JPH0717899B2 - Luminescent composition - Google Patents
Luminescent compositionInfo
- Publication number
- JPH0717899B2 JPH0717899B2 JP2110559A JP11055990A JPH0717899B2 JP H0717899 B2 JPH0717899 B2 JP H0717899B2 JP 2110559 A JP2110559 A JP 2110559A JP 11055990 A JP11055990 A JP 11055990A JP H0717899 B2 JPH0717899 B2 JP H0717899B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- conductive metal
- metal oxide
- light emitting
- homogeneous film
- 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 - Fee Related
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、蛍光表示管に用いられる低速電子線により励
起されて蛍光を発する発光組成物に係り、特に蛍光表示
管用に用いられる発光組成物に関する。Description: TECHNICAL FIELD The present invention relates to a luminescent composition used in a fluorescent display tube, which emits fluorescence when excited by a low-speed electron beam, and particularly to a luminescent composition used for a fluorescent display tube. Regarding
［従来の技術］ 低速電子線励起蛍光体は、低速電子線励起蛍光表示管
（以下、蛍光表示管と呼ぶ）用に用いられる蛍光体であ
る。蛍光表示管は、片面に蛍光膜を有する陽極プレート
と蛍光膜に対向した陰極とを容器内に封入し、容器内を
真空にした構造を有し、陰極から放射される加速電圧1k
V以下の低速電子線によって陽極プレート上の蛍光膜を
発光させるものである。[Prior Art] A slow electron beam excited phosphor is a phosphor used for a slow electron beam excited fluorescent display tube (hereinafter referred to as a fluorescent display tube). A fluorescent display tube has a structure in which an anode plate having a fluorescent film on one surface and a cathode facing the fluorescent film are enclosed in a container, and the inside of the container is evacuated, and an accelerating voltage of 1 k emitted from the cathode.
The phosphor film on the anode plate is caused to emit light by a slow electron beam of V or less.
蛍光表示管の蛍光膜を構成する蛍光体に要求される最も
重要な特性は、蛍光体が導電性を有するということであ
る。導電性が低いと、陰極から放射される電子線によっ
て陽極の蛍光膜表面が負帯電し、発光不能を生じる。し
たがって、蛍光膜に導電性を付与し、高まった電荷を逃
がすために従来数々の技術が開示されている。例えば、
特公昭52−23911号公報においてはZnS:Ag、Y2SiO5:Ce等
の青色発光蛍光体に10〜90重量％のIn2O3が混合された
発光組成物が開示されている。また、特公昭62−53554
号公報では、ZnS:Ag、Zn（SSe）:Ag,Al、SrGa2S4:Ce等
の青色発光蛍光体に粒径の規定されたIn2O3、SnO2等が
混合された発光組成物が開示されている。これらの技術
は、母体である蛍光体が導電性を持たないため、In
2O3、SnO2等の導電性金属酸化物をその蛍光体に混合す
ることによって、蛍光体及びその蛍光膜に導電性を付与
し、蛍光表示管の輝度を向上させるものである。The most important characteristic required for the phosphor forming the fluorescent film of the fluorescent display tube is that the phosphor has conductivity. If the conductivity is low, the surface of the fluorescent film of the anode is negatively charged by the electron beam emitted from the cathode, which makes it impossible to emit light. Therefore, various techniques have been disclosed in the past for imparting conductivity to the fluorescent film and allowing the increased electric charge to escape. For example,
Japanese Patent Publication No. 52-23911 discloses a light emitting composition in which a blue light emitting phosphor such as ZnS: Ag or Y 2 SiO 5 : Ce is mixed with 10 to 90% by weight of In 2 O 3 . In addition, Japanese Examined Japanese Patent Sho 62-53554
In the publication, blue light emitting phosphors such as ZnS: Ag, Zn (SSe): Ag, Al, and SrGa 2 S 4 : Ce are mixed with In 2 O 3 , SnO 2 and the like having a defined particle size. The thing is disclosed. In these technologies, since the base phosphor is not conductive, In
By mixing a conductive metal oxide such as 2 O 3 or SnO 2 with the phosphor, conductivity is imparted to the phosphor and its phosphor film, and the brightness of the fluorescent display tube is improved.
しかしながら、前述の導電性金属酸化物（以下、導電性
物質という）は、非発光物質であり、しかも黄色もしく
は褐色の体色を有する。このため、それらを蛍光体と多
量に混合して発光組成物とする上記技術は、前記導電性
物質が蛍光体の発光を阻害及び吸収してしまうために、
蛍光表示管の輝度低下をまねくという欠点がある。この
ような欠点は、従来より発光組成物中の導電性物質の混
合量を調節することにより解消が試みられてきたが、ま
だ不十分である。特に、最近の急速な表示デバイスの発
達に伴い、より高輝度の蛍光表示管が望まれている。However, the above-mentioned conductive metal oxide (hereinafter referred to as a conductive substance) is a non-luminous substance and has a yellow or brown body color. For this reason, the above technique of mixing them with a phosphor in a large amount to form a light emitting composition is because the conductive substance inhibits and absorbs the emission of the phosphor,
There is a drawback that the brightness of the fluorescent display tube is lowered. Although such drawbacks have hitherto been attempted to be solved by adjusting the mixing amount of the conductive substance in the light emitting composition, they are still insufficient. In particular, with the recent rapid development of display devices, fluorescent display tubes with higher brightness are desired.
［発明が解決しようとする課題］ 本発明は、上記事情を鑑みてなされたものであり、加速
電圧1kV以下特に100V以下の低速電子線励起のものとで
十分な導電性及び発光輝度を有する発光組成物を提供す
ることを目的とする。[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and emits light having sufficient conductivity and emission brightness with an accelerating voltage of 1 kV or less, particularly 100 V or less of low-speed electron beam excitation. It is intended to provide a composition.
［課題を解決するための手段］ 本発明者らは、蛍光表示管の輝度を向上するために、発
光組成物に含まれる数々の導電性物質の種類及び蛍光体
に対する添加方法、添加量等について鋭意研究を重ねた
結果、蛍光体表面全体に均質膜状または半均質膜状に導
電性金属酸化膜を被覆し、次いでこれに適切な量の導電
性金属酸化物を混合または付着することにより、低速電
子線励起下で発光組成物の輝度が飛躍的に向上すること
を見出だし本発明を成すに至った。[Means for Solving the Problems] In order to improve the brightness of the fluorescent display tube, the present inventors have studied the types of various conductive substances contained in the light emitting composition, the addition method to the phosphor, the addition amount, and the like. As a result of repeated intensive research, by coating the entire surface of the phosphor with a conductive metal oxide film in a homogeneous film form or a semi-homogeneous film form, and then mixing or adhering an appropriate amount of the conductive metal oxide film thereto, The inventors have found that the brightness of the light-emitting composition is dramatically improved under low-speed electron beam excitation, and completed the present invention.
本発明の発光組成物は、蛍光体表面全体を均質膜状また
は半均質膜状の導電性金属酸化物で被覆された低速電子
線励起発光体と、該蛍光体に混合または付着された粒状
導電性金属酸化物とを含むことを特徴とする。The light-emitting composition of the present invention comprises a slow-electron-beam-excited luminescent material whose entire phosphor surface is coated with a conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film, and a granular conductive material mixed or attached to the phosphor. And a conductive metal oxide.
前記均質膜状または半均質膜状の導電性物質が蛍光体を
被覆している状態とは、粒状の導電性物質を混合した従
来の発光組成物のように蛍光体と導電性物質が点で接触
している状態とは異なり、蛍光体と導電性物質とが面で
つながっている状態を指す。したがって、一部塊状の付
着物を含んだり、ムラになって付着している場合もあり
得る。The homogeneous film-like or semi-homogeneous film-like conductive substance covering the phosphor means that the phosphor and the conductive substance are the same as in the conventional luminescent composition in which the granular conductive substance is mixed. Unlike the state in which they are in contact with each other, it means the state in which the phosphor and the conductive substance are connected by a surface. Therefore, there may be a case where a part of lump-like adhered matter is included or unevenly adhered.
