JP2936902B2 - Manufacturing method of EL fluorescent material - Google Patents

Manufacturing method of EL fluorescent material

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Publication number
JP2936902B2
JP2936902B2 JP21364992A JP21364992A JP2936902B2 JP 2936902 B2 JP2936902 B2 JP 2936902B2 JP 21364992 A JP21364992 A JP 21364992A JP 21364992 A JP21364992 A JP 21364992A JP 2936902 B2 JP2936902 B2 JP 2936902B2
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JP
Japan
Prior art keywords
phosphor
sulfate
luminance
heat treatment
life
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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JP21364992A
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Japanese (ja)
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JPH0633053A (en
Inventor
明 西原
年治 林
昌宏 関口
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】この発明は実用上の発光素子とし
て充分な高輝度、長寿命特性を有し、かつ特性のばらつ
きが極めて小さく、しかも収率、歩留りの極めて高い優
れたエレクトロルミネッセンス（ＥＬ）蛍光体の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroluminescent (EL) device which has a sufficiently high luminance and a long life as a practical light emitting device, has a very small variation in characteristics, and has a very high yield and a high yield. A) a method for producing a phosphor;

【０００２】[0002]

【従来の技術】ＥＬ蛍光体は、これを有機誘電バインダ
ーに分散して一方が透明である２枚の電極間にはさみ、
両電極間に交流電圧を印加することによって発光する。
このように構成された素子は薄型面発光光源として液晶
ディスプレイのバックライト等に採用されている。2. Description of the Related Art An EL phosphor is dispersed in an organic dielectric binder and sandwiched between two electrodes, one of which is transparent,
Light is emitted by applying an AC voltage between both electrodes.
The element configured as described above is employed as a thin surface emitting light source in a backlight of a liquid crystal display or the like.

【０００３】従来から採用されているＥＬ蛍光体として
は、硫化亜鉛結晶に発光中心としてＣｕを付活したもの
がある。しかし従来この蛍光体を用いて作製された発光
素子は、他の発光素子に比べて発光輝度や発光寿命が悪
い為、種々の改良がなされている。これらのうちで発光
輝度、寿命特性の向上については、同一出願人が、蛍光
体を酸でエッチングした後に、酸化剤を含むキレート剤
で洗浄する方法、及び酸化剤を含む酢酸、及び硫酸の一
種または、これらの混合で洗浄する方法を提案してい
る。また(イ)米国特許３,１１３,９２９号には蛍光体を
酸素雰囲気中で加熱して輝度を向上する方法、(ロ)米国
特許５,００５,８０５号、及び特開昭６１−２９６０８
５号には硫化亜鉛、銅化合物、ハロゲン化物の混合物を
１１００〜１２００℃で焼成することによって六方晶形
（ウルツァイト型）硫化亜鉛蛍光体を製造し、これにボ
ールミルあるいは静水圧などのメカノケミカル処理を加
えて六方晶形よりも輝度、寿命特性の優れた立方晶形
（閃亜鉛鉱型）に変換させた蛍光体を大気中で開放アニ
ール(７００〜９５０℃)する方法、(ハ)特開平２−９４
２８７号には蛍光体を酸素より活性なオゾンで処理する
ことによって蛍光体表面層に酸素層を形成し、寿命特性
を改善する方法が開示されている。[0003] As an EL phosphor conventionally used, there is a phosphor obtained by activating Cu as an emission center in a zinc sulfide crystal. However, a light-emitting element conventionally manufactured using the phosphor has various improvements since the light-emitting luminance and the light-emitting life are lower than those of other light-emitting elements. Among these, for the improvement of the emission luminance and the life characteristics, the same applicant, after etching the phosphor with an acid, a method of washing with a chelating agent containing an oxidizing agent, and one of acetic acid and sulfuric acid containing the oxidizing agent Alternatively, a method of cleaning by mixing these is proposed. Also, (a) U.S. Pat. No. 3,113,929 discloses a method of improving luminance by heating a phosphor in an oxygen atmosphere, (B) U.S. Pat. No. 5,005,805, and JP-A-61-29608.
No. 5 manufactures a hexagonal (wurtzite type) zinc sulfide phosphor by firing a mixture of zinc sulfide, copper compound, and halide at 1100 to 1200 ° C. In addition, a method of subjecting a phosphor converted to a cubic (sphalerite type) having better luminance and life characteristics than a hexagonal type to open annealing (700 to 950 ° C.) in the air, (c) Japanese Patent Laid-Open No. 2-94
No. 287 discloses a method of treating a phosphor with ozone that is more active than oxygen to form an oxygen layer on the phosphor surface layer and improve the life characteristics.

