JP2971496B2 - Method for producing slow electron beam excited phosphor - Google Patents
Method for producing slow electron beam excited phosphorInfo
- Publication number
- JP2971496B2 JP2971496B2 JP2030433A JP3043390A JP2971496B2 JP 2971496 B2 JP2971496 B2 JP 2971496B2 JP 2030433 A JP2030433 A JP 2030433A JP 3043390 A JP3043390 A JP 3043390A JP 2971496 B2 JP2971496 B2 JP 2971496B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- speed
- low
- film
- emitting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は低速電子線により励起され蛍光を発する低速
電子線励起蛍光体の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a slow electron beam excited phosphor that emits fluorescence when excited by a slow electron beam.
［従来の技術とその問題点］ 低速電子線励起蛍光表示管（以下、蛍光表示管と略記
する。）は片面に蛍光膜を有する陽極プレートとその蛍
光膜に対向した陰極とを容器内に封入し真空にした構造
を有し、陰極から放射される1KV以下の低速電子線によ
って陽極プレートの蛍光膜を発光せしめるものである。[Conventional technology and its problems] A low-speed electron-beam-excited fluorescent display tube (hereinafter abbreviated as a fluorescent display tube) encloses an anode plate having a fluorescent film on one surface and a cathode facing the fluorescent film in a container. The fluorescent film on the anode plate emits light by a low-speed electron beam of 1 KV or less emitted from the cathode.
前記蛍光膜を構成する低速電子線励起蛍光体（以下低
速蛍光体と略記する。）に求められる最も重要な特性
は、蛍光体が導電性を有しているということである。そ
の導電性が悪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に帯電しまい発光不能を生じる。
従って蛍光膜に塗布された蛍光体に導電性を付与しチャ
ージアップした負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が乾式混合された低速青色発光蛍光体が開
示されている。また特公昭62−53554号公報ではZnS:A
g、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等が乾式混合
された低速青色蛍光体が開示されている。即ち従来の技
術はそのほとんどが、母体である蛍光体の導電性が悪い
ために低速電子線励起において微弱にしか発光しない蛍
光体に対し、In2O3、SnO2等の導電性金属酸化物（以下
導電性物質と略記する。）を乾式混合することによって
蛍光体及び蛍光膜に導電性を付与して輝度を高めるとい
う技術である。The most important characteristic required of the low-speed electron-beam excited phosphor (hereinafter, abbreviated as the low-speed phosphor) constituting the phosphor film is that the phosphor has conductivity. If the conductivity is poor, by the electron beam emitted from the cathode,
The fluorescent film surface of the anode is negatively charged, so that light emission is disabled.
Therefore, various techniques have been disclosed in the prior art for imparting conductivity to the phosphor applied to the phosphor film and releasing the charged negative charge. For example, in Japanese Patent Publication 52-23911 discloses ZnS: Ag, Y 2 SiO 5 : slow blue light-emitting phosphors 10 to 90 wt% of In 2 O 3 were dry blended in a blue-emitting phosphor such as Ce are disclosed ing. Japanese Patent Publication No. 62-53554 discloses ZnS: A
g, Zn (SSe): Low-speed blue fluorescence obtained by dry-mixing In 2 O 3 , SnO 2, etc. with a defined particle size to a blue-emitting phosphor such as Ag, Al, SrGa 2 S 4 : Ce,. The body is disclosed. That is, most of the conventional techniques are based on conductive metal oxides such as In 2 O 3 and SnO 2 for phosphors that emit only weakly when excited by a slow electron beam due to poor conductivity of the base phosphor. (Hereinafter, abbreviated as a conductive substance) is a technique of imparting conductivity to the phosphor and the phosphor film by dry mixing to increase luminance.
しかし上記In2O3、SnO2等の導電性物質は非発光物質
であり、しかも黄色若しくは褐色の体色を有している。
従ってそれらを蛍光体と混合するという技術は、前記導
電性物質が蛍光体自体の発光を阻害、吸収してしまうた
め、蛍光体及び蛍光表示管の輝度低下を招くという欠点
があった。However, the above-mentioned conductive substances such as In 2 O 3 and SnO 2 are non-luminous substances and have a yellow or brown body color.
