JP2001214160A - Fluorescent substance and fluorescent display tube - Google Patents
Fluorescent substance and fluorescent display tubeInfo
- Publication number
- JP2001214160A JP2001214160A JP2000025369A JP2000025369A JP2001214160A JP 2001214160 A JP2001214160 A JP 2001214160A JP 2000025369 A JP2000025369 A JP 2000025369A JP 2000025369 A JP2000025369 A JP 2000025369A JP 2001214160 A JP2001214160 A JP 2001214160A
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- Japan
- Prior art keywords
- phosphor
- display tube
- fluorescent display
- anode
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
- Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イオウを母体成分
として含む蛍光体と、この蛍光体を使用した蛍光表示管
に関する。本発明の蛍光体は、特に酸化抑制物質を添加
することにより蛍光表示管の陽極に使用した際に管内の
酸素分圧を低く押さえることができ、優れた寿命特性が
得られるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor containing sulfur as a host component and a fluorescent display tube using the phosphor. The phosphor of the present invention can keep the oxygen partial pressure in the tube low when used for an anode of a fluorescent display tube, particularly by adding an oxidation inhibiting substance, and can obtain excellent life characteristics.
【０００２】[0002]
【従来の技術】一般的な蛍光表示管は、ガラスなどの絶
縁性の材料からなる略箱型の外囲器を有している。この
外囲器の一部を構成する基板の内面には陽極導体が設け
られ、陽極導体の上には蛍光体が設けられ、発光表示部
としての陽極を構成している。外囲器内において、陽極
の上方には制御電極が設けられ、さらに制御電極の上方
には電子源である線状の陰極が張設されている。陰極か
ら放出された電子は制御電極によって加速・制御され、
陽極電圧が引火された陽極に射突し、当該陽極の蛍光体
を発光させる。2. Description of the Related Art A general fluorescent display tube has a substantially box-shaped envelope made of an insulating material such as glass. An anode conductor is provided on the inner surface of the substrate constituting a part of the envelope, and a phosphor is provided on the anode conductor to constitute an anode as a light emitting display unit. In the envelope, a control electrode is provided above the anode, and a linear cathode as an electron source is provided above the control electrode. The electrons emitted from the cathode are accelerated and controlled by the control electrode,
The anode voltage strikes the ignited anode, causing the phosphor of the anode to emit light.
【０００３】前記従来の蛍光表示管において、陽極の蛍
光体層を形成するには、蛍光体粒子を含むペーストを所
望のパターンで陽極導体に塗布し、これを焼成してペー
スト中に含まれるバインダ成分を分解除去して行なって
いた。In the conventional fluorescent display tube, in order to form a phosphor layer of an anode, a paste containing phosphor particles is applied to an anode conductor in a desired pattern, and the paste is baked to form a binder contained in the paste. The components were decomposed and removed.
【０００４】例えばＺｎＯ蛍光体の場合には、上述した
蛍光体層の焼成工程は４５０〜５５０℃で行ない、これ
によって残渣なしで蛍光体層を形成することができた。For example, in the case of a ZnO phosphor, the above-described sintering step of the phosphor layer was performed at 450 to 550 ° C., whereby the phosphor layer could be formed without any residue.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、イオウ
を母体成分として含む蛍光体、即ち硫化物系の蛍光体は
分解温度が低く、高温で焼成することができず、３５０
℃以上の温度で焼成すると表面酸化が進行して蛍光体と
しての実力が低下してしまう。このため、従来、硫化物
系の蛍光体を用いる場合には分解を避け、できるだけ表
面酸化が進行しないような低い温度で焼成していた。こ
のような焼成工程では有機残渣等が発生する懸念があ
り、場合によっては劣化して輝度が低下する等、信頼性
低下につながることもあった。また、このような蛍光体
を用いた蛍光表示管では、寿命が短いという問題があっ
た。However, a phosphor containing sulfur as a base component, that is, a sulfide phosphor, has a low decomposition temperature, cannot be fired at a high temperature, and cannot be burned at a high temperature.
If baked at a temperature of not less than ° C., surface oxidation proceeds and the ability as a phosphor is reduced. For this reason, conventionally, when a sulfide-based phosphor is used, decomposition is avoided and firing is performed at such a low temperature that surface oxidation does not proceed as much as possible. In such a firing step, there is a concern that an organic residue or the like may be generated, and in some cases, the luminance may be reduced due to deterioration, leading to a reduction in reliability. Further, a fluorescent display tube using such a phosphor has a problem that its life is short.