本発明の発光組成物に用いられる蛍光体としては、一般
に良く知られた低速電子線励起蛍光体を用いることがで
きる。例えば、青色発光蛍光体としては、銀付活硫化亜
鉛（ZnS:Ag）、セリウム付活ケイ酸イットリウム（Y2Si
2O5）、自己付活タングステン酸カルシウム（CaWO4）
等、緑色発光蛍光体としては銅付活硫化亜鉛（ZnS:C
u）、銅付活硫化亜鉛カドミウム｛（ZnCd）S:Cu｝、テ
ルビウム付活希土類酸硫化物（Ln2O2S:Tb）、マンガン
付活ケイ酸亜鉛（Zn2SiO4）等、赤色発光蛍光体として
はユーロピウム付活酸硫化イットリウム（Y2O2S:Eu）、
銅付活硫化亜鉛カドミウム｛（ZnCd）:Cu｝等の蛍光体
を用いることができる。As the phosphor used in the light emitting composition of the present invention, a generally well-known slow electron beam excited phosphor can be used. For example, as the blue-emitting phosphor, silver activated zinc sulfide (ZnS: Ag), cerium activated yttrium silicate (Y 2 Si)
2 O 5 ), self-activated calcium tungstate (CaWO 4 ).
As a green light emitting phosphor, copper activated zinc sulfide (ZnS: C
u), copper activated zinc cadmium sulfide {(ZnCd) S: Cu}, terbium activated rare earth oxysulfide (Ln 2 O 2 S: Tb), manganese activated zinc silicate (Zn 2 SiO 4 ), etc., red Europium activated yttrium oxysulfide (Y 2 O 2 S: Eu),
A phosphor such as copper activated zinc cadmium sulfide {(ZnCd): Cu} can be used.
特に前記蛍光体は、一般式ZnS:M1,M2または一般式（ZnC
d）S:M1,M2で表される蛍光体からなる群から選択された
少なくとも１種であることが好ましい。但し、M1はAg、
Zn、Cu及びAuからなる群から選択された少なくとも１種
の元素であり、M2はAl、Ｆ、Cl、Br及びＩからなる群か
ら選択された少なくとも１種の元素である。このような
蛍光体を蛍光表示管に用いると、特に輝度が良好となる
傾向がある。またその発光色は、前記一般式中のM1、M2
の種類及び添加量、及びCdの添加量を変化させることに
より、自由に変えることができる。例えばM1、M2の種類
の変化により、（ZnS:Ag,Al）、（ZnS:Zn,Cl）及び
｛（ZnCd）S:Ag,Cl｝等は青色発光蛍光体、（ZnS:Cu,C
l）、（ZnS:Cu,Au,Al）及び｛（ZnCd）S:Ag,Al｝等は緑
色蛍光体、（ZnS:Au,Al）、（ZnS:Cu,Au,Al）及び｛（Z
nCd）S:Ag,Cl｝等は黄色発光蛍光体、｛ZnS:Zn,Clと（Z
nCd）S:Ag,Cu,Al｝、｛ZnS:Ag,AlとZnS:Au,Alの混合
物｝及び｛（ZnCd）S:Ag,Au,Al｝等は白色発光蛍光体、
｛（ZnCd）S:Cu,Cl｝、｛（ZnCd）S:Au,Al｝、｛（ZnC
d）S:Ag,Cl｝及びZnS:Mn等は橙色発光蛍光体、｛（ZnC
d）S:Cu,Al｝、｛（ZnCd）S:Au,Al｛（ZnCd）S:Ag,Al｝
及び（ZnCd）S:Mn等は赤色発光蛍光体として用いられ
る。In particular, the phosphor has the general formula ZnS: M 1 , M 2 or the general formula (ZnC
d) It is preferably at least one selected from the group consisting of phosphors represented by S: M 1 and M 2 . However, M 1 is Ag,
It is at least one element selected from the group consisting of Zn, Cu and Au, and M 2 is at least one element selected from the group consisting of Al, F, Cl, Br and I. When such a phosphor is used in a fluorescent display tube, the brightness tends to be particularly good. The emission color is M 1 , M 2 in the above general formula.
It can be freely changed by changing the kind and addition amount of Cd and the addition amount of Cd. For example, due to changes in the types of M 1 and M 2 , (ZnS: Ag, Al), (ZnS: Zn, Cl) and {(ZnCd) S: Ag, Cl} are blue-emitting phosphors, (ZnS: Cu, C
l), (ZnS: Cu, Au, Al) and {(ZnCd) S: Ag, Al} are green phosphors, (ZnS: Au, Al), (ZnS: Cu, Au, Al) and {(Z
nCd) S: Ag, Cl} and the like are yellow-emitting phosphors, {ZnS: Zn, Cl and (ZnS: Zn, Cl
nCd) S: Ag, Cu, Al}, {ZnS: Ag, Al and ZnS: Au, Al mixture} and {(ZnCd) S: Ag, Au, Al} are white-emitting phosphors,
{(ZnCd) S: Cu, Cl}, {(ZnCd) S: Au, Al}, {(ZnC
d) S: Ag, Cl} and ZnS: Mn are orange-emitting phosphors, {(ZnC
d) S: Cu, Al}, {(ZnCd) S: Au, Al {(ZnCd) S: Ag, Al}
And (ZnCd) S: Mn are used as the red-emitting phosphor.
均質膜状または半均質膜状の導電性金属酸化物及び粒状
導電性金属酸化物としては、例えばIn2O3、SnO2、ZnO、
TiO2、WO3またはNb2O5等を用いることができ、特に、優
れた導電率を有することから、In2O3またはSnO2が好ま
しい。Examples of the homogeneous film-like or semi-homogeneous film-like conductive metal oxides and granular conductive metal oxides include In 2 O 3 , SnO 2 , ZnO,
TiO 2 , WO 3, Nb 2 O 5 or the like can be used, and In 2 O 3 or SnO 2 is particularly preferable because it has excellent conductivity.
粒状導電性金属酸化物の体積平均粒径は0.05μｍ以上2.
0μｍ以下であることが好ましい。The volume average particle size of the granular conductive metal oxide is 0.05 μm or more 2.
It is preferably 0 μm or less.
均質膜状または半均質膜状導電性金属酸化物及び粒状導
電性金属酸化物の被覆量は、前記蛍光体量の0.01〜5.0
重量％であることが好ましく、前記粒状導電性金属酸化
物の含有量は、前記蛍光体の0.5〜10重量％であること
が好ましい。The coating amount of the homogeneous film-like or semi-homogeneous film-like conductive metal oxide and the granular conductive metal oxide is 0.01 to 5.0 of the phosphor amount.
The content of the granular conductive metal oxide is preferably 0.5 to 10% by weight of the phosphor.
蛍光体表面に均質膜状または半均質膜状金属酸化物を形
成するには、以下のような方法を用いることができる。In order to form a homogeneous film-like or semi-homogeneous film-like metal oxide on the phosphor surface, the following method can be used.
まず第１の方法としては、スパッタリングもしくは蒸着
法により、導電性金属酸化物の均質膜または半均質膜を
蛍光体表面に形成することが挙げられる。The first method is to form a homogeneous film or a semi-homogeneous film of a conductive metal oxide on the surface of the phosphor by sputtering or vapor deposition.