Therefore, the technique of mixing them with the phosphor has a drawback that the conductive substance inhibits and absorbs the light emission of the phosphor itself, which causes a decrease in luminance of the phosphor and the fluorescent display tube.
以上のように蛍光表示管にとって、導電性物質は不可
欠なものであるため、通常はその導電性物質の混合量の
最適化により輝度低下の対策を試みているが、最近急速
な表示デバイスの発達に伴い、より以上の蛍光表示管の
輝度向上が望まれている。As described above, conductive materials are indispensable for fluorescent display tubes, so we usually try to reduce the luminance by optimizing the amount of the conductive materials mixed, but recently the rapid development of display devices Accordingly, it is desired to further improve the brightness of the fluorescent display tube.
［発明が解決しようとする問題点］ そこで本発明は上記事情を鑑みて成されたものであ
り、蛍光体に対する導電性物質を改良することによっ
て、加速電圧が1KV以下、特に100V以下の低速電子線励
起の元で優れた導電性と輝度を有する低速蛍光体及びそ
れを利用した主として蛍光表示管用の蛍光膜を提供する
ことを目的とするものである。[Problems to be Solved by the Invention] Accordingly, the present invention has been made in view of the above circumstances, and by improving a conductive material for a phosphor, an acceleration voltage of 1 KV or less, particularly 100 V or less, has been improved. It is an object of the present invention to provide a low-speed phosphor having excellent conductivity and brightness under line excitation and a phosphor film mainly for a fluorescent display tube using the same.
［問題点を解決するための手段］ 本発明者らは低速蛍光体及び蛍光表示管の輝度を向上
するため、数々の導電性物質の種類及び蛍光体に対する
添加方法等について鋭意研究を重ねた結果、導電性物質
を蛍光体の少なくとも表面全体に均質膜状又は半均質膜
状に被覆することによって低加速電圧において、低速蛍
光体及び蛍光表示管の輝度が飛躍的に向上することを新
たに見いだし本発明を成すに至った。[Means for Solving the Problems] The present inventors have conducted intensive studies on various types of conductive substances and methods of adding to the phosphors in order to improve the brightness of the low-speed phosphor and the fluorescent display tube. It has been newly found that the brightness of the low-speed phosphor and the fluorescent display tube is dramatically improved at a low acceleration voltage by coating the conductive material on at least the entire surface of the phosphor in a uniform film or semi-homogeneous film. The present invention has been accomplished.
本発明の蛍光体は、一般式ZnS:M1,M2（但しM1はAg、Z
n、Cu、Auの群から選ばれた少なくとも一種の元素であ
り、M2はAl、Ｆ、Cl、Br、Ｉの群から選ばれた少なくと
も一種の元素である。）又は一般式（ZnCd）S:M1,M2で
表される蛍光体のうちから選ばれた少なくとも一種の蛍
光体の少なくとも表面全体を、均質膜状又は半均質膜状
の導電性金属酸化物が被覆して成ることを特徴とする低
速蛍光体である。The phosphor of the present invention has the general formula ZnS: M1, M2 (where M1 is Ag, Z
At least one element selected from the group consisting of n, Cu, and Au, and M2 is at least one element selected from the group consisting of Al, F, Cl, Br, and I. ) Or at least the entire surface of at least one phosphor selected from the phosphors represented by the general formula (ZnCd) S: M1 and M2 is formed of a conductive metal oxide in a homogeneous or semi-homogeneous film form. A low-speed phosphor characterized by being coated.