【０００６】硫化物系の蛍光体の代替品としてＣｄを母
体成分として含む蛍光体を用いるという提案もなされて
いるようであるが、Ｃｄ系の蛍光体の採用は環境衛生面
で検討すべき課題が少なくなく、また蛍光体としての特
性の劣化が進みやすく、実用とするには寿命レベルに問
題がある。Although it has been proposed to use a phosphor containing Cd as a host component as a substitute for a sulfide-based phosphor, the use of a Cd-based phosphor is a problem to be studied from an environmental hygiene point of view. In addition, the characteristics of the phosphor are easily deteriorated, and there is a problem in the life level for practical use.
【０００７】本発明は、高温で焼成しても表面が酸化し
ないために輝度の低下が少なく、蛍光表示管用の蛍光体
として優れた特性を発揮できる硫化物系蛍光体と、係る
蛍光体を用いた蛍光表示管を提供することを目的として
いる。The present invention relates to a sulfide-based phosphor capable of exhibiting excellent characteristics as a phosphor for a fluorescent display tube because the surface does not oxidize even when fired at a high temperature, and a phosphor using the phosphor. The purpose of the present invention is to provide a fluorescent display tube.
【０００８】[0008]
【課題を解決するための手段】請求項１に記載された蛍
光体は、イオウを母体成分として含む蛍光体に酸化抑制
物質を添加したことを特徴としている。The phosphor according to the present invention is characterized in that an oxidation inhibitor is added to a phosphor containing sulfur as a base component.
【０００９】請求項２に記載された蛍光体は、請求項１
記載の蛍光体において、酸化抑制物質が水素放出材料で
あることを特徴としている。[0009] The phosphor according to the second aspect is the first aspect.
The phosphor described above is characterized in that the oxidation suppressing substance is a hydrogen releasing material.
【００１０】請求項３に記載された蛍光体は、請求項２
記載の蛍光体において、前記水素放出材料が、Ｚｒ
Ｈ2 、ＴｉＨ2 、ＴｉＯ2 、ＴｉＮ、α−Ｓｉ、ＢＣＮ
Ｔからなる群から選択されたことを特徴としている。[0010] The phosphor according to the third aspect is the second aspect.
The phosphor according to claim 1, wherein the hydrogen releasing material is Zr.
H 2 , TiH 2 , TiO 2 , TiN, α-Si, BCN
T is selected from the group consisting of T.
【００１１】請求項４に記載された蛍光体は、請求項１
記載の蛍光体において、酸化抑制物質が酸化性ガス吸着
物質であることを特徴としている。[0011] The phosphor according to the fourth aspect is the first aspect.
The phosphor described above is characterized in that the oxidation suppressing substance is an oxidizing gas adsorbing substance.
【００１２】請求項５に記載された蛍光体は、請求項４
記載の蛍光体において、前記酸化性ガス吸着物質が、Ｎ
ｉ、ＴｉＯx 、ＣａＯ、ＭｇＯ、ＢａＯ、ＳｒＯ殻なる
群から選択されたことを特徴としている。[0012] The phosphor described in claim 5 is a phosphor according to claim 4.
3. The phosphor according to claim 1, wherein the oxidizing gas adsorbing substance is N
i, TiO x , CaO, MgO, BaO, and SrO shells.
【００１３】請求項６に記載された蛍光体は、請求項１
又は２又は３又は４又は５記載の蛍光体において、イオ
ウを母体成分として含む前記蛍光体が、ＺｎＳ、Ｌｎ2
Ｏ2Ｓ：Ｒｅ（Ｌｎ＝Ｙ、Ｌａ、Ｇｄ，Ｒｅ＝Ｅｕ、Ｔ
ｂ）からなる群から選択されたことを特徴としている。[0013] The phosphor according to the sixth aspect is the first aspect.
Or 2 or 3 or 4 or 5, wherein the phosphor containing sulfur as a host component is ZnS, Ln 2
O 2 S: Re (Ln = Y, La, Gd, Re = Eu, T
b) is selected from the group consisting of:
【００１４】請求項７に記載された蛍光表示管は、電子
を放出する陰極と、陽極導体と前記陽極導体に設けられ
て前記陰極から放出された電子が射突して発光する蛍光
体層とを有する陽極とが、気密外囲器内に設けられた蛍
光表示管であって、前記蛍光体が、イオウを母体成分と
して含む蛍光体に酸化抑制物質を添加したものであるこ
とを特徴としている。According to a seventh aspect of the present invention, there is provided a fluorescent display tube comprising: a cathode which emits electrons; an anode conductor; and a phosphor layer provided on the anode conductor and which emits light by emitting electrons emitted from the cathode. And a fluorescent display tube provided in an airtight envelope, wherein the phosphor is obtained by adding an oxidation inhibitor to a phosphor containing sulfur as a base component. .