第２の方法としては、加熱、酸化することにより、容易
に導電性物質となり得るIn、Sn、Ti及びＷ等の有機化合
物例えばトリメチルインジウム（III）トリス（シクロ
ペンタジエニル）インジウム、トリフェニルインジウ
ム、ジエチルスズ、ジプロピルスズ、ジフェニルスズ、
トリクロロメチルチタン、テトラベンジルチタン、ヘキ
サメチルタングステン、ジクロロトリメチルニオブ等を
適当な有機溶媒例えばメタノール、エタノール等の低級
アルコール、エーテル等に溶解した溶液、またはこれら
の金属イオンをイオン会合体もしくはキレート化合物と
して有機溶媒中に抽出された溶液を用いる方法が挙げら
れる。具体的には、まず、これらの溶液中に蛍光体を分
散し、その後加温して有機溶媒を揮散させることによ
り、有機金属化合物を蛍光体表面にほぼ均一に付着させ
る。次に、得られた蛍光体を空気または弱還元雰囲気中
で450℃以上の温度で焼成することにより有機化合物が
分解し、金属酸化物が蛍光体表面を均質膜状または半均
質膜状に被覆する。As a second method, organic compounds such as In, Sn, Ti and W, which can easily become conductive substances by heating and oxidizing, such as trimethylindium (III) tris (cyclopentadienyl) indium, triphenylindium. , Diethyltin, dipropyltin, diphenyltin,
Trichloromethyltitanium, tetrabenzyltitanium, hexamethyltungsten, dichlorotrimethylniobium and the like dissolved in a suitable organic solvent such as lower alcohols such as methanol and ethanol, ether or the like, or these metal ions as an ion associate or chelate compound. The method of using the solution extracted in the organic solvent is mentioned. Specifically, first, the phosphor is dispersed in these solutions, and then heated to volatilize the organic solvent, thereby causing the organometallic compound to adhere to the phosphor surface almost uniformly. Next, the organic compound is decomposed by baking the obtained phosphor at a temperature of 450 ° C. or higher in air or a weak reducing atmosphere, and the metal oxide covers the phosphor surface in a homogeneous film or semi-homogeneous film form. To do.
第３の方法としては、第２の方法で用いたものと同様の
加熱、酸化を行うことにより、容易に導電性物質となり
得る金属を、水溶液中または水溶性有機溶媒中で硝酸
塩、硫酸塩及び塩化物として蛍光体表面に付着させる方
法が挙げられる。例えば硝酸塩として被覆するには、前
記金属の硝酸塩を水溶液中に溶解し、得られた水溶液に
蛍光体を懸濁させ、加熱することにより水分を蒸発させ
る。得られた蛍光体を450℃以上で焼成することによ
り、蛍光体表面に均質膜または半均質膜状の導電性金属
酸化物で被覆された低速電子線励起蛍光体が得られる。As a third method, by heating and oxidizing in the same manner as that used in the second method, a metal that can easily become a conductive substance is treated with nitrates, sulfates and salts in an aqueous solution or a water-soluble organic solvent. As a chloride, a method of attaching it to the surface of the phosphor can be mentioned. For example, to coat as a nitrate, the nitrate of the metal is dissolved in an aqueous solution, the phosphor is suspended in the obtained aqueous solution, and the water is evaporated by heating. By calcining the obtained phosphor at 450 ° C. or higher, a low-speed electron beam excitation phosphor in which the surface of the phosphor is coated with a conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film can be obtained.
また、上記方法の他に、他の産業分野で用いられている
例えばITO（酸化インジウム鉛）の導電膜を製造する方
法を用いてもよい。In addition to the above method, a method of manufacturing a conductive film of, for example, ITO (indium lead oxide) used in other industrial fields may be used.
このようにして蛍光体表面に均質膜状または半均質膜状
の導電性金属酸化物の被膜を形成し、更に、粒状導電性
金属酸化物を付着または混合することにより、本発明の
発光組成物が得られる。In this way, a film of a conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film is formed on the surface of the phosphor, and further, a granular conductive metal oxide is attached or mixed to give the luminescent composition of the present invention. Is obtained.
粒状導電性金属酸化物の付着方法としては、陰極線管用
蛍光体に顔料を付着させる方法と同じ方法を適用するこ
とができる。例えば、水中に低速電子線励起蛍光体及び
導電性金属酸化物を懸濁させ、ユリア樹脂エマルジョン
とゼラチンまたはゼラチンとアラビアゴムの組み合わ
せ、もしくはアクリル樹脂エマルジョン等の一般によく
用いられる有機バインダーを添加し、導電性金属酸化物
を蛍光体に付着させ、分離、乾燥することにより、粒状
導電性金属酸化物が付着された蛍光体を得ることができ
る。As the method for depositing the granular conductive metal oxide, the same method as the method for depositing the pigment on the phosphor for a cathode ray tube can be applied. For example, a slow electron beam excited phosphor and a conductive metal oxide are suspended in water, and a commonly used organic binder such as a urea resin emulsion and gelatin or a combination of gelatin and gum arabic, or an acrylic resin emulsion is added, By attaching the conductive metal oxide to the phosphor, separating and drying the phosphor, the phosphor having the particulate conductive metal oxide attached thereto can be obtained.
このようにして得られた発光組成物を用い、通常の方法
を用いて傾向表示管を製造することができる。例えば、
まず主として発光組成物とバインダーが練り合わされた
ペーストを形成し、次にそのペーストをスクリーン塗布
法、電着塗布法、沈殿塗布法等従来用いられている塗布
法を用いて通常５〜30mg/cm2の範囲で陽極プレートに塗
布する。そのプレートを乾燥した後、450℃以上で焼成
し、陽極プレート上に蛍光膜を作成する。その後通常の
一定距離をおいて陽極プレートを対向させ、一対の電極
とし、その電極をガラス等の容器内に封入し、10-5Torr
以上の真空度になったところで排気を止め封止する。そ
の後封止ゲッターを飛ばし、内部の真空度をさらに高
め、蛍光表示管が得られる。また、前記発光組成物の代
わりに、蛍光体と、加熱酸化することにより容易に導電
性金属酸化物となり得る金属の硝酸塩、硫酸塩、塩化物
及び有機化合物等が溶解された水溶液を用い、これらを
バインダーと混合してペーストを形成し、このペースト
を陽極プレート上に塗布し、同様にして450℃で焼成す
ることにより、蛍光膜を形成することもできる。Using the luminescent composition thus obtained, a trend display tube can be manufactured by a usual method. For example,
First, a paste in which the light-emitting composition and a binder are mainly kneaded is formed, and then the paste is usually used in an amount of 5 to 30 mg / cm by using a conventionally used coating method such as a screen coating method, an electrodeposition coating method, or a precipitation coating method. Apply to the anode plate in the range of 2 . After the plate is dried, it is baked at 450 ° C. or higher to form a fluorescent film on the anode plate. After that, the anode plates are opposed to each other at a regular distance to form a pair of electrodes, and the electrodes are sealed in a container such as glass and the temperature is 10 -5 Torr.
When the above degree of vacuum is reached, the exhaust is stopped and sealing is performed. After that, the sealing getter is skipped to further increase the degree of vacuum inside, and a fluorescent display tube is obtained. Further, instead of the light-emitting composition, a phosphor and an aqueous solution in which a metal nitrate, a sulfate, a chloride, an organic compound, or the like, which can easily become a conductive metal oxide by being heated and oxidized, are used, It is also possible to form a paste by mixing with a binder to form a paste, apply the paste on an anode plate, and similarly bake at 450 ° C. to form a fluorescent film.
本発明の発光組成物において、蛍光体に被覆、付着また
は混合する導電性金属酸化物の量は、発光組成物及びこ
れを用いた蛍光膜を使用した蛍光表示管の発光輝度と密
接な関係がある。均質膜または半均質膜状の導電性金属
酸化物の場合、被覆量は蛍光体量に対し好ましくは0.01
〜5.0重量％の範囲更に好ましくは0.05〜3.0重量％の範
囲であり、粒状導電性金属酸化物の場合、添加量は蛍光
体量に対し、0.5〜10.0重量％の範囲である。また前記
粒状導電性金属酸化物は、0.1〜2.0μｍの半径粒径を有
することがより好ましい。In the light emitting composition of the present invention, the amount of the conductive metal oxide coating, adhering to or mixing with the phosphor has a close relationship with the light emitting brightness of the fluorescent display tube using the light emitting composition and the fluorescent film using the same. is there. In the case of a homogeneous or semi-homogeneous film-like conductive metal oxide, the coating amount is preferably 0.01 with respect to the phosphor amount.
