JPS6254785A - Sulfide phosphor - Google Patents

Abstract

PURPOSE:To obtain the titled phosphor which can effectively prevent the yellowing of a film without causing the lowering in luminance and variation in luminescent color, by incorporating a small amt. of Ce in a sulfide phosphor comprising a matrix material such as ZnS, an activator, and a coactivator. CONSTITUTION:ZnS, (Zn, Cd)S, or CdS used as the matrix material is kneaded with an activator comprising 10-900ppm of at least one member selected from among Ag, Zn, Au, and Cu (e.g., AgNO3), a coactivator comprising 5-1,000ppm of at least one member selected from among Cl, Br, I, F, B, Al, Ga, In, Sb, Bi, Pb, Mn and Eu (e.g., NaCl), 1-100ppm of Ce [e.g., Ce2(CO3)3.5H2O], and optionally 5-500ppm of a fusing agent such as H3BO3, BCl3 or BF3. The mixture is dehydrated and dried to obtain a mixture of phosphor materials. The mixture is packed in a heat-resistant container and calcined in a sulfiding atmosphere at 800 deg.-1,100 deg.C for 1-8hr.

Description

【発明の詳細な説明】 Ａ、産業上の利用分野 本発明は、主として、テレビジョンのブラウン管に使用
される蛍光体に間し、特にコンピュータ一端末などのデ
ィスプレイブラウン管用蛍光体に使用されて、優れた特
性を有する硫化物蛍光体、即ち、硫化亜鉛、硫化亜鉛カ
ドミウム、硫化カドミウム蛍光体に間する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates primarily to phosphors used in cathode ray tubes for televisions, and particularly to phosphors for display cathode ray tubes in computer terminals. Among the sulfide phosphors with excellent properties, ie, zinc sulfide, zinc cadmium sulfide, and cadmium sulfide phosphors.

Ｂ、従来の技術並びにその問題点 硫化亜鉛、硫化亜鉛カドミウム、硫化カドミウム蛍光体
は、ＪＥＤＥＣＮＯ，Ｐ４、ｐＨ、Ｐ２Ｏ、Ｐ２２（緑
、青）、Ｐ２Ｏ、Ｐ３１、Ｐ２Ｏ、Ｐ５４（緑）、Ｐ５
５等としてブラウン管に幅広く使われている。最近、特
に、ディスプレイ用として用いられる場合、膜焼は特性
が問題となってきた。というのは、ディスプレイ用に使
用されるブラウン管は、特定箇所を高い電流密度で連続
的に刺激して発光させる為、決まった部分が劣化して、
蛍光体の輝度が低下した。B. Prior art and its problems Zinc sulfide, zinc cadmium sulfide, and cadmium sulfide phosphors include JEDECNO, P4, pH, P2O, P22 (green, blue), P2O, P31, P2O, P54 (green), P5
It is widely used in cathode ray tubes as a 5th magnitude. Recently, the properties of film firing have become a problem, especially when used for displays. This is because cathode ray tubes used for displays emit light by continuously stimulating specific areas with high current density, so certain areas deteriorate.
The brightness of the phosphor has decreased.

特に、硫化亜鉛蛍光体は、蛍光体の中では発光効率の高
い蛍光体であるが、ディスプレイ管に使用された場合膜
焼けが現れ、これを効果的に解決する手段が切望されて
いる。In particular, zinc sulfide phosphors have a high luminous efficiency among phosphors, but when used in display tubes, film burning occurs, and a means to effectively solve this problem is desperately needed.

本発明は、従来の硫化亜鉛、硫化亜鉛カドミウム、硫化
カドミウム蛍光体の欠点であった膜焼は特性を改良する
ことを第１の目的とする。The first object of the present invention is to improve the film burning characteristics, which is a drawback of conventional zinc sulfide, zinc cadmium sulfide, and cadmium sulfide phosphors.

Ｃ０従来の問題点を解決するための手段本発明の蛍光体
は、硫化亜鉛（ＺｎＳ）、硫化亜鉛カドミウムＣ（Ｚｎ
、Ｃｄ）Ｓｌ　、Ｒ化カドミウム（Ｃｄ　Ｓ）のいずれ
かの硫化物を母体とし、銀、銅、金、亜鉛（自己付活）
の少なくともいずれか一種を付活剤とし、Ｃｌ、Ｂｒ、
Ｔ、Ｆ、Ａ１．８％Ｇａ、Ｉ　ｎ、Ｓｂ、Ｂ　ｉ、Ｐｂ
、Ｍｎ。Means for Solving the Problems of the Conventional C0 The phosphor of the present invention contains zinc sulfide (ZnS), zinc cadmium sulfide
, Cd)Sl, cadmium Ride (CdS) as a matrix, silver, copper, gold, zinc (self-activated)
Cl, Br,
T, F, A1.8% Ga, In, Sb, Bi, Pb
, Mn.