【０００４】しかしながら、上述した(イ)〜(ハ)の製
法、あるいは処理法を用いて蛍光体を作製しても、実用
的な発光素子として輝度、寿命特性が不充分であるばか
りか特性のばらつきも大きく、しかも製造上の収率、歩
留りが悪いため製造コストがかかり市場の要求に添う蛍
光体を提供するには難しい。However, even if a phosphor is manufactured by using the above-mentioned manufacturing methods (a) to (c) or the processing method, not only the luminance and the life characteristics are insufficient as a practical light emitting element but also the characteristics are not sufficient. Since the dispersion is large and the production yield and yield are poor, the production cost is high, and it is difficult to provide a phosphor that meets market requirements.

【０００５】[0005]

【発明が解決しようとする課題】そこで本発明者らは、
まず上記課題を解決するために、従来より公知の以下の
製法、即ち(１)硫化亜鉛、銅化合物、及び融剤(粒成長
剤)としてのアルカリ金属塩化物、アルカリ土類金属塩
化物、塩化アンモニウム等のハロゲン化物を混合してフ
タを閉めた坩堝中１１００〜１３００℃で焼成して蛍光
体に必要な平均３０μｍ程度の粒子に成長させ、(２)次
にこの焼成によって得られたウルツァイト型ＺｎＳ結晶
をボールミル等を用いた機械的応力（メカノケミカル効
果）を加えることによって、より輝度、寿命特性の優れ
た閃亜鉛鉱型ＺｎＳ結晶形に変換し、(３)最後にこの蛍
光体を７００〜９５０℃大気中開放アニールする方法か
らなる製造プロセスを基本骨子として、上記(イ)〜(ハ)
の技術を含めて再度見直し、検討することを試みた。SUMMARY OF THE INVENTION Accordingly, the present inventors
First, in order to solve the above-mentioned problems, the following known production methods, namely, (1) zinc sulfide, a copper compound, and alkali metal chlorides, alkaline earth metal chlorides as fluxes (grain growing agents), and chlorides, are used. A halide such as ammonium is mixed and fired at 1100 to 1300 ° C. in a crucible with a closed lid to grow particles having an average of about 30 μm required for the phosphor. (2) Next, the wurtzite type obtained by this firing By applying mechanical stress (mechanochemical effect) using a ball mill or the like to the ZnS crystal, the ZnS crystal is converted into a zinc-blende ZnS crystal form having more excellent luminance and life characteristics. The above (a) to (c) are based on a manufacturing process consisting of a method of annealing at 950 ° C.
I reviewed it again, including the technology, and tried to consider it.