【００１５】請求項８に記載された蛍光表示管は、請求
項７記載の蛍光表示管において、イオウを母体成分とし
て含む前記蛍光体が、ＺｎＳ、Ｌｎ2 Ｏ2 Ｓ：Ｒｅ（Ｌ
ｎ＝Ｙ、Ｌａ、Ｇｄ，Ｒｅ＝Ｅｕ、Ｔｂ）からなる群か
ら選択されたことを特徴としている。According to an eighth aspect of the present invention, in the fluorescent display tube according to the seventh aspect, the phosphor containing sulfur as a base component is ZnS, Ln 2 O 2 S: Re (L
n = Y, La, Gd, Re = Eu, Tb).
【００１６】請求項９に記載された蛍光表示管は、電子
を放出する陰極と、陽極導体と前記陽極導体に設けられ
て前記陰極から放出された電子が射突して発光する蛍光
体層とを有する陽極とが、気密外囲器内に設けられた蛍
光表示管において、前記蛍光体がイオウを母体成分とし
て含む蛍光体であり、前記蛍光体層が設けられた陽極の
近傍に、酸化抑制物質を有する層が設けられたことを特
徴としている。According to a ninth aspect of the present invention, there is provided a fluorescent display tube, comprising: a cathode which emits electrons; an anode conductor; and a phosphor layer provided on the anode conductor and which emits light by emitting electrons emitted from the cathode. And an anode having a phosphor layer, wherein the phosphor is a phosphor containing sulfur as a host component in a fluorescent display tube provided in an airtight envelope, and oxidation is suppressed in the vicinity of the anode provided with the phosphor layer. A layer having a substance is provided.
【００１７】以上の構成によれば、蛍光体の焼成時には
添加した酸化抑制物質のために酸化しにくく、蛍光体の
劣化が抑えられる。また、蛍光表示管に実装して発光駆
動する際には、管内の酸素などの酸化性ガスの影響を低
減するので寿命特性が向上する。According to the above structure, the phosphor is hardly oxidized due to the added oxidation inhibitor during the firing of the phosphor, and the deterioration of the phosphor is suppressed. In addition, when mounted on a fluorescent display tube and driven to emit light, the effect of an oxidizing gas such as oxygen in the tube is reduced, so that the life characteristics are improved.
【００１８】[0018]
【実施例】（１）第１実施例 ＺｎＳ：Ｚｎ青色発光蛍光体に、導電材料としてＩｎ2
Ｏ3 を５％添加し、また酸化抑制物質としての水素放出
材料である水素化ジルコニウム（ＺｒＨ2 ）を蛍光体に
対して０．０１％から５０％の範囲で変化させて添加
し、水素化ジルコニウムの添加量が異なる複数種類の蛍
光体ペーストを作製した。各々について蛍光表示管を作
製する。即ち、各ペーストを蛍光表示管の陽極基板上の
陽極導体上に塗布し、５００℃で焼成する。内部に制御
電極と陰極を設けた状態で陽極基板と容器部で外囲器を
組み立てて封着し、さらに内部を排気して封着する。比
較のために水素化ジルコニウムを添加しない蛍光体を用
いた蛍光表示管も作製した。なお、本例で用いた蛍光体
の平均粒径は約４μｍ、添加剤の粒径は２μｍであっ
た。EXAMPLES (1) First Example A ZnS: Zn blue light emitting phosphor was prepared by using In 2 as a conductive material.
O 3 is added by 5%, and zirconium hydride (ZrH 2 ) as a hydrogen releasing material as an oxidation inhibitor is added in a range of 0.01% to 50% with respect to the phosphor, and hydrogenation is performed. A plurality of types of phosphor pastes having different addition amounts of zirconium were produced. A fluorescent display tube is manufactured for each. That is, each paste is applied on the anode conductor on the anode substrate of the fluorescent display tube and baked at 500 ° C. An envelope is assembled and sealed with the anode substrate and the container in a state where the control electrode and the cathode are provided inside, and the inside is further evacuated and sealed. For comparison, a fluorescent display tube using a phosphor to which zirconium hydride was not added was also manufactured. The average particle size of the phosphor used in this example was about 4 μm, and the particle size of the additive was 2 μm.
【００１９】これらの蛍光表示管を、陽極電圧３０Ｖを
印加して発光させ、輝度の評価を行なった。水素化ジル
コニウム５％添加試料で未添加試料に比べて約１５０％
の輝度が得られた。図１に水素化ジルコニウム添加量と
初期輝度の関係を示す。この実験結果から分かるよう
に、水素化ジルコニウム（ＺｒＨ2 ）の有効な添加量は
蛍光体に対して０．０１％から５０％の範囲であり、特
に０．０５％から４０％の範囲で未添加試料に比べて約
１２０％の輝度が得られ、０．２％から１０％の範囲で
未添加試料に比べて約１４０％の輝度が得られた。These fluorescent display tubes were made to emit light by applying an anode voltage of 30 V, and the luminance was evaluated. Approximately 150% of the sample containing 5% zirconium hydride compared to the sample not containing
Was obtained. FIG. 1 shows the relationship between the amount of zirconium hydride added and the initial luminance. As can be seen from the experimental results, the effective addition amount of zirconium hydride (ZrH 2 ) is in the range of 0.01% to 50%, particularly 0.05% to 40% with respect to the phosphor. A brightness of about 120% was obtained as compared with the added sample, and a brightness of about 140% was obtained in the range of 0.2% to 10% as compared with the unadded sample.