Ｅｕの少なくとも一種を共付活剤としており、更に、Ｃ
ｅを含有している。At least one type of Eu is used as a co-activator, and furthermore, C
Contains e.

付活剤である銀、銅、金の含有量によって発光輝度と発
光色が変化する０発光輝度は付活剤の量が多すぎても、
又少なすぎても低下する。Emission brightness and emission color change depending on the content of silver, copper, and gold, which are activators.
Also, if it is too small, it will decrease.

付活剤の量と種類とは、蛍光体に要求される発光輝度、
発光色並びに原料コストを考慮して最適値に決定される
が、通常母体に対してｌＯ〜９０Ｏｐｐｍ、好ましくは
、５０〜５００ｐｐｍに決定される。The amount and type of activator depend on the luminance required for the phosphor,
The optimum value is determined in consideration of the emission color and raw material cost, but it is usually determined to be 10 to 90 Oppm, preferably 50 to 500 ppm, relative to the base material.

更に、共付活剤は、材料の種類と含有量によって発光輝
度と発光色が変化し、含有量が最適値から多すぎても、
少なすぎても発光輝度が低下する。Furthermore, the luminance and color of co-activators change depending on the type and content of the material, and even if the content is too high from the optimum value,
If it is too small, the luminance will decrease.

従って、これ等の材料は、要求される発光輝度と発光色
とから最適値が決定されが、母体の硫化物に対して、通
常５〜１１０００１）ｐ、好ましくは５０〜５００ｐｐ
ｍ、含有される。Therefore, the optimum value for these materials is determined based on the required luminance brightness and luminescent color, but it is usually 5 to 110,000 pp, preferably 50 to 500 pp, relative to the base sulfide.
m, contained.

Ｃｅの含有量は、多すぎると蛍光体の発光輝度が低下し
、少なすぎると好ましい膜焼は防止効果が実現できない
。従って、膜焼は特性と発光輝度を考慮して母体に対し
て、通常１〜１１００ｐｐ。If the content of Ce is too high, the luminance of the phosphor will decrease, and if the content is too low, the desired effect of preventing film burning cannot be achieved. Therefore, film firing is usually 1 to 1100 ppp relative to the base material, taking into consideration the characteristics and luminance.

好ましくはｌＯ〜６０ｐｐｍ含有される。　　・第１図
と第２図に、Ｃｅ含有量に対する膜焼は特性を示す。第
１図の測定に於て、膜焼は特性は、次の状態で測定した
。パイレックスグラスに蛍光体を沈澱塗布し、アクリル
ラッカーフィルミング、メタルバックを施して、蛍光体
輝度測定装置にて、２７ｋＶ、２０μＡ／ｃｍ２で電子
線を３０分間走査させて強制劣化させ、走査してない蛍
光体の輝度を、２７ｋＶ、０．５μＡ／ｃｍ２で測定し
たものを１００％として強制劣化後の相対輝度を表わし
である。Preferably it is contained in an amount of 10 to 60 ppm.・Figures 1 and 2 show the characteristics of film firing with respect to Ce content. In the measurements shown in FIG. 1, the film properties were measured under the following conditions. Pyrex glass was precipitated and coated with phosphor, acrylic lacquer filmed, and metal backed. Using a phosphor luminance measuring device, the glass was forcibly degraded by scanning with an electron beam at 27 kV and 20 μA/cm2 for 30 minutes. The relative brightness after forced deterioration is taken as 100%, which is the brightness measured at 27 kV and 0.5 μA/cm 2 of the phosphor.

第１図はＺｎＳ　：Ａｇ、Ｃｌ、Ｃｅ蛍光体の膜焼は特
性を示す、この図から明らかなように、この蛍光体は、
Ｃｅの含有量が増加するに従って、膜焼けが減少し、Ｃ
ｅを含有しない従来の蛍光体は、前記の条件で強制劣化
させると、３０分後に輝度が最初の８６％に低下したの
に対し、本発明の蛍光体は、Ｃｅの含有ｊｌｌｐｐｍで
、３０分後の相対発光輝度が８７．６％と従来品に対し
て発光輝度の低下が１．５％改善され、Ｃｅ含有ｉｌｌ
Ｏｐｐｍでは、これが２．８％、２０ｐｐｍでは３％も
改善された。Figure 1 shows the characteristics of the film firing of ZnS:Ag, Cl, Ce phosphor.As is clear from this figure, this phosphor has
As the Ce content increases, film burning decreases and C
When a conventional phosphor containing no Ce was forcibly degraded under the above conditions, the luminance decreased to 86% of the initial level after 30 minutes, whereas the phosphor of the present invention degraded after 30 minutes with a Ce content of 1 ppm. The relative luminance after that was 87.6%, which was an improvement of 1.5% in luminance reduction compared to the conventional product, and the Ce-containing illumination
This was improved by 2.8% at Oppm and 3% at 20ppm.