To 5.0% by weight, more preferably 0.05 to 3.0% by weight, and in the case of granular conductive metal oxide, the addition amount is 0.5 to 10.0% by weight based on the amount of the phosphor. Further, the granular conductive metal oxide more preferably has a radius particle diameter of 0.1 to 2.0 μm.
［作用］ 本発明の発光組成物では、蛍光体粒子表面に均質膜状ま
たは半均質膜状の導電性金属酸化物が被覆されていると
ともに、この蛍光体粒子にさらに粒状導電性金属酸化物
が混合または付着している。これら膜状及び粒状の２種
の導電性金属酸化物の存在により、低い駆動電圧によっ
ても、すなわち低速電子線によっても、励起され高輝度
の発光が可能となる。[Operation] In the light-emitting composition of the present invention, the surface of the phosphor particles is coated with a conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film, and the phosphor particles are further coated with a granular conductive metal oxide. Mixed or adhered. The presence of these two kinds of conductive metal oxides, film-like and granular, enables high-luminance light emission by being excited by a low driving voltage, that is, by a low-speed electron beam.
一方、粒状導電性金属酸化物の存在により、膜状の導電
性金属酸化物の被覆量は少なくてすむため、電子線はそ
れに妨げられることなく、容易に蛍光体に到達し、輝度
が低下することがない。On the other hand, due to the presence of the granular conductive metal oxide, the coating amount of the film-shaped conductive metal oxide can be small, so that the electron beam can easily reach the phosphor without lowering it and the brightness is reduced. Never.
［実施例］ 以下、図面を参照し、本発明の作用及び効果を説明す
る。[Examples] Hereinafter, the operation and effects of the present invention will be described with reference to the drawings.
第１図（ａ）及び第１図（ｂ）は、本発明の発光組成物
粒子の構造を示す電子顕微鏡写真図である。第１図
（ａ）は、青色発光蛍光体（ZnS:Ag,Al）に1.0重量％の
In2O3の均一膜または半均一膜を被覆した低速電子線励
起蛍光体粒子の構造を示し、第１図（ｂ）は、第１図
（ａ）の蛍光体に粒状のIn2O3を乾式混合して得られた
本発明の発光組成物粒子の構造を示す。本発明の蛍光体
は、蛍光体表面に第１図（ａ）に示すような均一膜状ま
たは半均一膜状の導電性金属酸化物を形成し、さらに、
粒状のIn2O3を混合した構造を有する。1 (a) and 1 (b) are electron micrographs showing the structure of the luminescent composition particles of the present invention. FIG. 1 (a) shows a blue light emitting phosphor (ZnS: Ag, Al) containing 1.0% by weight.
FIG. 1B shows the structure of a slow electron beam excited phosphor particle coated with a uniform or semi-uniform film of In 2 O 3 , and FIG. 1B shows granular In 2 O 3 in the phosphor of FIG. 1A. The structure of the luminescent composition particles of the present invention obtained by dry-mixing is shown. The phosphor of the present invention has a uniform metal film-like or semi-uniform film-like conductive metal oxide as shown in FIG.
It has a structure in which granular In 2 O 3 is mixed.
第２図は、青色発光蛍光体（ZnS:Ag,Al）に対し、2.5重
量％の均質膜状のIn2O3が被覆された低速電子線励起蛍
光体に、さらに、平均粒径１μｍの粒状のIn2O3を5.0重
量％の乾式混合した本発明に係る発光組成物（ａ）、2.
5重量％の均質膜状のIn2O3を被覆した低速電子線励起蛍
光体（ｂ）、平均粒径３μｍのIn2O3を前記青色発光蛍
光体に対し、1.0重量％乾式混合した従来の発光組成物
（ｃ）及びIn2O3を10.0重量％乾式混合する以外は発光
組成物（ｃ）と同様にして得られた従来の発光組成物
（ｄ）を各々蛍光表示管に実装し、駆動電圧（陽極プレ
ート）を変化させた際の駆動電圧と相対発光輝度の関係
を表すグラフ図である。なお、相対輝度は発光組成物
（ｄ）を実装した蛍光表示管を50Vで駆動させたときの
発光輝度を100％として表した。FIG. 2 shows a slow-electron-beam-excited phosphor coated with 2.5% by weight of a homogeneous film of In 2 O 3 on a blue-emitting phosphor (ZnS: Ag, Al), and further with an average particle size of 1 μm. 2. Luminescent composition (a) according to the present invention in which 5.0% by weight of granular In 2 O 3 is dry mixed.
5 wt% of the homogeneous membrane of In 2 O 3 low voltage electron beam excitation phosphor coated with (b), wherein the In 2 O 3 having an average particle diameter of 3μm to blue-emitting phosphor, 1.0 wt% dry mixed with conventional The conventional light-emitting composition (d) obtained in the same manner as the light-emitting composition (c) except that the light-emitting composition (c) and the In 2 O 3 of 10.0 wt% were dry mixed were mounted on a fluorescent display tube. FIG. 6 is a graph showing the relationship between the drive voltage and the relative light emission brightness when the drive voltage (anode plate) is changed. The relative luminance is represented by assuming that the emission luminance when the fluorescent display tube having the light emitting composition (d) mounted thereon is driven at 50 V is 100%.
第２図から明らかなように、In2O3の被覆された低速電
子線励起蛍光体（ｂ）を実装した蛍光表示管は、70V以
下の低駆動電圧域では導電性が優れているために発光開
始電圧が低く、従来の発光組成物（ｄ）を実装した蛍光
表示管よりも輝度は高くなる。しかし、駆動電圧が70V
を越えると、発光組成物（ｄ）の方が導電性が勝ってい
るために、発光組成物（ｂ）を実装した蛍光表示管と輝
度が変わらなくなる。これに対し、本発明にかかる発光
組成物（ａ）を実装した蛍光表示管は、導電性金属酸化
物を均質膜状または半均質膜状に被覆し、かつ粒状に混
合することにより、導電性金属酸化物を被覆させたもの
（発光組成物（ｂ））と混合させたもの（発光組成物
（ｃ），（ｄ）との特徴を生かし、高駆動電圧域におい
ても高い発光輝度を維持することができる。As is apparent from FIG. 2, the fluorescent display tube mounted with the In 2 O 3 -coated slow electron beam excitation phosphor (b) has excellent conductivity in a low driving voltage range of 70 V or less. The light emission starting voltage is low, and the brightness is higher than that of the conventional fluorescent display tube mounted with the light emitting composition (d). However, the drive voltage is 70V
Beyond the above, since the light emitting composition (d) is superior in conductivity, the brightness is not different from that of the fluorescent display tube mounted with the light emitting composition (b). On the other hand, the fluorescent display tube on which the light emitting composition (a) according to the present invention is mounted has a conductive metal oxide coated in a homogeneous film form or a semi-homogeneous film form, and is mixed in a granular form so as to have a conductive property. Utilizing the characteristics of the one coated with a metal oxide (light emitting composition (b)) and the one mixed with one (light emitting composition (c), (d), high emission brightness is maintained even in a high driving voltage range. be able to.
第３図は、青色発光蛍光体（ZnS:Ag,Al）に対し、In2O3
を0.1、1.0、2.0、5.0重量％被覆した低速電子線励起蛍
光体に、さらに平均粒径1.0μｍの粒状In2O3をその混合
量を変化させて、各々蛍光表示管に実装し、駆動電圧50
Vの条件下で発光させた場合の相対輝度を示す。この被
覆量及び混合量の合計であるIn2O3の添加量と相対輝度
との関係を第３図に実線で示す。また、参考のためIn2O
3の均質膜を被覆した青色発光蛍光体の被覆量を変化さ
せたときの相対輝度を破線で、平均粒径３μｍの粒状In
2O3を混合量を変化させたときの相対輝度を一点鎖線で
表し、同グラフに示す。なお、相対輝度は、In2O3を蛍
光体に対し10重量％乾式混合した従来の発光組成物を実
装した蛍光表示管の輝度を100％としたときの相対輝度
である。Fig. 3 shows In 2 O 3 for blue light emitting phosphor (ZnS: Ag, Al).
