysis, it is preferable to add an appropriate amount of aqueous ammonia and heat with stirring to 30 to 40 ° C. Further, the precipitate is centrifuged and then calcined in air at 800 to 900 ° C. Preferably. By this method, CoO · Z having an average particle size of 0.5 micron or less
The nO.SiO 2 type blue pigment can be easily manufactured.
【００１１】本発明は、このようにして得た、０．５ミ
クロン以下のＣｏＯ・ＺｎＯ・ＳｉＯ2 系青色顔料を青
色発光蛍光体の表面に付着した顔料付青色発光蛍光体で
ある。なお、青色顔料の好ましい平均粒子径は、０．１
〜０．３ミクロンの範囲である。The present invention is a pigment-containing blue light-emitting phosphor in which a CoO.ZnO.SiO 2 blue pigment of 0.5 micron or less thus obtained is attached to the surface of the blue light-emitting phosphor. The preferable average particle size of the blue pigment is 0.1
Is in the range of ~ 0.3 microns.
【００１２】[0012]
【作用】本発明者等は、各種の青色顔料について、その
平均粒子径と付着力の関係を調べたところ、図１のよう
な関係を得た。ここで、付着力とは、界面活性剤を０．
１％加えた水中で顔料付蛍光体を振り混ぜた後、２時間
放置し、上澄みの６００ｎｍにおける透過率を測定した
ものである。数値が小さい場合は、顔料が水中で剥離さ
れ、透過率を低下させたものであり、顔料の付着力が弱
いことを示している。図１から明らかなように、顔料の
平均粒子径が０．５ミクロン以下では付着力が弱く、実
用上問題があることが分かる。The inventors of the present invention investigated the relationship between the average particle diameter and the adhesive force of various blue pigments and found that the relationship shown in FIG. Here, the adhesive force means that the surfactant is 0.
The pigment-containing phosphor was shaken in 1% of water and left for 2 hours, and the transmittance of the supernatant at 600 nm was measured. When the numerical value is small, the pigment is peeled off in water to reduce the transmittance, which indicates that the adhesive force of the pigment is weak. As is clear from FIG. 1, when the average particle size of the pigment is 0.5 μm or less, the adhesive force is weak and there is a practical problem.
【００１３】本発明者等は、ＣｏＯ・ＺｎＯ・ＳｉＯ2
系青色顔料付青色発光蛍光体を種々検討する過程で、平
均粒子径が０．５ミクロン以下の顔料を用いると、蛍光
体への付着力と着色力が向上することを見出し、同時
に、かかる平均粒子径の顔料の製造方法も確立すること
に成功した。図２は、下記実施例で得た平均粒子径０．
３ミクロンのＣｏＯ・ＺｎＯ・ＳｉＯ2 青色顔料のＳＥ
Ｍ写真である。この写真から明らかなように、本発明の
方法で得たＣｏＯ・ＺｎＯ・ＳｉＯ2 系青色顔料は、表
面が滑らかで独特の形状を有し、かつ、極めてシャープ
な粒度分布を有していることが分かる。このような形態
が、本発明の特徴である蛍光体への付着力や着色力、さ
らにはコントラストの向上に寄与しているものと考えら
れる。The present inventors have found that CoO.ZnO.SiO 2
In the process of examining various blue light-emitting phosphors with a blue pigment, it was found that the use of a pigment having an average particle size of 0.5 micron or less improves the adhesiveness and coloring power to the phosphor, and at the same time We have also succeeded in establishing a method for producing pigments of particle size. FIG. 2 shows the average particle size of 0.
SE of 3 micron CoO / ZnO / SiO 2 blue pigment
It is an M photograph. As is clear from this photograph, the CoO.ZnO.SiO 2 blue pigment obtained by the method of the present invention has a smooth surface and a unique shape, and has an extremely sharp particle size distribution. I understand. It is considered that such a form contributes to the improvement in the adhesiveness to the phosphor, the coloring power, and the contrast, which are the features of the present invention.