第２図はＣｄＳ：Ａｇ％Ｃｌ、Ｃｅ蛍光体の膜焼は特性
を示す。この図から明らかなように、この蛍光体は、Ｃ
ｅの含有量が増加するに従フて、膜焼けが減少し、Ｃｅ
を含有しない従来の蛍光体は、前記の条件で強制劣化さ
せると、３０分後に相対発光輝度が最初の９１％に低下
したのに対し、本発明の蛍光体は、Ｃｅの含有量ｌｐｐ
ｍで、３０分後の相対発光輝度が９３，０％と従来品に
対して相対発光輝度の低下が２％改善され、Ｃｅ含有量
１０ｐｐｍでは、これが３．５％も改善され机 Ｃｅの含有量が増加するに従って、膜端は特性は向上す
るが、Ｃｅは蛍光体には関与しないので、含有量が多す
ぎると、第３図に示すように、蛍光体の発光輝度が低下
する。FIG. 2 shows the film characteristics of CdS:Ag%Cl,Ce phosphor. As is clear from this figure, this phosphor is C
As the content of Ce increases, film burning decreases and
When a conventional phosphor containing no Ce was forcibly degraded under the above conditions, the relative luminance decreased to 91% of the initial level after 30 minutes, whereas the phosphor of the present invention has a Ce content of lpp.
m, the relative luminance after 30 minutes was 93.0%, which is a 2% improvement in the decrease in relative luminance compared to the conventional product, and with a Ce content of 10 ppm, this was improved by 3.5%, and the Ce content was 93.0%. As the amount increases, the properties of the film edge improve, but since Ce does not participate in the phosphor, if the content is too large, the luminance of the phosphor decreases as shown in FIG.

第３図は、Ｃｅを含有しない従来のＺｎＳ　：Ａｇ、Ｃ
ｌ蛍光体の相対発光輝度を１００％として、Ｃｅ含有量
に対する本発明の蛍光体の発光輝度を表している。Figure 3 shows conventional ZnS containing no Ce:Ag,C
The luminance of the phosphor of the present invention is expressed relative to the Ce content, assuming that the relative luminance of the phosphor is 100%.

第３図に示す本発明の蛍光体は、Ｃｅの含有量が１０ｐ
ｐｍで、０．３％、１１００ｐｐで１゜５％低下した。The phosphor of the present invention shown in FIG. 3 has a Ce content of 10p.
It decreased by 0.3% in pm and 1.5% at 1100pp.

Ｃｅの含有量に対する膜端け、並びに相対発光輝度は、
蛍光体の種類により多少異なるが、すべての蛍光体に於
て、前述の傾向、即ち、Ｃｅの含有量が増加するに従っ
て膜端は特性は向上するが、多すぎると発光輝度が低下
する特性を示す、ただ、Ｃｅの含有量が５〜３０ｐｐｍ
の範囲に於ては、Ｃｅを含有しない従来の蛍光体にＣｅ
を含有させることによフて、発光輝度が向上する例も実
測された。The film edge and relative luminance with respect to Ce content are as follows:
Although it differs somewhat depending on the type of phosphor, all phosphors exhibit the above-mentioned tendency, that is, as the Ce content increases, the film edge properties improve, but if it is too much, the luminance decreases. However, the Ce content is 5 to 30 ppm.
In the range of
In some cases, it has been actually measured that the luminance of light emission is improved by containing .

これ等のことを考慮して、本発明の蛍光体は、Ｃｅの含
有量が前述の範囲に特定されるが、特に好ましくは１０
〜６０ｐｐｍが最適含有量であった。Taking these things into consideration, the Ce content of the phosphor of the present invention is specified to be within the above-mentioned range, and is particularly preferably 10
The optimum content was ~60 ppm.

Ｄ、好ましい実施例 まず、本発明の蛍光体がいかに優れた膜端は特性を有す
るかを説明する為に、従来の蛍光体を試　　　　　□作
し、同一条件で本発明の蛍光体も試作し、膜端は特性を
測定し比較した。D. Preferred Embodiment First, in order to explain how the phosphor of the present invention has excellent film edge characteristics, a conventional phosphor was made on a trial basis, and a phosphor of the present invention was also made on a trial basis under the same conditions. , the properties of the membrane edges were measured and compared.

従来の蛍光体並びに本発明の蛍光体は、以下に述べる方
法で製造される。The conventional phosphor and the phosphor of the present invention are manufactured by the method described below.

蛍光体原料として、 （イ）母体原料として、Ｚ　ｎ　Ｓ　−（Ｚ　ｎ　＊　
Ｃｄ　）Ｓ、ＣｄＳのいずれか、 （ロ）付活剤として、Ａｇ、Ｃｕ、Ａｕ、Ｚｎの少なく
とも一種 （ハ）共付活剤として、Ｃｌ、Ｂｒ、ｒ、Ｆのアンモニ
ウム塩、又はＡｌ、Ｇａ、Ｉ　ｎ、Ｓｂ、Ｂｔ　ＳＰｂ
ＳＭｎ−Ｅｕ、Ｂの塩化物塩、硫酸塩、硝酸塩のうち少
なくとも一種を使用する。As a phosphor raw material, (a) As a matrix raw material, Z n S − (Z n *
Cd) Either S or CdS; (b) As an activator, at least one of Ag, Cu, Au, or Zn; (c) As a co-activator, an ammonium salt of Cl, Br, r, or F, or Al; Ga, In, Sb, Bt SPb
At least one of SMn-Eu and B chloride, sulfate, and nitrate is used.