なお均質膜状又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、導電性物質を混合した従来の低
速蛍光体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、導電性物質と蛍光体とが面でつなが
っている状態を指す。従って一部塊状の付着物を含んだ
り、むらになって付着している場合もある。Note that a state in which the phosphor is covered with a homogeneous or semi-homogeneous film of a conductive material means that the phosphor and the conductive material come into contact at a point like a conventional low-speed phosphor mixed with a conductive material. In contrast to the state in which the conductive material is in contact with the conductive material, the conductive material and the phosphor are connected in a plane. Therefore, there may be a case where a part of the adhered substance is included or adhered in an uneven manner.
本発明の低速蛍光体に用いられる蛍光体は通常陰極線
管で用いられている蛍光体又は導電性物質と混合されて
従来の低速蛍光体となる公知の蛍光体である。そしてそ
の蛍光体の発光色は上記一般式においてM1、M2の種類、
量及びCdの量を任意に変える事によって自由に変えるこ
とができる。例えば青色発光蛍光体においては（ZnS:A
g,Al）、（ZnS:Zn,Cl）、｛（ZnCd）S:Ag,Cl｝等が知ら
れており、緑色発光蛍光体においては（ZnS:Cu,Cl）、
（ZnS:Cu,Au,Al）、｛（ZnCd）S:Ag,Al｝等、黄色発光
蛍光体では、（ZnS:Au,Al）、（ZnS:Cu,Au,Al）、｛（Z
nCd）S:Ag,Cl｝等、白色発光蛍光体では｛ZnS:Zn,Clと
（ZnCd）S:Cu,Alの混合物｝、｛ZnS:Ag,AlとZnS:Au,Al
の混合物｝、｛（ZnCd）S:Ag,Au,Al｝等、橙色発光蛍光
体では｛（ZnCd）S:Cu,Cl｝、｛（ZnCd）S:Au,Al｝、
｛（ZnCd）S:Ag,Cl｝等、赤色発光蛍光体では｛（ZnC
d）S:Cu,Al｝、｛（ZnCd）S:Au,Al｝、｛（ZnCd）S:Ag,
Al｝等が良く知られている。The phosphor used in the low-speed phosphor of the present invention is a known phosphor which is mixed with a phosphor usually used in a cathode ray tube or a conductive material to become a conventional low-speed phosphor. And the luminescent color of the phosphor is the type of M1, M2 in the above general formula,
It can be freely changed by arbitrarily changing the amount and the amount of Cd. For example, in a blue light-emitting phosphor, (ZnS: A
g, Al), (ZnS: Zn, Cl), {(ZnCd) S: Ag, Cl} and the like are known, and (ZnS: Cu, Cl),
(ZnS: Au, Al), (ZnS: Cu, Au, Al), (ZnS: Cu, Au, Al), (ZnS: Cu, Au, Al), (ZnS: Cu, Au, Al), (｛(ZnCd) S: Ag, Al)
nCd) S: Ag, Cl}, etc. For white light-emitting phosphors, {mixture of ZnS: Zn, Cl and (ZnCd) S: Cu, Al}, {ZnS: Ag, Al and ZnS: Au, Al
Mixtures of ｛, {(ZnCd) S: Ag, Au, Al}, etc. for orange-emitting phosphors, {(ZnCd) S: Cu, Cl}, {(ZnCd) S: Au, Al},
赤色 (ZnCd) S: Ag, Cl｝, etc.
d) S: Cu, Al｝, ｛(ZnCd) S: Au, Al｝, ｛(ZnCd) S: Ag,
Al｝ and others are well known.
また本発明の蛍光体において表面に被覆される導電性
物質は、In2O3、SnO2、ZnO、TiO2、WO3、Nb2O5等がある
が特に好ましくはIn2O3、SnO2内の少なくとも一種であ
る。The conductive material coated on the surface of the phosphor of the present invention includes In 2 O 3 , SnO 2 , ZnO, TiO 2 , WO 3 , Nb 2 O 5, etc., and particularly preferably In 2 O 3 , SnO 2 At least one of the two .
ところで本発明の蛍光体の特徴である、表面に均質膜
状又は半均質膜状に前記導電性物質を被覆するには以下
に述べる方法によって達成できる。By the way, the following method described below can be used to coat the conductive material on the surface in a uniform or semi-homogeneous film, which is a feature of the phosphor of the present invention.