0.1%, 1.0%, 2.0%, 5.0% by weight of a low-speed electron beam excited phosphor, and granular In 2 O 3 having an average particle size of 1.0 μm was mixed and changed, and each was mounted on a fluorescent display tube and driven. Voltage 50
The relative luminance when light is emitted under the condition of V is shown. The relationship between the added amount of In 2 O 3 , which is the total of the coating amount and the mixing amount, and the relative luminance is shown by a solid line in FIG. Also, for reference, In 2 O
The relative brightness when the coating amount of the blue light-emitting phosphor coated with the homogeneous film of 3 was changed with a broken line, and the average In particle size of 3 μm
The relative brightness when changing the mixing amount of 2 O 3 is shown by a dashed line and is shown in the same graph. The relative brightness is a relative brightness when the brightness of a fluorescent display tube mounted with a conventional light emitting composition in which In 2 O 3 is dry mixed with a phosphor is 10% by weight is 100%.
また第４図は、赤色発光蛍光体｛（ZnCd）S:Cu,Cl｝に
対し、同じくIn2O3を0.05、0.2、0.5、2.0重量％被覆し
た低速電子線励起蛍光体に対し、粒状のIn2O3をその混
合量を変化させて各々蛍光表示管に実装し、駆動電圧50
V条件下で発光させた場合の相対輝度を示す。このIn2O3
の添加量と相対輝度との関係を第４図に実線で示す。ま
た、参考のためIn2O3の均質膜を被覆した青色発光蛍光
体の被覆量を変化させたときの相対輝度を破線で、平均
粒径３μｍの粒状In2O3を混合量を変化させたときの相
対輝度を一点鎖線で表し、同グラフに示す。なお、相対
輝度は、In2O3を蛍光体に対し10重量％乾式混合した従
来の発光組成物を実装した蛍光表示管の輝度を100％と
したときの輝度である。In addition, FIG. 4 shows that the red light emitting phosphor {(ZnCd) S: Cu, Cl} is coated with 0.05, 0.2, 0.5 and 2.0% by weight of In 2 O 3 in the slow electron beam excited phosphor, and In 2 O 3 of the above are mounted on the respective fluorescent display tubes by changing the mixing amount, and the driving voltage is 50
The relative luminance when light is emitted under V conditions is shown. This In 2 O 3
The relationship between the amount of addition of R and the relative luminance is shown by the solid line in FIG. For reference, the relative brightness when the coating amount of the blue light emitting phosphor coated with a homogeneous film of In 2 O 3 is changed is a broken line, and the mixing amount of granular In 2 O 3 having an average particle diameter of 3 μm is changed. The relative brightness at that time is shown by a chain line and is shown in the same graph. The relative brightness is the brightness when the brightness of a fluorescent display tube mounted with a conventional light emitting composition in which In 2 O 3 is dry mixed with 10% by weight is 100%.
第３図及び第４図から明らかなように、発光を開始する
ためには、、多くのIn2O3の添加を必要とするが、本発
明の発光組成物を実装した蛍光表示管は、わずかな膜状
のIn2O3の被覆でも発光を開始し、順次粒状In2O3を混合
していくことによって輝度が増加していく、しかし膜状
のIn2O3が10重量％被覆された低速電子線励起蛍光体に
粒状のIn2O3を混合した発光組成物は、非発光物質であ
るIn2O3が蛍光体の発光を吸収し、また蛍光表示管の陽
極プレート上にある単位面積当たりの蛍光体量が少なく
なってしまうため、多きな輝度の増加が望めない。その
ため、本発明の発光組成物において膜状の導電性物質の
被覆量と、粒状の導電性物質の混合量の組み合わせは、
膜状の導電性物質が0.05〜3.0重量％被覆された低速電
子線励起発光体に1.0〜5.0重量％の粒状の導電性物質の
混合がさらに好ましい。As is clear from FIGS. 3 and 4, a large amount of In 2 O 3 needs to be added to start light emission, but the fluorescent display tube mounted with the light emitting composition of the present invention has Light emission starts even with a small amount of film-like In 2 O 3 coating, and the brightness increases as the granular In 2 O 3 is mixed in sequence, but 10% by weight of film-like In 2 O 3 is coated. low voltage electron beam excitation phosphor emission composition comprising a mixture of in 2 O 3 of granular material which is in, in 2 O 3 is a non-luminescent material absorbs the light emitted from the phosphor, also on the anode plate of a fluorescent display tube Since the amount of phosphor per unit area decreases, a large increase in luminance cannot be expected. Therefore, in the luminescent composition of the present invention, the combination of the coating amount of the film-shaped conductive substance and the mixed amount of the granular conductive substance is
It is more preferable to add 1.0 to 5.0% by weight of the granular conductive material to the slow electron beam excited luminescent material coated with 0.05 to 3.0% by weight of the film-shaped conductive material.
次に、第５図は、青色発光蛍光体（ZnS:Ag,Cl）に対しI
n2O31重量％を被覆した低速電子線励起蛍光体に、混合
する粒状のIn2O3の粒径を変化させた各々の本発明の発
光組成物を蛍光表示管に実装し、その輝度を測定して、
その相対輝度と平均粒径との関係を示すグラフ図であ
る。第５図から明らかなように、本発明の発光組成物に
おいては混合する導電性金属酸化物の平均粒径は0.1〜
２μｍであることが好ましいことがわかる。Next, FIG. 5 shows the relationship between the blue emission phosphor (ZnS: Ag, Cl) and I
A slow electron beam excited phosphor coated with 1% by weight of n 2 O 3 was mounted on a fluorescent display tube with each light emitting composition of the present invention in which the particle size of the granular In 2 O 3 to be mixed was changed. Measure the brightness,
It is a graph figure which shows the relationship between the relative brightness | luminance and average particle diameter. As is clear from FIG. 5, in the light emitting composition of the present invention, the average particle diameter of the conductive metal oxide mixed is 0.1 to
It can be seen that the thickness is preferably 2 μm.
以上のことから、蛍光体は膜状の導電性金属酸化物で被
覆されることにより、低い駆動電圧でも発光を開始する
ことができるようになり、高輝度を発することができ
る。From the above, by coating the phosphor with the film-shaped conductive metal oxide, it becomes possible to start light emission even at a low drive voltage, and high brightness can be emitted.
しかし、蛍光体表面に膜状の導電性金属酸化物が被覆さ
れた発光組成物は、導電性酸化物量が増加するに従い、
陰極から発せられた電子線が逆に被覆がバリヤーとなっ
てしまうために蛍光体に到達しがたくなり、輝度が低下
する傾向がある。一方、粒状の導電性金属酸化物のみが
混合された従来の発光組成物は、電子線に対するバリヤ
ー効果は少ないが、導電性物質としての効果が高いた
め、多量に添加しないとその効果は得られない傾向があ
る。However, the light-emitting composition in which a film-shaped conductive metal oxide is coated on the surface of the phosphor has an increase in the amount of the conductive oxide,
On the contrary, the electron beam emitted from the cathode makes it difficult for the electron beam to reach the phosphor because the coating becomes a barrier, and the brightness tends to decrease. On the other hand, the conventional light-emitting composition in which only the granular conductive metal oxide is mixed has a small barrier effect against the electron beam, but since the effect as a conductive substance is high, the effect can be obtained unless added in a large amount. Tend not to.
そこで本発明の発光組成物は、バリヤー効果の少ない範
囲で導電性物質の被膜を形成し、さらに粒状の導電性物
質を補うことにより両者の特性をいかし、輝度を向上さ
せたものである。Therefore, the light-emitting composition of the present invention forms a film of a conductive substance in a range having a small barrier effect, and further supplements the granular conductive substance to make use of the characteristics of both to improve the brightness.