更に、好ましくは、融剤として、Ｈ３Ｂ　Ｏ＊、ＢＣｌ
３、ＢＦ３等をを使用する。融剤として使用されるオル
トホウ酸の量は母体に対して５〜５００ｐｐｍが適当で
ある。Furthermore, preferably H3B O*, BCl
3. Use BF3 etc. The amount of orthoboric acid used as a flux is suitably 5 to 500 ppm based on the base material.

蛍光体は上記原料を最適量混練し、脱水乾燥し、得られ
た蛍光体原料混合物を石英ルツボ、石英管等の耐熱性容
器に充填して焼成を行う、焼成は硫化水素雰囲気、硫黄
Ｍ気雰ｙＢ気、二硫化炭素雰囲気等の硫化性雰囲気中で
行う、焼成温度は８ｏ。The phosphor is made by kneading the above raw materials in an optimum amount, dehydrating and drying the mixture, filling the obtained phosphor raw material mixture into a heat-resistant container such as a quartz crucible or a quartz tube, and firing.The firing is performed in a hydrogen sulfide atmosphere or a sulfur M atmosphere. The firing temperature is 8o, which is carried out in a sulfidic atmosphere such as atmosphere YB or carbon disulfide atmosphere.

℃〜１１００℃が適当である。焼成時間は焼成温度、蛍
光体原料混合物の量等により異なるが、１〜８時間が適
当である。焼成後、得られた焼成物を充分水洗し、脱水
乾燥させ、ふるいにかけ本発明の蛍光体を得る。℃~1100℃ is suitable. The firing time varies depending on the firing temperature, the amount of the phosphor raw material mixture, etc., but 1 to 8 hours is appropriate. After firing, the obtained fired product is thoroughly washed with water, dehydrated and dried, and sieved to obtain the phosphor of the present invention.

実施例１゜ 硫化亜鉛　　　　ＺｎＳ　　　　　　１０００ｇ硝酸銀
　　　　　ＡｇＮＯｓ　　　　　Ｏ，３ｇ炭酸セリウム
　　Ｃｅ２＜ＣＯｓ＞ｓ◆５Ｈｔｏ　　　　１２　ｇ塩
化ナトリウム　ＮａＣ１１Ｂｇ オルトホウ酸　　ＨｔＢＯｚ　　　　　　　１８ｇ上記
原料を水と共に充分に混練し、脱水乾燥し、得られた蛍
光体原料混合物に硫黄および活性炭素を適当量加えて石
英ルツボに充填した０石英ルツボに蓋をした後、電気炉
に入れ、９５０’Ｃの温度で３時間焼成を行った。焼成
後、得られた焼成物を充分に水洗し、脱水乾燥し、ふる
いにかけた。Example 1 Zinc sulfide ZnS 1000g Silver nitrate AgNOs O,3g Cerium carbonate Ce2<COs>s◆5Hto 12g Sodium chloride NaC11Bg Orthoboric acid HtBOz 18g The above raw materials were thoroughly kneaded with water, dehydrated and dried to obtain a phosphor. Appropriate amounts of sulfur and activated carbon were added to the raw material mixture, and the quartz crucible was filled with a lid, placed in an electric furnace, and fired at a temperature of 950'C for 3 hours. After firing, the obtained fired product was thoroughly washed with water, dehydrated and dried, and passed through a sieve.

このようにして、ＺｎＳ：Ａｇ％Ｃｌ、’Ｃｅ蛍光体を
得た。In this way, a ZnS:Ag%Cl,'Ce phosphor was obtained.

この蛍光体は、母体であるＺｎＳに対して、２８ｐｐｍ
のセリウムを含有していた。This phosphor has a concentration of 28 ppm with respect to the base material ZnS.
It contained cerium.

実施例菫の原料からＣｅ２　（Ｃｏ３）　３・５Ｈ２０
を除いてその他の条件は同一で従来品１の蛍光体を試作
した。Example: Ce2 (Co3) 3.5H20 from raw material of violet
A prototype phosphor of Conventional Product 1 was manufactured under the same conditions except for .