すなわち、In、Sn、Ti、Ｗ等加熱酸化によって、容易
に導電性物質となり得る金属の有機化合物、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
ルメタン、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有機溶媒に溶解
した溶液、又は前記金属のキレート化合物若しくはイオ
ン会合体として有機溶媒に溶解、抽出した溶液、即ち有
機溶媒可溶性の有機金属化合物を用いる方法である。具
体的に述べると、蛍光体を前記金属を含む有機溶媒中に
懸濁させた後、加温して有機溶媒のみを揮散させる。そ
れによって前記金属の有機化合物が蛍光体粒子に均一に
付着した状態となる。その蛍光体を空気雰囲気中若しく
は弱還元雰囲気中で450℃以上の温度で焼成することに
よって有機物は分解し、前記金属の酸化物は均質膜状又
は半均質膜状となって、蛍光体表面を被覆する。That is, an organic compound of a metal which can easily become a conductive substance by thermal oxidation such as In, Sn, Ti, W, etc., for example, trimethylindium (III) tris (cyclopentadienyl) indium, triphenylindium, diethyltin, dipropyltin, diphenyltin , A solution of trichloromethylmethane, tetrabenzyltitanium, hexamethyltungsten, dichlorotrimethylniobium or the like dissolved in an organic solvent, or a solution of the metal as a chelate compound or an ion associate dissolved in an organic solvent, a solution extracted, that is, an organic solvent-soluble This is a method using an organic metal compound. Specifically, the phosphor is suspended in the organic solvent containing the metal, and then heated to evaporate only the organic solvent. As a result, the organic compound of the metal is uniformly attached to the phosphor particles. The organic substance is decomposed by firing the phosphor at a temperature of 450 ° C. or more in an air atmosphere or a weak reducing atmosphere, and the oxide of the metal becomes a homogeneous film or a semi-homogeneous film, and the phosphor surface is treated. Cover.
また後に蛍光表示管の蛍光膜を作成する際、蛍光膜を
450℃以上で焼成する工程があるため、上記方法におい
て450℃以上で焼成せずとも有機溶媒を揮散させただけ
の蛍光体でも良い。Also, when creating the fluorescent film of the fluorescent display tube later,
Since there is a step of baking at 450 ° C. or higher, a phosphor which does not bake at 450 ° C. or higher but only volatilizes the organic solvent may be used.
さらに被覆する導電性物質の量は、蛍光体が青色発光
蛍光体の場合はその蛍光体に対し0.1重量％以上10.0重
量％未満の範囲に、緑色発光蛍光体若しくは白色発光蛍
光体の場合は同じく蛍光体に対し0.08重量％以上9.0重
量％以下の範囲に、蛍光体が黄色発光蛍光体の場合は同
じく0.06重量％以上8.0重量％以下の範囲に、蛍光体が
橙色発光蛍光体若しくは赤色発光蛍光体の場合は同じく
0.05重量％以上7.0重量％以下の範囲に調整する。なぜ
ならその量が上記最小値以下であると十分な導電性が蛍
光体に付与できず、特性は元の蛍光体に近いものとなる
ため、特に100V以下の低速電子線励起下では十分な輝度
が得られない。逆に上記最大値以上であると、導電性物
質の被覆厚が大きくなることによって、電子線が蛍光体
まで到達しにくくなり同じく十分な輝度が得られない。
また発光の導電性物質による吸収も大きくなってしま
う。そのためより好ましい被覆量は青色発光蛍光体にお
いては、1.0〜5.0重量％、緑色若しくは白色発光蛍光体
においては0.5〜3.0重量％、黄色発光蛍光体においては
0.3〜2.0重量％、橙色若しくは赤色発光蛍光体において
は0.2〜2.0重量％の範囲に調整する。Further, the amount of the conductive material to be coated is in the range of 0.1% by weight or more and less than 10.0% by weight based on the phosphor when the phosphor is a blue light emitting phosphor, and the same when the phosphor is a green light emitting phosphor or a white light emitting phosphor. In the range of 0.08% by weight or more and 9.0% by weight or less with respect to the fluorescent substance, when the fluorescent substance is a yellow light-emitting fluorescent substance, in the same range of 0.06% by weight or more and 8.0% by weight or less, the fluorescent substance is an orange-emitting fluorescent substance or a red-emitting fluorescent Same for body
Adjust to be in the range of 0.05% by weight to 7.0% by weight. If the amount is less than the above-mentioned minimum value, sufficient conductivity cannot be imparted to the phosphor, and the characteristics are close to those of the original phosphor. I can't get it. On the other hand, if it is not less than the above maximum value, the coating thickness of the conductive material becomes large, so that the electron beam hardly reaches the phosphor, so that sufficient luminance cannot be obtained.