以下、本発明の種々の実施例を示す。Hereinafter, various examples of the present invention will be shown.
実施例１ In2O3ターゲットをスパッタ装置に設置し、緑色発光蛍
光体（ZnS:Cu,Al）50gの表面にIn2O3のスパッタリング
を行なった。Example 1 An In 2 O 3 target was set in a sputtering apparatus, and In 2 O 3 was sputtered on the surface of 50 g of a green light emitting phosphor (ZnS: Cu, Al).
In2O3被膜の付着量が蛍光体に対し、１重量％になるま
でスパッタリングを行い、低速電子線励起蛍光体を得
た。Sputtering was performed until the amount of the In 2 O 3 coating deposited on the phosphor was 1% by weight to obtain a low-speed electron beam excited phosphor.
さらに、この蛍光体に平均粒径1.0μｍのIn2O3蛍光体に
対し8.0重量％となるよう添加し、十分乾式混合して本
発明の緑色発光組成物を得た。次にこの緑色発光組成物
に5.0重量％のPVA水溶液30gを添加し、十分練り合わせ
た後、セラミック基板に指示された1cm2の金属の陽極プ
レート上にスクリーン塗布し、乾燥した。その陽極プレ
ートをセラミック基板ごと450℃で30分間焼成してPVAを
分解し、蛍光膜を得た。さらにカルシウム、ストロンチ
ウム及びバリウムの酸化物によって被覆されたタングス
テン線状ヒータの陰極を前記蛍光膜から約5mmの間隔を
おいて設置し、これら一対の電極をガラス容器内に設置
した。ガラス容器内の排気を行い10-5Torrぐらいの圧力
でガラス容器を封止し、次いでゲッターを飛して真空度
を高め、蛍光表示管を得た。Further, to this phosphor, 8.0 wt% was added to In 2 O 3 phosphor having an average particle diameter of 1.0 μm, and sufficiently dry mixed to obtain a green light emitting composition of the present invention. Next, 30 g of a 5.0 wt% PVA aqueous solution was added to this green light emitting composition, and after sufficiently kneading, screen coating was performed on a 1 cm 2 metal anode plate indicated on the ceramic substrate, and drying was performed. The anode plate together with the ceramic substrate was baked at 450 ° C. for 30 minutes to decompose PVA and obtain a fluorescent film. Further, a cathode of a tungsten linear heater covered with oxides of calcium, strontium and barium was placed at a distance of about 5 mm from the phosphor film, and a pair of these electrodes was placed in a glass container. The inside of the glass container was evacuated, and the glass container was sealed at a pressure of about 10 −5 Torr, and then the getter was blown to increase the degree of vacuum to obtain a fluorescent display tube.
また比較例１として同様の緑色発光蛍光体に対し、平均
粒径４μｍのIn2O3を10重量％混合した従来の発光組成
物を作成し、同様にして蛍光表示管を作成した。これら
蛍光表示管を陽極プレート電圧（駆動電圧）50V、陰極
電圧1.2V、電流密度2mA/cm2の条件下でそれぞれ発光さ
せたところ、従来の低速電子線励起緑色発光蛍光体を実
装した蛍光表示管の輝度を100％とすると、本発明の緑
色発光組成物を実装した蛍光表示管のの輝度は170％で
あった。Further, as Comparative Example 1, a conventional light emitting composition was prepared by mixing 10% by weight of In 2 O 3 having an average particle size of 4 μm with the same green light emitting phosphor, and a fluorescent display tube was prepared in the same manner. When these fluorescent display tubes were made to emit light under the conditions of an anode plate voltage (driving voltage) of 50 V, a cathode voltage of 1.2 V, and a current density of 2 mA / cm 2 , the fluorescent display mounted with a conventional slow-electron-beam-excited green-emitting phosphor. When the brightness of the tube was 100%, the brightness of the fluorescent display tube mounted with the green light-emitting composition of the present invention was 170%.
実施例２ SnO2ターゲットを使用しただけで後は実施例１と同様に
して青色発光蛍光体（ZnS:Ag,Al）50gに対し1.0重量％
のSnO2の均一被膜を形成し、さらに平均粒径1.0μｍのS
nO2を青色発光蛍光体量に対し7.0重量％混合し、本発明
の青色発光組成物を得た。また比較例２として従来の平
均粒径３μｍのSnO2を混合させた青色発光組成物を用
い、実施例１と同様にして各々蛍光表示管を作成して発
光させたところ、従来の低速電子線励起青色発光組成物
を実装した蛍光表示管の輝度を100％とすると、本発明
の青色発光組成物を実装した蛍光表示管の輝度は165％
であった。Example 2 The same procedure as in Example 1 except that the SnO 2 target was used, and 1.0% by weight based on 50 g of the blue light emitting phosphor (ZnS: Ag, Al).
A uniform SnO 2 film is formed, and S with an average particle size of 1.0 μm is formed.
7.0% by weight of nO 2 was mixed with the amount of the blue light emitting phosphor to obtain a blue light emitting composition of the present invention. Further, as Comparative Example 2, a conventional blue light-emitting composition in which SnO 2 having an average particle diameter of 3 μm was mixed was used, and a fluorescent display tube was produced in the same manner as in Example 1 to emit light. When the brightness of the fluorescent display tube mounted with the excited blue light emitting composition is 100%, the brightness of the fluorescent display tube mounted with the blue light emitting composition of the present invention is 165%.
Met.
実施例３ 加熱酸化により導電性金属酸化物となり得る有機溶媒可
溶性金属化合物としてIn2O3換算で５重量％、SnO2換算
で0.5重量％を含むアトロンNIn（商標 日本曹達（株）
製）を用いた。Example 3 Atron NIn (trademark Nippon Soda Co., Ltd.) containing 5% by weight as In 2 O 3 and 0.5% by weight as SnO 2 as an organic solvent-soluble metal compound capable of becoming a conductive metal oxide by thermal oxidation.
Manufactured) was used.
このアトロンNIn20gをエタノール100mlに溶解し、この
エタノール中に黄色発光蛍光体｛（ZnCd）S:Ag,Al｝100
gを添加し、十分懸濁させた後、60℃に加温してエタノ
ールを輝散させた。20 g of this Atron NIn is dissolved in 100 ml of ethanol, and the yellow light emitting phosphor {(ZnCd) S: Ag, Al} 100 is dissolved in this ethanol.
After adding g and suspending sufficiently, it was heated to 60 ° C. and ethanol was diffused.
この蛍光体を取り出し、空気中で500℃にて１時間焼成
を行った後、黄色発光蛍光体に対しIn2O3が1.0重量％、
SnO2が0.1重量％含まれる導電性金属酸化物の均質膜に
よって被覆された低速電子線励起黄色発光蛍光体を得
た。This phosphor was taken out and baked in air at 500 ° C. for 1 hour, and then 1.0% by weight of In 2 O 3 was added to the yellow light-emitting phosphor.
A slow-electron-beam-excited yellow-emitting phosphor covered with a homogeneous film of a conductive metal oxide containing 0.1% by weight of SnO 2 was obtained.
得られた低速電子線励起黄色発光蛍光体にさらに最初の
黄色発光蛍光体に対し5.0重量％のIn2O3を混合し、本発
明の黄色発光組成物を得た。The obtained slow-electron-beam-excited yellow light-emitting phosphor was further mixed with 5.0% by weight of In 2 O 3 based on the first yellow light-emitting phosphor to obtain a yellow light-emitting composition of the present invention.
比較例３として実施例３と同様の黄色発光蛍光体に対
し、平均粒径４μｍとIn2O3を10.0重量％混合した従来
の黄色発光蛍光体を作成した。As Comparative Example 3, a conventional yellow light emitting phosphor was prepared by mixing the same yellow light emitting phosphor as in Example 3 with an average particle size of 4 μm and In 2 O 3 at 10.0% by weight.