実施例１の蛍光体は、第１表に示すように、発光色が、
ＣｌＥ色度表示のＸ値、ｙ値に於て、Ｘ＝０．１４７、
Ｖ＝０．０６３と、従来品１と同等の色純度の高い青色
発光を示した。従来品ｌの蛍光体ＺｎＳ　：Ａｇ、Ｃｌ
の相対発光輝度（１００％）に比べて初期の発光輝度が
９９．８％と従来品に匹敵し、強制劣化試験後の相対発
光輝度は、９０．２％と従来品１　（８６，０％）より
も４゜２％も向上した。As shown in Table 1, the phosphor of Example 1 has the following luminescent colors:
In the X value and y value of ClE chromaticity display, X = 0.147,
V=0.063, which showed blue light emission with high color purity equivalent to that of Conventional Product 1. Conventional product 1 phosphor ZnS: Ag, Cl
Compared to the relative luminance of conventional product 1 (100%), the initial luminance was 99.8%, which is comparable to the conventional product, and the relative luminance after the forced deterioration test was 90.2%, which was 86.0% of conventional product 1. ) was improved by 4.2%.

この蛍光体は、製造工程に於て、Ｃｅ２（ＣＯｉ）３・
５Ｈ２０の混合量を調整して、膜端は特性の変化を測定
した。その結果を第１図に示す。This phosphor is manufactured by Ce2(COi)3,
The amount of 5H20 mixed was adjusted, and changes in the properties of the film edge were measured. The results are shown in FIG.

第１図から明らかなように、Ｃｅの含有量が増加するに
従って膜端は特性が改善され、特に、ＣＣの含有量が１
０ｐｐｍ以上ですぐれた特性を示した。As is clear from Fig. 1, as the Ce content increases, the film edge properties are improved, especially when the CC content is 1.
Excellent properties were shown at 0 ppm or more.

実施例２゜ 硫化亜鉛　　　　　ＺｎＳ　　　　　１０００ｇ硫酸銅
　　　　　　Ｃｕ５ＯＪ　　　ｏ、１８ｇ硝酸ｉ１　　
　　　　　ＡｇＮＯ３０，１２ｇ塩化アンモニウム　Ｎ
Ｈ４Ｃｌ　　　　　　１０ｇ第１表 硝酸アルミニウム　Ａｌ（ＮＯａ）３９Ｈ２００、５６
ｇ炭酸セリウム　　　Ｃｅ２（ＣＯｓ）ｚ５Ｈ２００、
０８ｇ上記原料を１０２０℃で２．５時間焼成すること
以外、実施例１と同様の処理をして ＺｎＳ：ＣｕｌＡｇ、Ａｌ、Ｃｅ蛍光体を得た。Example 2゜Zinc sulfide ZnS 1000g Copper sulfate Cu5OJ o, 18g nitric acid i1
AgNO30, 12g Ammonium chloride N
H4Cl 10g Table 1 Aluminum nitrate Al (NOa) 39H200, 56
gCerium carbonate Ce2(COs)z5H200,
08g ZnS:CulAg, Al, Ce phosphor was obtained by carrying out the same treatment as in Example 1 except that the above raw material was fired at 1020° C. for 2.5 hours.

この蛍光体は、母体であるＺｎＳに対して１２ｐｐｍの
Ｃｅを含有していた。This phosphor contained 12 ppm of Ce based on the base ZnS.

この蛍光体は、第１表に示すように、発光色が、ＣｌＥ
色度表示のＸ値、ｙ値に於て、ｘ＝０．２６７、ｙ＝Ｑ
、５５７と緑色発光を示し、従来のＣｅを含まない蛍光
体である従来品２のＺｎＳ　：Ｃｕ、Ａｇ、Ａｌの相対
発光輝度（１００％）に比べて初期の発光輝度が１０１
．１％と高く、しかも電子線強制劣化試験後の発光輝度
は、９２゜０％と従来品２の８７．０％に比べて５％も
向上した。As shown in Table 1, this phosphor has a luminescent color of ClE
In the X value and y value of chromaticity display, x=0.267, y=Q
, 557, and the initial luminescence luminance was 101 compared to the relative luminance (100%) of ZnS:Cu, Ag, Al of conventional product 2, which is a conventional Ce-free phosphor.
．． The luminance was as high as 1%, and the luminance after the electron beam forced deterioration test was 92.0%, an improvement of 5% compared to 87.0% for conventional product 2.

従来品２の蛍光体ＺｎＳ　：　Ｃｕ、Ａｇ、Ａｌは実施
例２の原料からＣｅ２（ＣＯ３）８・５Ｈ２０を除いて
、実施例２と同様の条件で試作したものである。The phosphor ZnS of conventional product 2: Cu, Ag, and Al was experimentally produced under the same conditions as in Example 2, except that Ce2(CO3)8.5H20 was removed from the raw materials in Example 2.