【０００６】しかしながら上記の製法では特に寿命特性
が悪く、実用に供する高輝度、長寿命特性の蛍光体を得
ることはできなかった。特に従来の製法の中で上記(３)
の工程において、フタを開放した坩堝中で蛍光体を大気
中アニールするため、ＺｎＳが酸化分解してＺｎＯに変
化し、従って蛍光体の収率、歩留りが非常に悪化し、し
かも焼成時の蛍光体は坩堝中の上部と下部では酸素分圧
が異なるため蛍光体特性のばらつきが大きく、また焼成
時には毒性の ＳＯ2酸性ガスが大量に発生するために、
環境及び衛生上の問題、更にこの発生ガスによる焼成炉
の劣化等、非常に多くの問題が含まれていることが判明
した。However, the above-mentioned production method has particularly poor life characteristics, and it has not been possible to obtain a phosphor having high luminance and long life characteristics which can be practically used. Especially in the conventional manufacturing method, the above (3)
In the step (3), the phosphor is annealed in the air in a crucible with an open lid, so that ZnS is oxidized and decomposed to change to ZnO, so that the yield and the yield of the phosphor are extremely deteriorated. The body has a large variation in phosphor characteristics due to different oxygen partial pressures in the upper and lower parts of the crucible, and a large amount of toxic SO 2 acid gas is generated during firing.
It has been found that there are numerous problems, such as environmental and sanitary problems, and deterioration of the firing furnace due to the generated gas.

【０００７】そこで本発明の第一の着眼点としては、再
焼成時に蛍光体が大気中の酸素に影響されないように
(ＺｎＯ、ＳＯ2ガスが大量に発生しないように）フタを
した密閉坩堝中で焼成して特性を向上する方法を検討し
た結果、蛍光体に硫酸塩として硫酸亜鉛、硫酸バリウ
ム、硫酸ストロンチウムの一種、あるいはこれらの混合
物を混合して５５０〜９００℃でアニールすると収率、
歩留りが極めて高く、また焼成時には毒性の ＳＯ2酸性
ガスの発生がなく、しかも特性のばらつきがほとんどな
い安定した高輝度、長寿命蛍光体が得られることが判明
した。Therefore, the first point of the present invention is to prevent the phosphor from being affected by atmospheric oxygen during refiring.
As a result of studying a method of improving the characteristics by firing in a closed crucible with a lid (so that a large amount of ZnO and SO 2 gas is not generated), zinc sulfate, barium sulfate, and strontium sulfate were used as a sulfate in the phosphor. Or a mixture thereof and annealed at 550-900 ° C., yield
It has been found that the yield is extremely high, and a stable, high-brightness, long-life phosphor free of toxic SO 2 acid gas during firing and having little variation in characteristics can be obtained.

【０００８】第二の着眼点としては、蛍光体表面層をエ
ッチング後、オゾン処理するといった特別な工程を経な
いでより優れた輝度、寿命特性を発現させるために、更
に低温熱処理するといった簡単な方法で特性を向上させ
る手段を検討した。即ち、エッチング処理した蛍光体の
表面ではＺｎ−Ｓの結合が切断され、表面エネルギーが
高く非常に不安定な状態になっており、またエッチング
によるダメージによって蛍光体表面近傍では結晶の格子
不整が発生しているため特性に大きく悪影響を与える。
このため大気中で低温熱処理することにより、この表面
層を適度に酸化して表面エネルギーを緩和させ、かつ表
面近傍の格子不整を再結晶させるとの考えに立って行わ
れた。この結果、蛍光体表面層をエッチングしたのち大
気中９０〜１６０℃、２５〜２５０時間熱処理すること
によって大幅に輝度、寿命特性が向上することが判明し
た。As a second point of view, a simple low-temperature heat treatment is performed in order to develop superior brightness and life characteristics without performing a special process such as ozone treatment after etching the phosphor surface layer. The means to improve the characteristics by the method were studied. In other words, Zn-S bonds are broken on the surface of the phosphor subjected to the etching treatment, the surface energy is high and the state is very unstable, and the lattice damage of the crystal occurs near the phosphor surface due to damage by etching. This has a significant adverse effect on the characteristics.
Therefore, the heat treatment was performed at low temperature in the air to moderately oxidize this surface layer to reduce surface energy and recrystallize lattice irregularities near the surface. As a result, it was found that the luminance and the life characteristics were significantly improved by performing the heat treatment in the air at 90 to 160 ° C. for 25 to 250 hours after etching the phosphor surface layer.