【００２０】（２）第２実施例 第１実施例と略同様に、Ｌａ2 Ｏ2 Ｓ：Ｅｕ赤橙発光蛍
光体に酸化抑制物質としての水素放出材料である水素化
チタン（ＴｉＨ2 ）を１０％添加した蛍光体ペーストを
作製し、これを用いて蛍光表示管を作製した。陽極電圧
４０Ｖを印加して発光させ、輝度の評価を行なった。未
添加試料に比べて約１６０％の輝度が得られた。また、
寿命試験の結果、１０００時間経過後の輝度残存率は未
添加品が４０％であったのに対し、約７０％と良好な値
を示した。また、最適量は同様にして評価したところ、
第１実施例とほぼ同様の結果が得られた。(2) Second Embodiment In substantially the same manner as in the first embodiment, titanium hydride (TiH 2 ) which is a hydrogen releasing material as an oxidation inhibitor is used for a La 2 O 2 S: Eu red-orange light-emitting phosphor. A phosphor paste to which 10% was added was prepared, and a fluorescent display tube was prepared using the phosphor paste. Light emission was performed by applying an anode voltage of 40 V, and the luminance was evaluated. Approximately 160% of the brightness was obtained as compared with the unadded sample. Also,
As a result of the life test, the luminance residual ratio after 1000 hours showed a good value of about 70%, compared to 40% for the non-added product. In addition, when the optimal amount was evaluated in the same manner,
Almost the same results as in the first embodiment were obtained.
【００２１】（３）第３実施例 Ｌａ2 Ｏ2 Ｓ：Ｅｕ赤橙発光蛍光体のペーストを陽極導
体に塗布して焼成した後、これに酸化抑制物質としての
水素放出材料であるＴｉＯ2 をスプレーなどで吹き付け
て乾燥し、以後第２実施例と同様に蛍光表示管を作製し
た。同様に評価した結果、所期輝度は未添加試料に比べ
て１２０％改善された。(3) Third Embodiment A paste of a La 2 O 2 S: Eu red-orange light-emitting phosphor is applied to an anode conductor and fired, and then a TiO 2 , which is a hydrogen releasing material as an oxidation inhibitor, is added thereto. The resultant was dried by spraying with a spray or the like, and thereafter, a fluorescent display tube was manufactured in the same manner as in the second embodiment. As a result of the same evaluation, the expected luminance was improved by 120% as compared with the sample without addition.
【００２２】（４）第４実施例 Ｌａ2 Ｏ2 Ｓ：Ｅｕ赤橙発光蛍光体に導電材料としてＺ
ｎＯを１０％添加し、さらに酸化抑制物質として機能す
る酸化性ガス吸着物質として、Ｎｉの粉末を蛍光体に対
して０．０１％から５０％の範囲で変化させて添加し、
Ｎｉ粉末の添加量が異なる複数種類の蛍光体ペーストを
作製した。各々について蛍光表示管を作製する。即ち、
各ペーストを蛍光表示管の陽極基板上の陽極導体上に塗
布し、４５０℃で焼成する。内部に制御電極と陰極を設
けた状態で陽極基板と容器部で外囲器を組み立てて封着
し、さらに内部を排気して封着する。比較のためにＮｉ
粉末を添加しない蛍光体を用いた蛍光表示管も作製し
た。なお、本例で用いた蛍光体の平均粒径は約４μｍ、
添加したＮｉ粉末の粒径は４μｍであった。(4) Fourth Embodiment La 2 O 2 S: Eu red-orange light-emitting phosphor has a Z
10% of nO is added, and as an oxidizing gas adsorbing material that functions as an oxidation inhibitor, Ni powder is added in a range of 0.01% to 50% with respect to the phosphor, and added.
A plurality of types of phosphor pastes having different amounts of Ni powder were produced. A fluorescent display tube is manufactured for each. That is,
Each paste is applied on the anode conductor on the anode substrate of the fluorescent display tube and baked at 450 ° C. An envelope is assembled and sealed with the anode substrate and the container in a state where the control electrode and the cathode are provided inside, and the inside is further evacuated and sealed. Ni for comparison
A fluorescent display tube using a phosphor to which no powder was added was also manufactured. The average particle size of the phosphor used in this example was about 4 μm,
The particle size of the added Ni powder was 4 μm.