【００１４】なお、本発明で使用することのできる青色
発光蛍光体としては、３８０〜５００ｎｍの範囲内に発
光スペクトルの主要部を有するもので、具体的には銀付
活硫化亜鉛系蛍光体〔ＺｎＳ：Ａｇ，Ｘ（Ｘはハロゲン
又はＡｌ）、ＺｎＳ：Ａｇ，Ｍ，Ｘ（ＭはＧａ，Ｉｎ
等、Ｘはハロゲン又はＡｌ）〕、Ｙ2 ＳｉＯ5 ：Ｃｅ、
Ｃａ2 Ｂ5 Ｏ9 Ｃｌ：Ｅｕ、（Ｂａx Ｍｇ1-x ) Ｏ・ｎ
Ａｌ2Ｏ3 ：Ｅｕ（０≦ｘ≦１，７≦ｎ≦８）、ＳｒＳ
ｉ3 Ｏ8 Ｃｌ4 ：Ｅｕ、ＣａＷＯ4 、ＣａＷＯ4 ：Ｐ
ｂ、ＢａＦＣｌ：Ｅｕ、Ｇｄ2 Ｏ2 Ｓ：Ｔｂ、ＺｎＳ：
Ｚｎ等を挙げることができる。上記の青色顔料の付着量
は、０．３〜３０重量％の範囲が好ましい。付着量が下
限値を下回るとフィルター効果が小さすぎ、また、上限
値を越えると、発光輝度が十分でなくなる場合がある。The blue light emitting phosphor that can be used in the present invention has a major part of the emission spectrum within the range of 380 to 500 nm, and specifically, a silver activated zinc sulfide based phosphor [ ZnS: Ag, X (X is halogen or Al), ZnS: Ag, M, X (M is Ga, In)
Etc., X is halogen or Al)], Y 2 SiO 5 : Ce,
Ca 2 B 5 O 9 Cl: Eu, (Ba x Mg 1-x ) O · n
Al 2 O 3 : Eu (0 ≦ x ≦ 1, 7 ≦ n ≦ 8), SrS
i 3 O 8 Cl 4: Eu , CaWO 4, CaWO 4: P
b, BaFCl: Eu, Gd 2 O 2 S: Tb, ZnS:
Zn etc. can be mentioned. The amount of the blue pigment attached is preferably in the range of 0.3 to 30% by weight. If the adhesion amount is less than the lower limit value, the filter effect is too small, and if it exceeds the upper limit value, the emission brightness may not be sufficient.
【００１５】[0015]
（実施例）塩化コバルト（６水和物）４．７部と塩化亜
鉛５．５部を脱塩水１００部に溶解した。これを攪拌し
ながら１Ｎの水酸化ナトリウム水溶液を少しずつ加えて
ｐＨを９とした。静置して上澄みを切った後、同じ体積
のエタノールを加え、再び静置して上澄みをエタノール
と置換した。これに２８％アンモニア水溶液２４部を加
えた。さらに、エタノール２０部にテトラエトキシシラ
ン２０部を溶解した溶液を加えて攪拌しながら４０℃に
加温し２時間保持した。反応終了後、遠心分離して得た
固形物を風乾してエタノールを除き、８００℃で２時間
焼成して平均粒子径０．３ミクロンのｘＣｏＯ・ｙＺｎ
Ｏ・ｚＳｉＯ2 顔料（ｘ＝０．３，ｙ＝０．６，ｚ＝
１．０）を得た。図２は、この顔料のＳＥＭ写真であ
る。(Example) 4.7 parts of cobalt chloride (hexahydrate) and 5.5 parts of zinc chloride were dissolved in 100 parts of demineralized water. While stirring this, 1N aqueous sodium hydroxide solution was added little by little to adjust the pH to 9. After allowing to stand and cutting the supernatant, the same volume of ethanol was added, and then allowed to stand again to replace the supernatant with ethanol. To this was added 24 parts of 28% aqueous ammonia solution. Further, a solution of 20 parts of tetraethoxysilane dissolved in 20 parts of ethanol was added, and the mixture was heated to 40 ° C. with stirring and held for 2 hours. After completion of the reaction, the solid matter obtained by centrifugation was air-dried to remove ethanol, and calcined at 800 ° C. for 2 hours to produce xCoO.yZn having an average particle diameter of 0.3 micron.
O · zSiO 2 pigment (x = 0.3, y = 0.6, z =
1.0) was obtained. FIG. 2 is an SEM photograph of this pigment.