これら低速電子線励起黄色発光組成物各々50gを用いて
実施例１と同様にして各々蛍光表示管を作成し、輝度を
測定したところ、従来の低速電子線励起黄色発光組成物
を実装した蛍光表示管の輝度を100％とすると、本発明
の蛍光組成物を実装した蛍光表示管の輝度は、160％で
あった。Using 50 g of each of these slow-electron-beam-excited yellow light-emitting compositions, a fluorescent display tube was prepared in the same manner as in Example 1 and the brightness was measured. When the brightness of the tube was 100%, the brightness of the fluorescent display tube mounted with the fluorescent composition of the present invention was 160%.
実施例４ 青色発光蛍光体（ZnS:Ag,Al）と黄色発光蛍光体（ZnS:A
u,Al）とを1:2の重量比で混合した白色発光組成物100g
を用意し、実施例３と同様にしてアトロンNInを用い、
前記白色発光組成物に対し、In2O31.0重量％、SnO2が0.
1重量％被覆された低速電子線励起白色発光組成物を得
た。Example 4 Blue light emitting phosphor (ZnS: Ag, Al) and yellow light emitting phosphor (ZnS: A)
u, Al) and a white light-emitting composition 100 g mixed in a weight ratio of 1: 2.
And using Atron NIn in the same manner as in Example 3,
1.0% by weight of In 2 O 3 and SnO 2 with respect to the white light emitting composition.
A low-electron-beam-excited white light-emitting composition coated with 1% by weight was obtained.
得られた発光組成物に平均粒径１μｍのIn2O3を最初の
白色発光組成物に対し5.0重量％混合し、本発明の低速
電子線励起白色発光蛍光体を得た。In 2 O 3 having an average particle size of 1 μm was mixed with the obtained light emitting composition in an amount of 5.0% by weight with respect to the initial white light emitting composition to obtain a slow electron beam excited white light emitting phosphor of the present invention.
比較例４として実施例４と同様の白色発光蛍光体に対
し、平均粒径４μｍのIn2O3を10重量％混合した白色発
光組成物を調製した。As Comparative Example 4, a white light emitting composition was prepared by mixing 10% by weight of In 2 O 3 having an average particle size of 4 μm with the same white light emitting phosphor as in Example 4.
これら低速電子線励起黄色発光組成物各々50gを用いて
実施例１と同様にして各々蛍光表示管を作成し、輝度を
測定したところ、従来の低速電子線励起白色発光組成物
を実装した蛍光表示管の輝度を100％とすると、本発明
の発光組成物を実装した蛍光表示管の輝度は、155％で
あった。Using 50 g of each of these slow-electron-beam-excited yellow light-emitting compositions, a fluorescent display tube was prepared in the same manner as in Example 1, and the brightness was measured. When the brightness of the tube was 100%, the brightness of the fluorescent display tube mounted with the light emitting composition of the present invention was 155%.
実施例５ 赤色発光蛍光体｛（ZnCd）S:Cu,Cl｝100gを50mlの水中
に添加し、十分撹拌した。Example 5 100 g of the red light emitting phosphor {(ZnCd) S: Cu, Cl} was added to 50 ml of water and sufficiently stirred.
この懸濁液にIn2O3換算含有1.0重量％のIn2（SO4）３水
溶液20gを添加し、再び十分撹拌した後、静置して80℃
に加温して水を蒸発させた。乾燥した蛍光体を500℃で
焼成し、低速電子線励起赤色発光蛍光体を得た。20 g of an In 2 (SO 4 ) 3 aqueous solution containing 1.0 wt% of In 2 O 3 was added to this suspension, and after sufficiently stirring again, the mixture was allowed to stand still at 80 ° C.
Warmed to evaporate the water. The dried phosphor was fired at 500 ° C. to obtain a slow electron beam excited red light emitting phosphor.
比較例５として実施例５と同様の赤色発光蛍光体に対
し、平均粒径４μｍのIn2O3を5.0重量％混合し、低速電
子線励起赤色発光蛍光体を得た。As Comparative Example 5, 5.0% by weight of In 2 O 3 having an average particle diameter of 4 μm was mixed with the same red light emitting phosphor as in Example 5 to obtain a slow electron beam excited red light emitting phosphor.
これらの蛍光体を各々50gを用いて実施例１と同様にし
て蛍光表示管を作成し、輝度を測定したところ、従来の
低速電子線励起赤色発光組成物を実装した蛍光表示管の
輝度を100％とすると、本発明の発光組成物を実装した
蛍光表示管の輝度は150％であった。Using 50 g of each of these phosphors, a fluorescent display tube was prepared in the same manner as in Example 1 and the brightness was measured. The brightness of the conventional fluorescent display tube mounted with the slow electron beam excited red light emitting composition was 100%. %, The brightness of the fluorescent display tube mounted with the light emitting composition of the present invention was 150%.
実施例６ 橙色発光蛍光体｛（ZnCd）S:Cu,Cl｝100gを50mlのエタ
ノール中に添加し、十分撹拌した。この懸濁液にIn2O3
換算含量1.0重量％のIn（NO3）３・3H2Oの水溶液20gを
添加し、再び十分撹拌した後、静置して50℃に加温し、
エタノール及び水を蒸発させた。このようにして乾燥し
た蛍光体を同じく500℃で焼成し、平均粒径1.0μｍのIn
2O3を4.0重量％乾式混合し、本発明に係る低速電子線励
起橙色発光蛍光体を得た。Example 6 100 g of the orange light emitting phosphor {(ZnCd) S: Cu, Cl} was added to 50 ml of ethanol and sufficiently stirred. In 2 O 3
Was added in terms of content 1.0 wt% of In (NO 3) 3 · 3H 2 O in aqueous solution 20g, was again thoroughly stirred, and left standing warmed to 50 ° C.,
The ethanol and water were evaporated. The phosphor thus dried was also fired at 500 ° C. to obtain an In particle having an average particle size of 1.0 μm.
4.0 wt% of 2 O 3 was dry mixed to obtain a slow electron beam excited orange light emitting phosphor according to the present invention.
比較例６として実施例６と同様の赤色発光蛍光体に対
し、平均粒径４μｍのIn2O3を5.0重量％混合し、低速電
子線励起橙色発光蛍光体を得た。As Comparative Example 6, 5.0% by weight of In 2 O 3 having an average particle size of 4 μm was mixed with the red light emitting phosphor similar to that of Example 6 to obtain a slow electron beam excited orange light emitting phosphor.
これらの蛍光体を各々50gを用いて実施例１と同様にし
て蛍光表示管を作成し、輝度を測定したところ、従来の
低速電子線励起橙色発光組成物を実装した蛍光表示管の
輝度を100％とすると、本発明の発光組成物を実装した
蛍光表示管の輝度は165％であった。Using 50 g of each of these phosphors, a fluorescent display tube was prepared in the same manner as in Example 1 and the brightness was measured. The brightness of the conventional fluorescent display tube mounted with the slow electron beam excited orange light emitting composition was 100%. %, The brightness of the fluorescent display tube mounted with the light emitting composition of the present invention was 165%.
以上実施例１〜６からわかるように、本発明の発光組成
物を用いると、50Vの低速電子線励起のものであって
も、従来の発光組成物よりも高輝度を有する優れた蛍光
表示管が得られる。As can be seen from Examples 1 to 6 above, when the light emitting composition of the present invention is used, an excellent fluorescent display tube having higher brightness than the conventional light emitting composition even if it is excited by a slow electron beam of 50V. Is obtained.
［発明の効果］ 以上説明したように、本発明によれば蛍光体表面に均質
膜または半均質膜状の導電性金属酸化物を被覆すること
により、発光開始電圧が低減され、1kV以下特に100V以
下の低速電子線励起のもとで十分な導電性及び発光輝度
をを有する蛍光体が得られ、さらに粒状導電性金属酸化
物を混合することにより、輝度がさらに向上する。[Effects of the Invention] As described above, according to the present invention, by coating the surface of the phosphor with the conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film, the light emission starting voltage is reduced, and the voltage is 1 kV or less, especially 100 V A phosphor having sufficient conductivity and emission brightness can be obtained under the following low-speed electron beam excitation, and the brightness is further improved by further mixing a granular conductive metal oxide.