In addition, absorption of light emission by the conductive substance also increases. Therefore, a more preferable coating amount is 1.0 to 5.0% by weight for the blue light emitting phosphor, 0.5 to 3.0% by weight for the green or white light emitting phosphor, and 0.5 to 3.0% by weight for the yellow light emitting phosphor.
It is adjusted to a range of 0.3 to 2.0% by weight, and to a range of 0.2 to 2.0% by weight for an orange or red light emitting phosphor.
次に本発明の蛍光膜は、上記方法によって表面に導電
性物質が均質膜状又は半均質膜状に被覆された低速蛍光
体が発光成分として陽極プレートに塗布されて成ること
を特徴とする蛍光膜である。Next, the fluorescent film of the present invention is characterized in that a low-speed phosphor whose surface is coated with a conductive material in a homogeneous or semi-homogeneous film by the above method is applied to the anode plate as a light emitting component. It is a membrane.
その陽極プレートに本発明の蛍光体を用いて蛍光膜を
形成するには、スクリーン塗布法、電着塗布法、沈澱塗
布法等従来知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。その後、そのプ
レートを乾燥し450℃以上で焼成することによって本発
明の蛍光膜を形成できるが、また以下に述べる方法によ
って形成することもできる。To form a fluorescent film on the anode plate using the phosphor of the present invention, a screen coating method, an electrodeposition coating method, using a conventionally known coating method such as a precipitation coating method, usually 5 to 30 mg
Apply to the anode plate in the range of / cm 2 . Thereafter, the plate is dried and fired at 450 ° C. or higher to form the fluorescent film of the present invention, but it can also be formed by the method described below.
まず、主として蛍光体とバインダーが練り合わされた
蛍光体ペーストを作成し、このペーストに上記加熱酸化
によって容易に導電性物質となり得る有機金属化合物が
溶解された有機溶媒を添加して再び混練してペースト状
とする。次にこのペーストを陽極プレートに塗布した
後、同じく450℃以上で焼成することによって蛍光膜を
作成する方法である。その様にして得られた蛍光膜を構
成する蛍光体も、本発明の蛍光体と同様に、表面は微粒
子状または均質膜状の前記導電性物質で被覆された構造
を有する低速蛍光体である。従って被覆する導電性物質
の量も上記範囲になるよう、上記導電性物質となり得る
金属化合物の添加量を調整する必要がある。First, a phosphor paste in which a phosphor and a binder are mainly kneaded is prepared, and an organic solvent in which an organometallic compound that can easily become a conductive substance by the above-described heat oxidation is dissolved is added to the paste, and the paste is kneaded again to form a paste. State. Next, this paste is applied to an anode plate and then baked at 450 ° C. or higher to form a fluorescent film. Similarly to the phosphor of the present invention, the phosphor constituting the phosphor film thus obtained is a low-speed phosphor having a structure in which the surface is coated with the conductive material in the form of fine particles or homogeneous film. . Therefore, it is necessary to adjust the amount of the metal compound that can be the conductive substance so that the amount of the conductive substance to be coated is also within the above range.