【００１６】次いで、銀付活硫化亜鉛青色発光蛍光体１
００部に対し、蒸留水１００部を加えてスラリーとし、
これに、上記の青色顔料３部を加えて４５℃に加温しな
がら、バインダーとしてゼラチン０．３６部及びアラビ
アゴム０．３部を水溶液にしたものを加え、酢酸によっ
てｐＨを４．１に調整してから室温まで放冷し、その
後、５０％のグルタルアルデヒド水溶液７．５部を加え
てバインダーを硬化させた。Next, silver activated zinc sulfide blue light emitting phosphor 1
To 100 parts, add 100 parts of distilled water to make a slurry,
While adding 3 parts of the above blue pigment and heating to 45 ° C., 0.36 parts of gelatin and 0.3 parts of gum arabic as an aqueous solution were added as a binder, and the pH was adjusted to 4.1 with acetic acid. After adjustment, the mixture was allowed to cool to room temperature, and then 7.5 parts of a 50% glutaraldehyde aqueous solution was added to cure the binder.
【００１７】（比較例）酸化コバルト１．７部、酸化亜
鉛２．６部、酸化珪素５．８部を乾式で混合し、空気中
で１３００℃で２時間焼成し、粉砕して平均粒子径０．
９ミクロンのｘＣｏＯ・ｙＺｎＯ・ｚＳｉＯ2 顔料（ｘ
＝０．３６，ｙ＝０．６，ｚ＝１．０）を得た。図３
は、この顔料のＳＥＭ写真である。この青色顔料を実施
例と同様の条件で銀付活硫化亜鉛青色発光蛍光体に付着
した。(Comparative Example) 1.7 parts of cobalt oxide, 2.6 parts of zinc oxide, and 5.8 parts of silicon oxide were dry-mixed, calcined in air at 1300 ° C. for 2 hours, and pulverized to obtain an average particle diameter. 0.
9 micron xCoO.yZnO.zSiO 2 pigment (x
= 0.36, y = 0.6, z = 1.0) was obtained. Figure 3
Is an SEM photograph of this pigment. This blue pigment was attached to a silver-activated zinc sulfide blue light emitting phosphor under the same conditions as in the examples.
【００１８】（フィルター効果の比較）実施例及び比較
例で得た顔料付蛍光体の拡散反射率を測定して図４に示
した。顔料を同量付着したものであるが、小粒子顔料を
付着した実施例の方が、６００ｎｍ付近の反射率が低く
フィルター効果が優れていることが分かる。(Comparison of Filter Effect) The diffuse reflectances of the pigmented phosphors obtained in Examples and Comparative Examples were measured and shown in FIG. It can be seen that, although the pigments are attached in the same amount, the example in which the small particle pigment is attached has a lower reflectance in the vicinity of 600 nm and an excellent filter effect.
【００１９】[0019]
【発明の効果】本発明は、上記の構成を採用することに
より、蛍光体への付着力及び着色力の優れた平均粒子径
０．５ミクロン以下のｘＣｏＯ・ｙＺｎＯ・ｚＳｉＯ2
系顔料を提供することができ、また、青色発光蛍光体に
該顔料を付着することにより、高輝度を保持しながら、
コントラストの向上を図ることができるようになった。According to the present invention, by adopting the above-mentioned constitution, xCoO.yZnO.zSiO 2 having an average particle diameter of 0.5 micron or less, which is excellent in adhesion to a phosphor and coloring power.
It is possible to provide a system pigment, and by attaching the pigment to the blue light emitting phosphor, while maintaining high brightness,
It has become possible to improve the contrast.
【図１】青色顔料の平均粒子系と付着力の関係を示した
グラフである。FIG. 1 is a graph showing the relationship between the average particle size of a blue pigment and the adhesive force.
【図２】実施例で得た平均粒子径０．３ミクロンのｘＣ
ｏＯ・ｙＺｎＯ・ｚＳｉＯ2 顔料（ｘ＝０．３，ｙ＝
０．６，ｚ＝１．０）の粒子構造を示したＳＥＭ写真で
ある。FIG. 2 xC having an average particle size of 0.3 micron obtained in the example.
oO · yZnO · zSiO 2 pigment (x = 0.3, y =
6 is a SEM photograph showing a grain structure of 0.6, z = 1.0).