【００２３】これらの蛍光表示管を、陽極電圧４０Ｖを
印加して発光させ、寿命試験を行なった。図２は、Ｎｉ
粉末の添加量が異なる蛍光体を備えた複数種類の蛍光表
示管と、Ｎｉ粉末無添加（添加量０％）の蛍光表示管に
ついて、初期輝度と１０００時間経過後の輝度残存率を
それぞれ測定して示したものである。These fluorescent display tubes were made to emit light by applying an anode voltage of 40 V, and a life test was performed. FIG.
The initial luminance and the luminance retention rate after 1000 hours were measured for a plurality of types of fluorescent display tubes provided with phosphors having different amounts of powder added and a fluorescent display tube without Ni powder added (addition amount 0%). It is shown.
【００２４】１０００時間経過後の輝度残存率は未添加
品が６０％であったのに対し、Ｎｉ粉末５％添加品では
約９２％と改善効果が見られた。本例では、添加量０．
１％から効果が見られ、２０％を超える値では蛍光体が
被覆され過ぎて効果が小さくなった。The luminance residual ratio after 1000 hours was 60% for the non-added product, while it was about 92% for the 5% Ni powder-added product, indicating an improvement effect. In this example, the amount of addition is 0.1.
The effect was observed from 1%, and when the value exceeded 20%, the phosphor was excessively coated and the effect was reduced.
【００２５】（５）第５実施例 Ｌａ2 Ｏ2 Ｓ：Ｅｕ赤橙発光蛍光体に導電材料としてＺ
ｎＯを１０％添加し、これを用いて蛍光体ペーストを作
製した。この蛍光体ペーストを、作製しようとする蛍光
表示管の陽極基板の陽極導体上に所定のパターンで塗布
した。酸化抑制物質としての酸化性ガス吸着物質である
Ｎｉの粉末をペースト状にし、これを陽極導体に設けた
蛍光体ペーストのパターンの周辺に適当なパターンで塗
布した。そして、この陽極基板を大気中で４５０℃で焼
成して有機物を分解・除去し、その後、前述した実施例
と同様にして蛍光表示管を作製した。(5) Fifth Embodiment La 2 O 2 S: Eu red-orange light-emitting phosphor has a Z
10% of nO was added, and a phosphor paste was prepared using this. This phosphor paste was applied in a predetermined pattern on an anode conductor of an anode substrate of a fluorescent display tube to be manufactured. A powder of Ni, which is an oxidizing gas-adsorbing substance as an oxidation-suppressing substance, was made into a paste, and this was applied in a suitable pattern around the phosphor paste pattern provided on the anode conductor. Then, the anode substrate was fired in air at 450 ° C. to decompose and remove organic substances, and thereafter, a fluorescent display tube was manufactured in the same manner as in the above-described embodiment.
【００２６】この蛍光表示管を、陽極電圧４０Ｖを印加
して発光させ、寿命試験を行なった。１０００時間経過
後の輝度残存率は、Ｎｉ粉末の層を持たない比較品が６
０％であったのに対し、Ｎｉ粉末の層を陽極周辺に配置
した本実施例の製品では約８５％と改善効果が見られ
た。The fluorescent display tube was caused to emit light by applying an anode voltage of 40 V, and a life test was performed. After 1000 hours, the luminance remaining rate was 6% for the comparative product having no Ni powder layer.
Compared with 0%, the product of this example in which the layer of Ni powder was arranged around the anode showed an improvement effect of about 85%.
【００２７】（６）第６実施例 Ｇｄ2 Ｏ2 Ｓ：Ｅｕ赤色発光蛍光体に導電材料としてＩ
ｎ2 Ｏ3 を１０％添加し、これを用いて蛍光体ペースト
を作製した。この蛍光体ペーストを、作製しようとする
蛍光表示管の陽極基板の陽極導体上に所定のパターンで
塗布した。酸化抑制物質としての酸化性ガス吸着物質で
あるＴｉＯX （１＜Ｘ＜２）の粉末をペースト状にし、
これを陽極導体に設けた蛍光体ペーストのパターンの周
辺に適当なパターンで塗布した。以下、第５実施例と同
様にして蛍光表示管を作製した。(6) Sixth Embodiment Gd 2 O 2 S: Eu
10% of n 2 O 3 was added, and this was used to prepare a phosphor paste. This phosphor paste was applied in a predetermined pattern on an anode conductor of an anode substrate of a fluorescent display tube to be manufactured. Powder of TiO x (1 <X <2), which is an oxidizing gas adsorbing substance as an oxidation inhibitor, is made into a paste,
This was applied in a suitable pattern around the phosphor paste pattern provided on the anode conductor. Thereafter, a fluorescent display tube was manufactured in the same manner as in the fifth embodiment.