また、本発明によれば、輝度だけでなく、陽極プレート
への塗布特性、蛍光体の劣化等についても従来の低速電
子線励起蛍光体と同等またはそれ以上の特性を示す発光
組成物が得られる。Further, according to the present invention, it is possible to obtain a luminescent composition exhibiting not only the brightness but also the coating characteristics on the anode plate, the deterioration of the phosphor, and the like, which are equal to or higher than those of the conventional slow electron beam excited phosphor. .
さらに、本発明に係る発光組成物を、蛍光表示管だけで
なく薄型陰極線管の蛍光面に適用することができる。さ
らに、原料として用いる蛍光体としてランプ用蛍光体を
用いると、導電性を有する蛍光体を必要とするラピッド
スタート型蛍光ランプ用発光組成物として使用すること
も可能である。Furthermore, the light emitting composition according to the present invention can be applied not only to the fluorescent display tube but also to the fluorescent surface of the thin cathode ray tube. Furthermore, when a fluorescent substance for a lamp is used as the fluorescent substance used as a raw material, it can be used as a light emitting composition for a rapid start type fluorescent lamp which requires a fluorescent substance having conductivity.
第１図（ａ）、本発明にかかる発光組成物において、導
電性金属酸化物が半均質膜が表面に形成された発光組成
物粒子の構造を示す電子顕微鏡写真図、第１図（ｂ）
は、本発明にかかる発光組成物において、導電性金属酸
化物粒子が導電性金属酸化物の半均質膜非表面に付着さ
れた発光組成物粒子の構造を示す電子顕微鏡写真図、第
２図は、本発明の一実施例及び比較例に係る駆動電圧と
相対発光輝度の関係を表すグラフ図、第３図は、本発明
の一実施例及び比較例に係る導電性物質の添加量と相対
輝度の関係を表すグラフ図、第４図は本発明の一実施例
及び比較例に係る導電性物質の添加量と相対輝度の関係
を表すグラフ図、第５図は相対輝度と平均粒径との関係
を示すグラフ図である。1 (a), an electron micrograph showing the structure of a luminescent composition particle in which a semi-homogeneous film of a conductive metal oxide is formed on the surface of the luminescent composition according to the present invention, FIG. 1 (b).
Is an electron micrograph showing the structure of the luminescent composition particles in which the conductive metal oxide particles are attached to the non-homogeneous film of the conductive metal oxide in the luminescent composition according to the present invention. FIG. 3 is a graph showing the relationship between the driving voltage and the relative light emission luminance according to the embodiment and the comparative example of the present invention, and FIG. FIG. 4 is a graph showing the relationship between the added amount of the conductive material and the relative brightness according to one example and comparative example of the present invention, and FIG. 5 is a graph showing the relative brightness and the average particle size. It is a graph which shows a relationship.
Claims (4)
導電性金属酸化物で被覆された低速電子線励起蛍光体
と、該蛍光体に混合または付着された粒状導電性金属酸
化物とを含む発光組成物であって、前記均質膜状または
半均質膜状の導電性金属酸化物及び粒状導電性金属酸化
物は、In2O3及びSnO2からなる群から選択された少なく
とも１種であり、前記均質膜状または半均質膜状の導電
性金属酸化物は、有機溶媒に溶解された前記導電性金属
の有機化合物を加熱により導電性金属化合物にせしめる
か、あるいは前記導電性金属を蒸着またはスパッタリン
グすることにより形成されることを特徴とする発光組成
物。1. A slow-electron-beam-excited phosphor whose surface is coated with a conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film, and a granular conductive metal oxide mixed or attached to the phosphor. And a conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film, and a granular conductive metal oxide, which are at least 1 selected from the group consisting of In 2 O 3 and SnO 2. The conductive metal oxide in the form of a homogeneous film or a semi-homogeneous film is a conductive metal compound obtained by heating an organic compound of the conductive metal dissolved in an organic solvent by heating, or the conductive metal. A luminescent composition formed by vapor-depositing or sputtering.
1はAg、Zn、Cu、Au及びMnからなる群から選択された少
なくとも１種の元素であり、M2はAl、Ｆ、Cl、Br及びＩ
からなる群から選択された少なくとも１種の元素であ
る。）で表される蛍光体及び一般式（ZnCd）S:M1,M2（M
1及びM2は上記と同じ）で表される蛍光体からなる群か
ら選択された少なくとも１種であることを特徴とする請
求項１に記載の発光組成物。2. The phosphor of the general formula ZnS: M 1 , M 2 (provided that M
1 is at least one element selected from the group consisting of Ag, Zn, Cu, Au and Mn, and M 2 is Al, F, Cl, Br and I
It is at least one element selected from the group consisting of: ) And the general formula (ZnCd) S: M 1 , M 2 (M
The luminescent composition according to claim 1, wherein 1 and M 2 are at least one selected from the group consisting of the phosphors represented by the above).
は、0.05μｍ以上2.0μｍ以下であることを特徴とする
請求項１〜３のいずれかに記載の発光組成物。3. The luminescent composition according to claim 1, wherein the volume average particle diameter of the granular conductive metal oxide is 0.05 μm or more and 2.0 μm or less.
酸化物の被覆量は、前記蛍光体量の0.01〜5.0重量％で
あり、前記粒状導電性金属酸化物の含有量は、前記蛍光
体の0.5〜10重量％である請求項１〜４のいずれかに記
載の発光組成物。4. The coating amount of the homogeneous film-like or semi-homogeneous film-like conductive metal oxide is 0.01 to 5.0% by weight of the phosphor amount, and the content of the granular conductive metal oxide is the above-mentioned. The luminescent composition according to claim 1, which is 0.5 to 10% by weight of the phosphor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2110559A JPH0717899B2 (en) | 1990-04-27 | 1990-04-27 | Luminescent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2110559A JPH0717899B2 (en) | 1990-04-27 | 1990-04-27 | Luminescent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH048794A JPH048794A (en) | 1992-01-13 |
| JPH0717899B2 true JPH0717899B2 (en) | 1995-03-01 |
Family
ID=14538903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2110559A Expired - Fee Related JPH0717899B2 (en) | 1990-04-27 | 1990-04-27 | Luminescent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717899B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5320507A (en) * | 1991-10-17 | 1994-06-14 | Copeland Corporation | Scroll machine with reverse rotation protection |
| US5593294A (en) * | 1995-03-03 | 1997-01-14 | Copeland Corporation | Scroll machine with reverse rotation protection |
| KR100280993B1 (en) * | 1997-12-31 | 2001-02-01 | 김순택 | Low voltage phosphor and its manufacturing method |
| JP4568952B2 (en) * | 2000-04-19 | 2010-10-27 | 三菱化学株式会社 | Phosphor surface treatment method and phosphor film |
| CA2363532A1 (en) * | 2000-12-18 | 2002-06-18 | Osram Sylvania Inc. | Preparation of high-brightness, long life, moisture resistant electroluminescent phosphor |
| JP4804646B2 (en) * | 2001-05-16 | 2011-11-02 | ノリタケ伊勢電子株式会社 | Low speed electron beam phosphor and fluorescent display tube |
| US20090212686A1 (en) * | 2008-02-21 | 2009-08-27 | Semiconductor Energy Laboratory Co., Ltd. | Inorganic el blue-light emitting body, method for manufacturing the same, and light emitting device |
Family Cites Families (1)
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|---|---|---|---|---|
| JP2525649B2 (en) * | 1988-08-01 | 1996-08-21 | 化成オプトニクス株式会社 | Luminescent composition |
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1990
- 1990-04-27 JP JP2110559A patent/JPH0717899B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH048794A (en) | 1992-01-13 |
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