実施例３゜ 硫化亜鉛　　　　　Ｚｎ９　　　　　　８５０ｇ硫化カ
ドミウム　　ＣｄＳ　　　　　　　１５０ｇ硫酸銅　　
　　　　Ｃｕ５Ｏａ　　　　０．２３ｇ塩化ナトリウム
　　ＮａＣｌ　　　　　　　１０ｇ炭酸セリウム　　　
Ｃｅ２（ＣＯ３）３５Ｈ２００，１６ｇオルトホウ酸　
　　Ｈ３Ｂ　０３　　　　　　　５　ｇ上記原料を１０
００℃で３．６時間焼成すること以外、実施例１と同様
の処理をして、（Ｚｎ、Ｃｄ）Ｓ：Ｃｕ、Ｃｍ　Ｃｅ蛍
光体を得た。Example 3 Zinc sulfide Zn9 850g Cadmium sulfide CdS 150g Copper sulfate
Cu5Oa 0.23g Sodium chloride NaCl 10g Cerium carbonate
Ce2(CO3)35H200, 16g orthoboric acid
H3B 03 5 g 10 of the above raw materials
A (Zn,Cd)S:Cu,CmCe phosphor was obtained by carrying out the same treatment as in Example 1 except for firing at 00°C for 3.6 hours.

この蛍光体は、母体である（Ｚｎ、Ｃｄ）Ｓに対して、
３２ｐｐｍのＣｅを含有していた。This phosphor is based on (Zn, Cd)S, which is the base material.
It contained 32 ppm of Ce.

この蛍光体は、第１表に示すように、発光色が、ＣｌＥ
色度表示のＸ値、ｙ値に於て、ｘ＝０．３２２、ｙ＝０
．３２２と緑色発光を示し、従来のＣｅを含まない蛍光
体である従来品３の（Ｚｎ。As shown in Table 1, this phosphor has a luminescent color of ClE
In the X value and y value of chromaticity display, x=0.322, y=0
．． 322 and green light emission, compared with conventional product 3 (Zn.

Ｃｄ）Ｓ：Ｃｕ、Ｃｌの相対発光輝度（１００％）に比
べて初期の発光輝度が９９．７％と高く、しかも電子線
強制劣化試験後の発光輝度は、９３゜６％と従来品３の
９０．０％に比へて３．５％も向上した。Cd) S: Compared to the relative luminance of Cu and Cl (100%), the initial luminance is high at 99.7%, and the luminance after the electron beam forced degradation test is 93.6%, which is higher than the conventional product 3. This was an improvement of 3.5% compared to 90.0%.

第１表に於て、従来のＣｅを含まない従来品３の（Ｚｎ
、Ｃｄ）Ｓ：Ｃｕ％Ｃｌは、実施例３の原料からＣｅ２
（ＣＯ３）３５Ｈ２０を除いて、実施例３と同様の条件
で試作したものである。In Table 1, conventional product 3 (Zn
,Cd)S:Cu%Cl is Ce2 from the raw material of Example 3
A prototype was produced under the same conditions as in Example 3 except for (CO3)35H20.

実施例４゜ 硫化カドミウム　　ＣｄＳ　　　　　　１０００ｇ硝酸
銀　　　　　　ＡｇＮ０ｉ　　　　　ｏ、ａｇ塩化ナト
リウム　　ＮａＣ１１０ｇ 炭酸セリウム　　　Ｃｅ２（ＣＯｚ）ｚ５ｆ（２００、
２４ｇ上記原料を９５０℃で３．５時間焼成すること以
外、実施例１．と同様の処理をして、 ＣｄＳ：Ａｇ、Ｃｌ、Ｃｅ蛍光体を得た。Example 4 Cadmium sulfide CdS 1000g Silver nitrate AgN0io, ag Sodium chloride NaC 110g Cerium carbonate Ce2(COz)z5f(200,
Example 1 except that 24g of the above raw material was calcined at 950°C for 3.5 hours. A CdS:Ag, Cl, Ce phosphor was obtained by the same treatment as above.

この蛍光体は、母体であるＣｄＳに対して、５６ｐｐｍ
のＣｅを含有していた。This phosphor has a concentration of 56 ppm relative to the base material CdS.
of Ce.

この蛍光体は、第１表に示すように、発光色が、ＣｌＥ
色度表示のＸ値、ｙ値に於て、ｘ＝０．６８５、ｙ＝ｏ
、ａｉ３と赤色発光を示し、従来品４の蛍光体ＣｄＳ：
Ａｇ、Ｃｌの相対発光輝度（１００％）に比べて発光輝
度が９９．１％とほぼこれに匹敵し、強制劣化試験の発
光輝度は、従来品４の９１．０％よりも３．５％高い９
４．５％となった。As shown in Table 1, this phosphor has a luminescent color of ClE
In the X value and y value of chromaticity display, x=0.685, y=o
, ai3 and red light emission, conventional product 4 phosphor CdS:
Compared to the relative luminance of Ag and Cl (100%), the luminance is 99.1%, which is almost comparable, and the luminance in the forced deterioration test is 3.5%, compared to 91.0% of conventional product 4. high 9
It was 4.5%.

第１表に於て、従来品４の蛍光体ＣｄＳ：Ａｇ、Ｃｔは
実施例４の原料からＧｅｔ＋（Ｃｏｔ）３・５Ｈ２０を
除いて、実施例４と同様の条件で試作したものである。In Table 1, the phosphor CdS:Ag, Ct of Conventional Product 4 was experimentally produced under the same conditions as Example 4, except that Get+(Cot)3.5H20 was removed from the raw materials of Example 4.