【００２８】この蛍光表示管を、陽極電圧４０Ｖを印加
して発光させ、寿命試験を行なった。１０００時間経過
後の輝度残存率は、ＴｉＯX 層を持たない比較品が６０
％であったのに対し、ＴｉＯX 層を陽極周辺に配置した
本実施例の製品では約８０％と改善効果が見られた。The fluorescent display tube was caused to emit light by applying an anode voltage of 40 V, and a life test was performed. After 1000 hours, the luminance remaining ratio was 60% for the comparative product having no TiO X layer.
%, Whereas the product of the present example in which the TiO X layer was arranged around the anode exhibited an improvement effect of about 80%.
【００２９】（７）第７実施例 Ｙ2 Ｏ2 Ｓ：Ｅｕ赤色発光蛍光体に導電材料としてＩｎ
2 Ｏ3 を１０％添加し、これを用いて蛍光体ペーストを
作製した。この蛍光体ペーストを、作製しようとする蛍
光表示管の陽極基板の陽極導体上に所定のパターンで塗
布した。黒鉛の粉末に対し、酸化抑制物質としての酸化
性ガス吸着物質である酸化カルシウム（ＣａＯ）の粉末
を１０％添加したものをペースト状にし、これを陽極導
体に設けた蛍光体ペーストのパターンの周辺に適当なパ
ターンで塗布した。以下、第５実施例と同様にして蛍光
表示管を作製した。(7) Seventh Embodiment A Y 2 O 2 S: Eu red light emitting phosphor is made of In as a conductive material.
10% of 2 O 3 was added, and this was used to prepare a phosphor paste. This phosphor paste was applied in a predetermined pattern on an anode conductor of an anode substrate of a fluorescent display tube to be manufactured. A graphite powder is added with 10% of a powder of calcium oxide (CaO), which is an oxidizing gas-adsorbing substance as an oxidation-suppressing substance, to form a paste, which is formed around the phosphor paste pattern provided on the anode conductor. In an appropriate pattern. Thereafter, a fluorescent display tube was manufactured in the same manner as in the fifth embodiment.
【００３０】この蛍光表示管を、陽極電圧４０Ｖを印加
して発光させ、寿命試験を行なった。１０００時間経過
後の輝度残存率は、ＣａＯ層を持たない比較品が６０％
であったのに対し、ＣａＯ層を陽極周辺に配置した本実
施例の製品では約８０％と改善効果が見られた。The fluorescent display tube was caused to emit light by applying an anode voltage of 40 V, and a life test was performed. The luminance remaining rate after 1000 hours is 60% for the comparative product having no CaO layer.
On the other hand, the product of this example in which the CaO layer was arranged around the anode showed an improvement effect of about 80%.
【００３１】酸化カルシウム以外に、酸化マグネシウム
（ＭｇＯ）、酸化バリウム（ＢａＯ）、酸化ストロンチ
ウム（ＳｒＯ）を用いても同様な効果が得られた。これ
らの物質は、蛍光表示管内にある水と反応して安定な水
酸化物となり、また二酸化炭素と反応して安定な炭酸化
物となるなど、蛍光表示管内に残存していた酸素を含む
ガス、物質を吸着して蛍光体への悪影響（酸化など）を
減少させる働きがある。Similar effects were obtained by using magnesium oxide (MgO), barium oxide (BaO), and strontium oxide (SrO) in addition to calcium oxide. These substances react with water in the fluorescent display tube to form a stable hydroxide, and also react with carbon dioxide to form a stable carbonate, such as a gas containing oxygen remaining in the fluorescent display tube, It functions to adsorb substances and reduce adverse effects on the phosphor (eg, oxidation).
【００３２】また、黒鉛の中に、酸化カルシウムの他に
水ガラス、又は珪酸カリウムを１〜２０％添加しても同
様の効果が得られる。Similar effects can be obtained by adding 1 to 20% of water glass or potassium silicate to graphite in addition to calcium oxide.
【００３３】蛍光表示管の駆動時、管内に残されていた
Ｏ2 、Ｈ2 Ｏ、ＣＯ2 などの酸素原子を含むガスが蛍光
体層の表面に吸着し、一部は蛍光体層の表面の蛍光体粒
子の内部に入り、蛍光体を経時的に酸化させて発光特性
を劣化させていく。しかしながら、本発明の第１〜第３
実施例によれば、水素放出物質が水素を放出して蛍光表
示管内の酸素分圧を低下させ、また第４〜第７実施例に
よれば、酸化性ガス吸着物質が酸素を吸収して蛍光表示
管内の酸素分圧を低下させる。その結果として蛍光表示
管内では酸素が蛍光体層に衝突する確率が減少し、蛍光
体の酸化が進みにくくなり、寿命が改善される。When the fluorescent display tube is driven, the gas containing oxygen atoms such as O 2 , H 2 O, and CO 2 remaining in the tube is adsorbed on the surface of the phosphor layer, and a part of the gas is adsorbed on the surface of the phosphor layer. Of the phosphor particles, and oxidizes the phosphor over time to degrade the emission characteristics. However, the first to third aspects of the present invention
According to the embodiment, the hydrogen releasing material releases hydrogen to lower the oxygen partial pressure in the fluorescent display tube, and according to the fourth to seventh embodiments, the oxidizing gas adsorbing material absorbs oxygen to emit fluorescent light. Reduce the oxygen partial pressure in the display tube. As a result, the probability of oxygen colliding with the phosphor layer in the fluorescent display tube is reduced, the oxidation of the phosphor becomes difficult to progress, and the life is improved.