【０００９】本発明は上記の考えに基づき従来の問題を
解決したＥＬ蛍光体の製造方法を提供するものであり、
本方法で作製したＥＬ蛍光体は従来の製造方法を用いた
ものに比べて初期輝度が２５％、輝度半減寿命が８０％
向上した特性を発現する。また本方法では蛍光体特性の
ばらつきが極めて小さく、収率、歩留りが極めて高いた
め製造コストも軽減され、しかも焼成時に毒性の ＳＯ2
酸性ガスの発生がない優れた製造方法が提供される。The present invention provides a method for manufacturing an EL phosphor which solves the conventional problems based on the above-mentioned idea.
The EL phosphor produced by this method has an initial luminance of 25% and a luminance half-life of 80% as compared with those using a conventional production method.
Develop improved properties. Further, in the present method, the dispersion of the phosphor characteristics is extremely small, the yield and the yield are extremely high, the production cost is reduced, and the toxic SO 2
An excellent manufacturing method without generation of an acid gas is provided.

【００１０】[0010]

【課題を解決するための手段】本発明は硫化亜鉛、銅化
合物および塩化物を含む混合物を焼成して中間蛍光体を
製造する工程と、この中間蛍光体に機械的応力を加えた
後再焼成する工程とを具備する蛍光体の製造方法であっ
て、前記再焼成工程が硫酸塩を混合し、大気をしゃ断し
て５５０〜９００℃で行われ、さらに、再焼成工程の後
に、得られた蛍光体の表面層をエッチング処理した後、
大気中、９０〜１６０℃で２０〜２５０時間熱処理する
工程を有することをからなるエレクトロルミネッセンス
蛍光体の製造方法を提供する。According to the present invention, there is provided a process for sintering a mixture containing zinc sulfide, a copper compound and a chloride to produce an intermediate phosphor, and re-sintering after applying a mechanical stress to the intermediate phosphor. Wherein the re-firing step is performed at 550-900 ° C. by mixing sulfate, shutting off the atmosphere, and further obtained after the re-firing step. After etching the phosphor surface layer,
A method for producing an electroluminescent phosphor, comprising a step of performing a heat treatment at 90 to 160 ° C. for 20 to 250 hours in the air.

【００１１】また本発明はその好適な態様として硫酸塩
が硫酸亜鉛、硫酸バリウム、硫酸ストロンチウムの一種
またはこれらの混合物であることを特徴とする。In a preferred aspect of the present invention, the sulfate is one of zinc sulfate, barium sulfate, and strontium sulfate, or a mixture thereof.

【００１２】本発明におけるＥＬ蛍光体の製造方法は、
硫化亜鉛に銅化合物、例えば酢酸銅(Ｃｕ濃度０.０３〜
０.１２ｗｔ％)を湿式混合し乾燥したのち、この混合物
に融剤としてアルカリ金属塩化物、アルカリ土類金属塩
化物、塩化アンモニウムの少なくとも一種を６〜１００
％混合し、フタを閉めた坩堝中１１００〜１３００℃、
２〜１０時間焼成して蛍光体に必要な平均３０μｍ程度
の粒子に成長させる。次に焼成後の蛍光体をイオン交換
水で数回洗浄し、乾燥する。The method for producing an EL phosphor according to the present invention comprises:
Copper compounds such as copper acetate (Cu concentration 0.03-
0.12% by weight) and dried, and at least one of an alkali metal chloride, an alkaline earth metal chloride and ammonium chloride as a flux is added to the mixture in an amount of 6 to 100%.
% In a crucible with a lid closed, 1100-1300 ° C,
It is baked for 2 to 10 hours to grow particles having an average of about 30 μm required for the phosphor. Next, the fired phosphor is washed several times with ion-exchanged water and dried.