この蛍光体は、製造工゛程に於て、Ｃｅ２（ＣＯ３）３
・５Ｈ２０の混合量を調整して、膜端は特性の変化を測
定した。その結果を第２図に示す。This phosphor is produced using Ce2(CO3)3 during the manufacturing process.
- The amount of 5H20 mixed was adjusted, and changes in the properties of the film edge were measured. The results are shown in FIG.

第２図から明らかなように、Ｃｅの含有量が増加するに
従フて膜端は特性が改善され、特に、Ｃｅの含有量が１
０ｐｐｍ以上ですぐれた特性を示した。As is clear from FIG. 2, as the Ce content increases, the properties of the film edge improve.
Excellent properties were shown at 0 ppm or more.

以下、原料組成を変更したものについて、従来の蛍光体
と本発明の蛍光体を試作し、膜端は特性を比較した一覧
表を第１表に示す。Table 1 below shows a list comparing the film edge properties of a conventional phosphor and a phosphor of the present invention produced as prototypes with different raw material compositions.

尚、従来品６〜ｌＯの蛍光体は、本発明の５〜ｌＯの蛍
光体からＣｅを除いて、他の組成を同一とし実施例と同
条件で試作したものである。Incidentally, the conventional phosphor of 6 to 1O was prepared as a prototype under the same conditions as the example, with the same composition except for Ce from the phosphor of 5 to 1O of the present invention.

ところで、第１表に於て、相対発光輝度（Ｙ）は、それ
ぞれの従来品１〜１０の蛍光体に於て、Ｃｅを含まない
蛍光体を１００％として表示した。Incidentally, in Table 1, the relative luminance (Y) of each of the conventional products 1 to 10 is expressed with the Ce-free phosphor as 100%.

従って、従来品１〜１０の蛍光体は相対発光輝度が全て
１００％と同一であるが、発光輝度は必ずしも同一でな
い。Therefore, although the phosphors of conventional products 1 to 10 all have the same relative luminance of 100%, the luminances are not necessarily the same.

共付活剤には、前記実施例で使用されたＣｌ　　・Ａｌ
のみでなくＢｒ、Ｉ％Ｆ、Ｂ、Ｇａ、Ｉｎ。The co-activator includes Cl and Al used in the above examples.
Not only Br, I%F, B, Ga, In.

Ｓｂ、Ｂ　ｉＳＰｂＳＭｎ、Ｅｕ等が使用できる。Sb, B iSPbSMn, Eu, etc. can be used.

共付活剤は、単独使用のみでなく、複数種を母体に含有
させることも可能である。The co-activator can not only be used alone, but also multiple types can be contained in the matrix.

共付活剤は、複数種が一緒に母体に含有される場合、母
体ＺｎＳに対する含有量は、共付活剤の総合有量のトー
タル量で調整される。When a plurality of types of co-activators are contained together in the matrix, the content with respect to the matrix ZnS is adjusted by the total amount of the co-activators.

Ｅ０発明の効果 本発明の蛍光体は、第１表並びに第１ｒＭ〜第２図に示
すように、微量のＣｅを含有させることによって、膜端
は特性を相当に向上できる。この為、本発明の蛍光体を
コンピュータ用のディスプレイに使用することによって
、特定部分の連結高密度電子線励起による膜端けを効果
的に防止できる。E0 Effects of the Invention In the phosphor of the present invention, as shown in Table 1 and Figures 1rM to 2, by containing a trace amount of Ce, the film edge characteristics can be considerably improved. Therefore, by using the phosphor of the present invention in a computer display, it is possible to effectively prevent film edges caused by coupled high-density electron beam excitation in specific parts.

又、本発明の硫化物蛍光体は、極めて少量のＣｅで十分
な膜端は防止効果が期待できる為、Ｃｅ含有量による弊
害、即ち、発光輝度の低下、並びに発光色の変化等を最
低限に防止できる。In addition, since the sulfide phosphor of the present invention can be expected to have a sufficient film edge prevention effect with a very small amount of Ce, the adverse effects caused by the Ce content, such as a decrease in luminance and a change in luminescent color, can be minimized. can be prevented.

更に、Ｃｅを含有させることによって膜端けが防止され
る効果は、本来膜焼けを起こし易い蛍光体、例えばＺｎ
Ｓ　：Ａｇ、Ｃｌ、ＺｎＳ　：　Ｃｕ。Furthermore, the effect of preventing film edge burn-out by including Ce can be achieved with phosphors that are naturally prone to film burn-out, such as Zn.
S: Ag, Cl, ZnS: Cu.

Ｃｔ及び（Ｚｎ、Ｃｄ）：Ａｇ、Ｃｌ蛍光体に於て特に
顕著に現れ、膜端けを起こし易く、改善の要求が強い蛍
光体を優れた特性とする効果が高かった。Ct and (Zn, Cd): This was particularly noticeable in Ag and Cl phosphors, and was highly effective in imparting excellent properties to phosphors that tend to cause film edge chipping and are in strong demand for improvement.