【００３４】また、第１〜第３実施例によれば、蛍光体
層を焼成する際に蛍光体を酸化雰囲気から保護するの
で、高温で焼成を行なうことができ、従って高温で焼成
して蛍光体ペーストに含まれるバインダなどの成分を確
実に除去することができる。According to the first to third embodiments, since the phosphor is protected from the oxidizing atmosphere when the phosphor layer is fired, the firing can be performed at a high temperature. Components such as a binder contained in the body paste can be reliably removed.
【００３５】第１〜第３実施例において、酸化抑制物質
としての水素放出材料として、ＴｉＮ、α−Ｓｉ、ＢＣ
ＮＴなどを用いても略同様の効果が得られる。In the first to third embodiments, TiN, α-Si, BC
Almost the same effects can be obtained by using NT or the like.
【００３６】イオウを母体成分として含む蛍光体Ｌｎ2
Ｏ2 Ｓ：Ｒｅ（Ｌｎ＝Ｙ、Ｌａ、Ｇｄ，Ｒｅ＝Ｅｕ）に
おいて、ＥｕをＴｂとした場合には、発光色は・・・で
あり、実施例２〜７と略同様の方法で寿命の改善につい
て同様の効果が得られる。Phosphor Ln 2 containing sulfur as a parent component
In the case of O 2 S: Re (Ln = Y, La, Gd, Re = Eu), when Eu is Tb, the emission color is..., And the lifetime is substantially the same as in Examples 2 to 7. A similar effect can be obtained for the improvement of.
【００３７】[0037]
【発明の効果】本発明によれば、イオウを母体成分とし
て含む蛍光体に酸化抑制物質（水素放出材料、酸化性ガ
ス吸着物質）を添加した。このため、酸化雰囲気から蛍
光体が保護されるので高い温度で焼成することが可能に
なり、バインダなどの不用成分を確実に除去できる。ま
た蛍光表示管に実装した場合には、管内に残存した酸化
性ガスを吸着するので、発光素子としての寿命が長くな
るという効果が得られる。According to the present invention, an oxidation inhibitor (hydrogen releasing material, oxidizing gas adsorbing material) is added to a phosphor containing sulfur as a base component. For this reason, since the phosphor is protected from the oxidizing atmosphere, baking can be performed at a high temperature, and unnecessary components such as a binder can be reliably removed. Further, when mounted on a fluorescent display tube, an oxidizing gas remaining in the tube is adsorbed, so that the effect of extending the life of the light emitting element is obtained.
【図１】本発明の第１実施例の効果を示す図であって、
水素化ジルコニウム添加量と初期輝度の関係を示す図で
ある。FIG. 1 is a diagram showing an effect of a first embodiment of the present invention,
It is a figure which shows the relationship between zirconium hydride addition amount and initial luminance.
【図２】本発明の第４実施例の効果を示す図であって、
Ｎｉ粉末の添加量が異なる蛍光体を備えた複数種類の実
施例の蛍光表示管と、Ｎｉ粉末無添加（添加量０％）の
蛍光表示管について、初期輝度と１０００時間経過後の
輝度残存率をそれぞれ測定して示した図である。FIG. 2 is a diagram showing an effect of a fourth embodiment of the present invention,
The initial luminance and the luminance retention rate after 1000 hours were passed for the fluorescent display tubes of the examples having phosphors with different amounts of Ni powder added and the fluorescent display tubes without Ni powder added (addition amount 0%). It is the figure which measured and shown each.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｊ 29/94 Ｈ０１Ｊ 29/94 31/15 31/15 Ｅ (72)発明者 秋元 百子 千葉県茂原市大芝629 双葉電子工業株式 会社内 (72)発明者 佐藤 義孝 千葉県茂原市大芝629 双葉電子工業株式 会社内 Ｆターム(参考） 4H001 CA06 CC03 CC05 CC09 CF01 XA08 XA16 XA30 XA39 XA57 XA64 YA30 YA63 YA65 5C032 AA06 JJ08 JJ10 5C036 EE01 EF02 EF05 EG36 EH16 EH26 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01J 29/94 H01J 29/94 31/15 31/15 E (72) Inventor Momoko Akimoto Mobara-shi, Chiba Shiba 629 Futaba Electronics Co., Ltd. (72) Inventor Yoshitaka Sato 629 Oshiba, Mobara-shi, Chiba Futaba Electronics Co., Ltd. JJ08 JJ10 5C036 EE01 EF02 EF05 EG36 EH16 EH26
Claims (9)
成分として含む蛍光体。1. A phosphor to which an oxidation inhibitor is added and which contains sulfur as a base component.