［作用］ 本発明の低速蛍光体における導電性物質の被覆量の適
正値は各発光色によって異なっている。これは各発光色
蛍光体の発光開始電圧の違いによるものであり、通常
青、緑、白、黄、橙、赤の順に発光開始電圧は低くな
る。従って発光開始電圧の高い青色発光蛍光体には多量
の導電性物質の被覆が必要となるが、逆に発光開始電圧
の低い赤色発光蛍光体では少量の導電性物質の被覆では
十分な導電性が蛍光体に付与できる。[Action] The appropriate value of the coating amount of the conductive substance in the low-speed phosphor of the present invention differs depending on each emission color. This is due to the difference in emission start voltage of each emission color phosphor, and the emission start voltage generally decreases in the order of blue, green, white, yellow, orange, and red. Accordingly, a blue light emitting phosphor having a high light emission starting voltage requires a large amount of coating with a conductive substance, while a red light emitting phosphor having a low light emission starting voltage requires a sufficient amount of conductive material to be coated with a small amount of a conductive substance. Can be applied to phosphors.
また本発明の蛍光体は、導電性物質の混合された従来
の低速蛍光体に比べ、導電性物質の蛍光体に対する付着
構造が全く異なることによって蛍光体全体の導電性が向
上している。従ってそれを塗布した蛍光膜は電気抵抗値
が下がり、その蛍光膜における電圧降下が減少すること
によって駆動電圧の損失が少なくなる。そのため蛍光体
励起に必要な電子が効率よく十分に加速される。また非
発光及び光吸収体である導電性物質の量を著しく低減し
たため蛍光体の発光が阻害されることが少なくなる。そ
れらの相乗効果によって本発明の蛍光体及び蛍光膜を有
した蛍光表示管の輝度は著しく向上した。Further, the phosphor of the present invention has improved conductivity as a whole due to the completely different adhesion structure of the conductive substance to the phosphor as compared with the conventional low-speed phosphor in which the conductive substance is mixed. Accordingly, the phosphor film coated with the phosphor has a reduced electric resistance value, and a voltage drop in the phosphor film is reduced, so that a loss of a driving voltage is reduced. Therefore, electrons required for exciting the phosphor are efficiently and sufficiently accelerated. In addition, since the amount of the non-light-emitting and light-absorbing conductive material is significantly reduced, the emission of the phosphor is less hindered. Due to the synergistic effect, the luminance of the fluorescent display tube having the phosphor of the present invention and the phosphor film was remarkably improved.
［実施例］ 以下実施例で本発明を詳説する。EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples.
（実施例１） 加熱酸化により導電性物質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（日本曹達製商品名）を用
いた。(Example 1) As an organic solvent-soluble metal compound that can become a conductive substance by thermal oxidation, 5% by weight in terms of In 2 O 3 and 5% by weight in terms of SnO 2
Atron NIn (trade name, manufactured by Nippon Soda) containing 0.5% by weight was used.
このアトロンNIn20gをエタノール100mlに溶解し、こ
のエタノール溶液中に黄色発光蛍光体｛（ZnCd）S:Ag,A
l｝100gを添加し、十分懸濁させた後、60℃に加温して
エタノールを揮散させた。20 g of this atron NIn is dissolved in 100 ml of ethanol, and the yellow light-emitting phosphor ｛(ZnCd) S: Ag, A
After adding l｝ 100 g and sufficiently suspending, the mixture was heated to 60 ° C. to evaporate ethanol.
この蛍光体を取り出し、空気中中性雰囲気で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％含まれる導電性物質の均
質膜によって被覆された本発明の低速黄色発光蛍光体を
得た。The phosphor was taken out, after 1 hour calcination at 500 ° C. in a neutral atmosphere in the air, an In 2 O 3 with respect to the yellow-emitting phosphor
Was obtained with a low-speed yellow light-emitting phosphor of the present invention, which was coated with a homogeneous film of a conductive substance containing 1.0% by weight and 0.1% by weight of SnO 2 .