【図面の簡単な説明】[Brief explanation of the drawing]

第１ＩＩおよび第２ｒ！ＭはＣｅ含有量に対する膜端は
特性を示すグラフ、第３図はＣｅ含有量に対する相対発
光輝度の変化を示すグラフである。 第１図 しｅ含有量（ｐＩ）ｍ） 第３図 Ｃｅ含有量（１）　ｐｍ）1II and 2R! M is a graph showing film edge characteristics with respect to Ce content, and FIG. 3 is a graph showing changes in relative luminance with respect to Ce content. Figure 1: E content (pI) m) Figure 3: Ce content (1) pm)

Claims (8)

【特許請求の範囲】[Claims] （１）母体がＺｎＳ（硫化亜鉛）、（Ｚｎ，Ｃｄ）Ｓ（
硫化亜鉛カドミウム）、ＣｄＳ（硫化カドミウム）のい
ずれかであり、Ａｇ（銀）、Ｚｎ（亜鉛自己付活）、Ａ
ｕ（金）、Ｃｕ（銅）のうち少なくとも一種を付活剤と
し、Ｃｌ（塩素）、Ｂｒ（シュウ素）、Ｉ（ヨウ素）、
Ｆ（フッ素）、Ｂ（ホウ素）、Ａｌ（アルミニウム）、
Ｇａ（ガリウム）、Ｉｎ（インジウム）、Ｓｂ（アンチ
モン）、Ｂｉ（ビスマス）、Ｐｂ（ナマリ）、Ｍｎ（マ
ンガン）およびＥｕ（ユーロピウム）のうち少なくとも
一種を共付活剤とする硫化物蛍光体において、Ｃｅ（セ
リウム）を、前記蛍光体の母体に対して重量比で１〜１
００ｐｐｍの範囲内で含有して成ることを特徴とする硫
化物蛍光体。(1) The matrix is ZnS (zinc sulfide), (Zn,Cd)S(
Zinc cadmium sulfide), CdS (cadmium sulfide), Ag (silver), Zn (zinc self-activation), A
At least one of u (gold) and Cu (copper) is used as an activator, and Cl (chlorine), Br (oxuine), I (iodine),
F (fluorine), B (boron), Al (aluminum),
In a sulfide phosphor using at least one of Ga (gallium), In (indium), Sb (antimony), Bi (bismuth), Pb (namali), Mn (manganese) and Eu (europium) as a coactivator. , Ce (cerium) in a weight ratio of 1 to 1 with respect to the matrix of the phosphor.
A sulfide phosphor containing a sulfide phosphor in an amount of 0.00 ppm. 　（２）Ｃｅの含有量が蛍光体母体に対して１０〜６０
ｐｐｍである特許請求の範囲第（１）項記載の硫化物蛍
光体。(2) Ce content is 10 to 60 relative to the phosphor matrix
The sulfide phosphor according to claim (1), which is ppm. 　（３）母体がＺｎＳで、付活剤がＡｇで、共付活剤が
Ｃｌである特許請求の範囲第（１）項記載の硫化物蛍光
体。(3) The sulfide phosphor according to claim (1), wherein the matrix is ZnS, the activator is Ag, and the co-activator is Cl. 　（４）母体がＺｎＳで、付活剤がＣｕとＡｇで、共付
活剤がＡｌである特許請求の範囲第（１）項記載の硫化
物蛍光体。(4) The sulfide phosphor according to claim (1), wherein the matrix is ZnS, the activators are Cu and Ag, and the co-activator is Al. 　（５）母体が（Ｚｎ，Ｃｄ）Ｓで、付活剤がＣｕで、
共付活剤がＣｌである特許請求の範囲第（１）項記載の
硫化物蛍光体。(5) The matrix is (Zn, Cd)S, the activator is Cu,
The sulfide phosphor according to claim (1), wherein the co-activator is Cl. 　（６）母体が（Ｚｎ，Ｃｄ）Ｓで、付活剤がＣｕで、
共付活剤がＡｌである特許請求の範囲第（１）項記載の
硫化物蛍光体。(6) The matrix is (Zn, Cd)S, the activator is Cu,
The sulfide phosphor according to claim (1), wherein the co-activator is Al. 　（７）母体がＺｎＳで、付活剤がＣｕで、共付活剤が
Ｃｌである特許請求の範囲第（１）項記載の硫化物蛍光
体。(7) The sulfide phosphor according to claim (1), wherein the matrix is ZnS, the activator is Cu, and the co-activator is Cl. 　（８）母体がＺｎＳで、付活剤がＣｕとＡｕで、共付
活剤がＡｌである特許請求の範囲第（１）項記載の硫化
物蛍光体。(8) The sulfide phosphor according to claim (1), wherein the matrix is ZnS, the activator is Cu and Au, and the co-activator is Al.