求項１記載の蛍光体。2. The phosphor according to claim 1, wherein the oxidation inhibitor is a hydrogen releasing material.
2 、ＴｉＯ2 、ＴｉＮ、α−Ｓｉ、ＢＣＮＴからなる群
から選択された請求項２記載の蛍光体。3. The method according to claim 1, wherein the hydrogen releasing material is ZrH 2 , TiH
2, TiO 2, TiN, α -Si, phosphor according to claim 2, wherein selected from the group consisting of BCNT.
ある請求項１記載の蛍光体。4. The phosphor according to claim 1, wherein the oxidation suppressing substance is an oxidizing gas adsorbing substance.
Ｏx 、ＣａＯ、ＭｇＯ、ＢａＯ、ＳｒＯ殻なる群から選
択された請求項４記載の蛍光体。5. The method according to claim 1, wherein the oxidizing gas adsorbing substance is Ni, Ti
O x, CaO, MgO, BaO , phosphor according to claim 4, wherein selected from SrO shell consisting groups.
が、ＺｎＳ、Ｌｎ2Ｏ2 Ｓ：Ｒｅ（Ｌｎ＝Ｙ、Ｌａ、Ｇ
ｄ，Ｒｅ＝Ｅｕ、Ｔｂ）からなる群から選択された請求
項１又は２又は３又は４又は５記載の蛍光体。6. The phosphor containing sulfur as a host component is ZnS, Ln 2 O 2 S: Re (Ln = Y, La, G
The phosphor according to claim 1, 2 or 3 or 4 or 5 selected from the group consisting of d, Re = Eu, Tb).
陽極導体に設けられて前記陰極から放出された電子が射
突して発光する蛍光体層とを有する陽極とが、気密外囲
器内に設けられた蛍光表示管において、 前記蛍光体が、酸化抑制物質が添加され、イオウを母体
成分として含む蛍光体である蛍光表示管。7. An airtight envelope comprising: a cathode for emitting electrons; an anode having an anode conductor and a phosphor layer provided on the anode conductor and emitting light emitted from the cathode by projecting from the cathode. The fluorescent display tube provided in the above, wherein the phosphor is a phosphor to which an oxidation inhibitor is added and sulfur is contained as a base component.
が、ＺｎＳ、Ｌｎ2Ｏ2 Ｓ：Ｒｅ（Ｌｎ＝Ｙ、Ｌａ、Ｇ
ｄ，Ｒｅ＝Ｅｕ、Ｔｂ）からなる群から選択された請求
項７記載の蛍光表示管。8. The phosphor containing sulfur as a host component is ZnS, Ln 2 O 2 S: Re (Ln = Y, La, G
8. The fluorescent display tube according to claim 7, wherein the fluorescent display tube is selected from the group consisting of d, Re = Eu, Tb).
陽極導体に設けられて前記陰極から放出された電子が射
突して発光する蛍光体層とを有する陽極とが、気密外囲
器内に設けられた蛍光表示管において、 前記蛍光体が、イオウを母体成分として含む蛍光体であ
り、 蛍光体層が設けられた陽極の近傍に、酸化抑制物質を有
する層が設けられたことを特徴とする蛍光表示管。9. An airtight envelope comprising: a cathode for emitting electrons; an anode having an anode conductor and a phosphor layer provided on the anode conductor and emitting light emitted from the cathode by projecting from the cathode. In the fluorescent display tube provided therein, the phosphor is a phosphor containing sulfur as a base component, and a layer having an oxidation suppressing substance is provided in the vicinity of the anode on which the phosphor layer is provided. Characteristic fluorescent display tube.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000025369A JP2001214160A (en) | 2000-02-02 | 2000-02-02 | Fluorescent substance and fluorescent display tube |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=18551235
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007317432A (en) * | 2006-05-24 | 2007-12-06 | Mitsubishi Electric Corp | Field emission type image display device and non-evaporating type getter |
-
2000
- 2000-02-02 JP JP2000025369A patent/JP2001214160A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007317432A (en) * | 2006-05-24 | 2007-12-06 | Mitsubishi Electric Corp | Field emission type image display device and non-evaporating type getter |
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