また比較例として同一の黄色発光蛍光体に対し10.0重
量％のIn2O3を混合した従来の低速黄色発光蛍光体も作
成した。As a comparative example, a conventional low-speed yellow light-emitting phosphor in which 10.0% by weight of In 2 O 3 was mixed with the same yellow light-emitting phosphor was also prepared.
これら低速黄色発光蛍光体50gを用いて実施例１と同
様にして蛍光表示管を作成し、実施例１と同一の条件で
発光させたところ本発明の低速黄色発光蛍光体を実装し
た蛍光表示管は145％の輝度を得た。A fluorescent display tube was prepared using 50 g of the low-speed yellow light-emitting phosphor in the same manner as in Example 1 and emitted under the same conditions as in Example 1. As a result, the fluorescent display tube equipped with the low-speed yellow light-emitting phosphor of the present invention was used. Gave a 145% brightness.
（実施例２） 青色発光蛍光体である（ZnS:Ag,Al）と黄色発光蛍光
体である（ZnS:Al,Al）とを重量比で1:2で混合した白色
発光蛍光体100gを用意し、実施例３と同様にアトロンNI
nを用い、白色発光蛍光体に対しIn2O3が1.0重量％、SnO
2が0.1重量％被覆した本発明の低速白色発光蛍光体を得
た。Example 2 100 g of a white light-emitting phosphor prepared by mixing a blue light-emitting phosphor (ZnS: Ag, Al) and a yellow light-emitting phosphor (ZnS: Al, Al) at a weight ratio of 1: 2 was prepared. Then, as in Example 3, Atron NI
n, using 1.0% by weight of In 2 O 3 with respect to the white light-emitting phosphor,
Thus, a low-speed white light-emitting phosphor of the present invention coated with 0.1% by weight was obtained.
また比較例として同一の白色発光蛍光体に対し10.0重
量％のIn2O3を混合した従来の低速白色発光蛍光体も作
成した。As a comparative example, a conventional low-speed white light-emitting phosphor in which 10.0% by weight of In 2 O 3 was mixed with the same white light-emitting phosphor was also prepared.
これら低速白色発光蛍光体50gを用いて実施例１と同
様にして蛍光表示管を作成し、実施例１と同一の条件で
発光させたところ本発明の低速白色発光蛍光体を実装し
た蛍光表示管は140％の輝度を得た。A fluorescent display tube was prepared in the same manner as in Example 1 using 50 g of the low-speed white light-emitting phosphor, and emitted under the same conditions as in Example 1. As a result, the fluorescent display tube mounted with the low-speed white light-emitting phosphor of the present invention was used. Gave a brightness of 140%.
［発明の効果］ 本発明の低速蛍光体及び蛍光膜において、蛍光体表面
で均質膜状又は半均質膜状となっている導電性物質の効
果は非常に大きく従来の低速蛍光体に比べて輝度が格段
に向上した。また輝度だけでなく、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蛍光体と
同等若しくはそれ以上であった。[Effects of the Invention] In the low-speed phosphor and the fluorescent film of the present invention, the effect of the conductive substance having a homogenous or semi-homogeneous film on the surface of the phosphor is very large, and the luminance is higher than that of the conventional low-speed phosphor. Has improved significantly. In addition to the brightness, the coating characteristics on the anode plate, the deterioration of the phosphor, and the like were equal to or higher than those of the conventional low-speed phosphor.
また本発明の蛍光体とIn2O3等の導電性物質を乾式混
合しても良好な結果が得られることは言うまでもない。Needless to say, good results can be obtained by dry mixing the phosphor of the present invention and a conductive substance such as In 2 O 3 .