【図３】比較例で得た平均粒子径０．９ミクロンのｘＣ
ｏＯ・ｙＺｎＯ・ｚＳｉＯ2 顔料（ｘ＝０．３６，ｙ＝
０．６，ｚ＝１．０）の粒子構造を示したＳＥＭ写真で
ある。FIG. 3 xC having an average particle size of 0.9 micron obtained in a comparative example.
oO · yZnO · zSiO 2 pigment (x = 0.36, y =
6 is a SEM photograph showing a grain structure of 0.6, z = 1.0).
【図４】実施例及び比較例で得た顔料付蛍光体の拡散反
射率を示したグラフである。FIG. 4 is a graph showing diffuse reflectance of pigmented phosphors obtained in Examples and Comparative Examples.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年１２月１２日[Submission date] December 12, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】[0012]
【作用】本発明者等は、各種の青色顔料について、その
平均粒子径と付着力の関係を調べたところ、図１のよう
な関係を得た。ここで、付着力とは、界面活性剤を０．
１％加えた水中で顔料付蛍光体を振り混ぜた後、２時間
放置し、上澄みの６００ｎｍにおける透過率を測定した
ものである。数値が小さい場合は、顔料が水中で剥離さ
れ、透過率を低下させたものであり、顔料の付着力が弱
いことを示している。図１から明らかなように、顔料の
平均粒子径が０．５ミクロン以上では付着力が弱く、実
用上問題があることが分かる。 ─────────────────────────────────────────────────────
The inventors of the present invention investigated the relationship between the average particle diameter and the adhesive force of various blue pigments and found that the relationship shown in FIG. Here, the adhesive force means that the surfactant is 0.
The pigment-containing phosphor was shaken in 1% of water and left for 2 hours, and the transmittance of the supernatant at 600 nm was measured. When the numerical value is small, the pigment is peeled off in water to reduce the transmittance, which indicates that the adhesive force of the pigment is weak. As is clear from FIG. 1, when the average particle size of the pigment is 0.5 μm or more , the adhesive force is weak and there is a problem in practical use. ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年８月２１日[Submission date] August 21, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１７】（比較例）酸化コバルト１．７部、酸化亜
鉛２．６部、酸化珪素５．８部を乾式で混合し、空気中
で１３００℃で２時間焼成し、粉砕して平均粒子径１．
７ミクロンのｘＣｏＯ・ｙＺｎＯ・ｚＳｉＯ2 顔料（ｘ
＝０．３６，ｙ＝０．６，ｚ＝１．０）を得た。図３
は、この顔料のＳＥＭ写真である。この青色顔料を実施
例と同様の条件で銀付活硫化亜鉛青色発光蛍光体に付着
した。(Comparative Example) 1.7 parts of cobalt oxide, 2.6 parts of zinc oxide, and 5.8 parts of silicon oxide were dry-mixed, calcined in air at 1300 ° C. for 2 hours, and pulverized to obtain an average particle diameter. 1.
7 micron xCoO.yZnO.zSiO 2 pigment (x
= 0.36, y = 0.6, z = 1.0) was obtained. Figure 3
Is an SEM photograph of this pigment. This blue pigment was attached to a silver-activated zinc sulfide blue light emitting phosphor under the same conditions as in the examples.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Name of item to be corrected] Brief explanation of the drawing
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図面の簡単な説明】[Brief description of drawings]
【図１】青色顔料の平均粒子径と付着力の関係を示した
グラフである。FIG. 1 is a graph showing the relationship between the average particle size of blue pigment and the adhesive force.
【図２】実施例で得た平均粒子径０．３ミクロンのｘＣ
ｏＯ・ｙＺｎＯ・ｚＳｉＯ2顔料（ｘ＝０．３，ｙ＝
０．６，ｚ＝１．０）の粒子構造を示したＳＥＭ写真で
ある。FIG. 2 xC having an average particle size of 0.3 micron obtained in the example.
oO · yZnO · zSiO 2 pigment (x = 0.3, y =
6 is a SEM photograph showing a grain structure of 0.6, z = 1.0).