本発明の均質膜状又は半均質膜状の導電性物質を被覆
させる蛍光体としては硫化亜鉛系蛍光体、硫化亜鉛カド
ミウム系蛍光体に限らず、低速蛍光体として適用し得る
他の蛍光体全てに適用できる。The phosphor coated with the conductive material in the form of a homogeneous or semi-homogeneous film of the present invention is not limited to a zinc sulfide-based phosphor, a zinc cadmium sulfide-based phosphor, and all other phosphors applicable as a low-speed phosphor. Applicable to
さらに本発明の蛍光体は薄型陰極線管の蛍光面を形成
するための蛍光体としても用いることができる。Further, the phosphor of the present invention can be used as a phosphor for forming a phosphor screen of a thin cathode ray tube.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−140284（ＪＰ，Ａ) 特開 昭55−131083（ＪＰ，Ａ) 特開 昭63−56593（ＪＰ，Ａ) 特開 昭63−15878（ＪＰ，Ａ) 特開 昭52−22587（ＪＰ，Ａ) 特開 昭62−112704（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09K 11/00 - 11/89 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-59-140284 (JP, A) JP-A-53-131083 (JP, A) JP-A-63-56593 (JP, A) JP-A-63-56593 15878 (JP, A) JP-A-52-22587 (JP, A) JP-A-62-112704 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C09K 11/00-11 / 89
Claims (1)
uの群から選ばれた少なくとも一種の元素であり、M2はA
l、Ｆ、Cl、Br、Ｉの群から選ばれた少なくとも一種の
元素である。）又は一般式（ZnCd）S:M1,M2で表される
蛍光体のうちから選ばれた少なくとも一種の蛍光体の表
面に、加熱酸化により酸化インジウム及び酸化錫からな
る導電性金属酸化物となり得る有機金属化合物を有機溶
媒に溶解させた溶液中に前記蛍光体を懸濁後、加温して
有機溶媒を揮散させ前記有機金属化合物を前記蛍光体に
付着させた後加熱酸化することにより、前記導電性金属
酸化物を均質膜状又は半均質膜状に被覆することを特徴
とする低速電子線励起蛍光体の製造方法。1. The general formula ZnS: M1, M2 (where M1 is Ag, Zn, Cu, A
u is at least one element selected from the group of u, and M2 is A
At least one element selected from the group consisting of l, F, Cl, Br, and I. ) Or at least one kind of phosphor selected from phosphors represented by the general formula (ZnCd) S: M1 and M2 can be converted to a conductive metal oxide composed of indium oxide and tin oxide by heat oxidation. After suspending the phosphor in a solution obtained by dissolving an organometallic compound in an organic solvent, heating and evaporating the organic solvent to adhere the organometallic compound to the phosphor, followed by heating and oxidation, whereby the A method for producing a slow-electron-beam-excited phosphor, characterized in that a conductive metal oxide is coated in a homogeneous or semi-homogeneous film form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2030433A JP2971496B2 (en) | 1990-02-10 | 1990-02-10 | Method for producing slow electron beam excited phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2030433A JP2971496B2 (en) | 1990-02-10 | 1990-02-10 | Method for producing slow electron beam excited phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03234789A JPH03234789A (en) | 1991-10-18 |
| JP2971496B2 true JP2971496B2 (en) | 1999-11-08 |
Family
ID=12303813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2030433A Expired - Lifetime JP2971496B2 (en) | 1990-02-10 | 1990-02-10 | Method for producing slow electron beam excited phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2971496B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2363532A1 (en) * | 2000-12-18 | 2002-06-18 | Osram Sylvania Inc. | Preparation of high-brightness, long life, moisture resistant electroluminescent phosphor |
| WO2006051601A1 (en) * | 2004-11-12 | 2006-05-18 | Kabushiki Kaisha Toshiba | Phosphor for display apparatus, process for producing the same and field emission display apparatus utilizing the same |
| 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 |
| JP4978846B2 (en) * | 2008-04-04 | 2012-07-18 | 昭栄化学工業株式会社 | Light emitting device |
| WO2010110452A1 (en) * | 2009-03-26 | 2010-09-30 | 国立大学法人静岡大学 | Fluorescent thin film, method for manufacturing fluorescent thin film, fine light source excitation apparatus, and optical microscope |
-
1990
- 1990-02-10 JP JP2030433A patent/JP2971496B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03234789A (en) | 1991-10-18 |
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