【図３】比較例で得た平均粒子径１．７ミクロンのｘＣ
ｏＯ・ｙＺｎＯ・ｚＳｉＯ2顔料（ｘ＝０．３６，ｙ＝
０．６，ｚ＝１．０）の粒子構造を示したＳＥＭ写真で
ある。FIG. 3 xC having an average particle size of 1.7 microns obtained in a comparative example
oO · yZnO · zSiO 2 pigment (x = 0.36, y =
6 is a SEM photograph showing a grain structure of 0.6, z = 1.0).
【図４】実施例及び比較例で得た顔料付蛍光体の拡散反
射率を示したグラフである。FIG. 4 is a graph showing diffuse reflectance of pigmented phosphors obtained in Examples and Comparative Examples.
Claims (3)
の、ＣｏＯ・ＺｎＯ・ＳｉＯ2 系青色顔料の製造方法に
おいて、コバルトと亜鉛を含む水溶液にアルカリ水溶液
を添加し、コバルトと亜鉛を水酸化物として共沈させ、
有機溶媒で水を置換した後、加水分解により酸化珪素を
沈殿の表面に沈着し、焼成することを特徴とする蛍光体
用青色顔料の製造方法。1. A method for producing a CoO.ZnO.SiO 2 -based blue pigment for adhering to the surface of a blue-emitting phosphor, wherein an alkaline aqueous solution is added to an aqueous solution containing cobalt and zinc to oxidize the cobalt and zinc. Co-precipitate as a thing,
A method for producing a blue pigment for a phosphor, comprising substituting water with an organic solvent, depositing silicon oxide on the surface of the precipitate by hydrolysis, and then firing.
用いることを特徴とする請求項１記載の蛍光体用青色顔
料の製造方法。2. The method for producing a blue pigment for a phosphor according to claim 1, wherein silicic acid alkoxide is used as the silicon raw material.
ＣｏＯ・ＺｎＯ・ＳｉＯ2 系青色顔料を青色発光蛍光体
の表面に付着してなる顔料付青色発光蛍光体。3. A pigmented blue light-emitting phosphor obtained by adhering the CoO.ZnO.SiO 2 blue pigment produced by the method according to claim 1 or 2 onto the surface of a blue light-emitting phosphor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24023791A JP3181635B2 (en) | 1991-08-28 | 1991-08-28 | Method for producing blue pigment for phosphor and blue light-emitting phosphor with pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24023791A JP3181635B2 (en) | 1991-08-28 | 1991-08-28 | Method for producing blue pigment for phosphor and blue light-emitting phosphor with pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0559358A true JPH0559358A (en) | 1993-03-09 |
| JP3181635B2 JP3181635B2 (en) | 2001-07-03 |
Family
ID=17056496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24023791A Expired - Fee Related JP3181635B2 (en) | 1991-08-28 | 1991-08-28 | Method for producing blue pigment for phosphor and blue light-emitting phosphor with pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3181635B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0587123A2 (en) * | 1992-09-07 | 1994-03-16 | Kasei Optonix, Ltd. | Pigment-attached blue-emitting phosphor and color cathode-ray tube |
| US6249328B1 (en) | 1997-09-10 | 2001-06-19 | International Business Machines Corporation | Liquid crystal display device having red, green, and blue fluorescent lamps having a particular phosphor composition or a double tube lamp |
| CN103682053A (en) * | 2013-12-04 | 2014-03-26 | 广西玖典电子新材料有限公司 | Blue fluorescent adhesive for LED |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9618077B2 (en) | 2015-07-23 | 2017-04-11 | Honeywell International Inc. | Isolators including main spring linear guide systems |
-
1991
- 1991-08-28 JP JP24023791A patent/JP3181635B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0587123A2 (en) * | 1992-09-07 | 1994-03-16 | Kasei Optonix, Ltd. | Pigment-attached blue-emitting phosphor and color cathode-ray tube |
| EP0587123A3 (en) * | 1992-09-07 | 1994-07-13 | Kasei Optonix | Pigment-attached blue-emitting phosphor and color cathode-ray tube |
| US6249328B1 (en) | 1997-09-10 | 2001-06-19 | International Business Machines Corporation | Liquid crystal display device having red, green, and blue fluorescent lamps having a particular phosphor composition or a double tube lamp |
| CN103682053A (en) * | 2013-12-04 | 2014-03-26 | 广西玖典电子新材料有限公司 | Blue fluorescent adhesive for LED |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3181635B2 (en) | 2001-07-03 |
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