【００１３】この焼成によって得られたＺｎＳ：Ｃｕ、
Ｃｌ蛍光体は大部分ウルツァイト型ＺｎＳ結晶(六方晶)
であるため、より輝度、寿命特性の優れた閃亜鉛鉱型Ｚ
ｎＳ結晶形に変換する必要から例えばボールミルを用い
て蛍光体粒子が粉砕されないように充分に機械的応力
(メカノケミカル効果)を加える。またこの蛍光体は１１
００〜１３００℃の高温で焼成しているためバルク結晶
中にはイオウが揮発して生じた空孔が多く発生し、これ
が寿命特性を大きく低下させる原因になっている。また
機械的応力を加えているため結晶のダメージが大きく、
発光、寿命特性を低下させる原因を加えている。The ZnS: Cu,
Cl phosphor is mostly wurtzite type ZnS crystal (hexagonal)
Therefore, the zinc-blende type Z having more excellent brightness and life characteristics
Since it is necessary to convert to the nS crystal form, sufficient mechanical stress is applied so that the phosphor particles are not crushed using, for example, a ball mill.
(Mechanochemical effect). This phosphor has 11
Since it is fired at a high temperature of 00 to 1300 ° C., a large number of vacancies are generated in the bulk crystal due to the volatilization of sulfur, which causes the life characteristics to be greatly reduced. In addition, crystal damage is large because mechanical stress is applied,
A cause for lowering the light emission and life characteristics is added.

【００１４】このため、次の段階ではＺｎＳバルク結晶
中のイオウ空孔を除去し、かつ結晶のダメージを取り除
くために硫酸塩を加え、フタをした密閉坩堝中で再焼成
される。この段階によって密閉坩堝中で固定化した硫酸
塩中の硫酸根 ＳＯ4 2-イオンによって、結晶中のイオウ
空孔がＳまたはＯ(いずれも同族元素)で置換され、また
このときの加熱処理で再結晶される。For this reason, in the next stage, the sulfur vacancies in the ZnS bulk crystal are removed, and a sulfate is added to remove the crystal damage, and the ZnS bulk crystal is refired in a closed crucible with a lid. At this stage, the sulfur vacancies in the crystal were replaced with S or O (both of the same family elements) by the sulfate SO 4 2- ions in the sulfate immobilized in the closed crucible, and the heat treatment at this time Recrystallized.

【００１５】硫酸塩としては硫酸亜鉛、硫酸バリウム、
硫酸ストロンチウムの一種またはこれらの混合物を蛍光
体に対して５〜２５ｗｔ％加えるのが適当であり、硫酸
塩が５ｗｔ％よりも少ないと充分にＳ空孔が除去できな
いため効果がなく、２５ｗｔ％より多いと焼成後の処理
工程で廃棄処理（エッチング）の負担が増すので好まし
くない。再焼成温度は５５０〜９００℃の範囲で１〜２
０時間焼成することが適当であり、５５０℃より低いと
Ｓ及びＯの拡散が不充分となり結晶中のＳ空孔が除去で
きないため効果がなく、９００℃より高いとイオウの揮
発が高くなり好ましくない。As sulfates, zinc sulfate, barium sulfate,
It is appropriate to add one kind of strontium sulfate or a mixture thereof to the phosphor in an amount of 5 to 25% by weight. If the amount of sulfate is less than 5% by weight, S vacancies cannot be sufficiently removed, so that there is no effect. If the amount is too large, the load of disposal processing (etching) in the processing step after firing increases, which is not preferable. Refiring temperature is 1-2 in the range of 550-900 ° C.
It is appropriate to bake for 0 hours. If the temperature is lower than 550 ° C., the diffusion of S and O becomes insufficient and the S vacancies in the crystal cannot be removed, so that there is no effect. Absent.

【００１６】次に焼成後の蛍光体を一般的に実施されて
いるエッチング処理により、蛍光体表面層に多く含まれ
る結晶の格子不整、過剰のＣｕxＳ(Ｘ＝１〜２)が除去
され、より輝度、寿命の優れた特性を発現するが、この
処理後の蛍光体表面ではＺｎ−Ｓの結合が切断され表面
エネルギーが高く非常に不安定な状態になっている。ま
たエッチングのダメージによって再び蛍光体表面近傍に
結晶の格子不整が発生するため寿命特性に影響を与え
る。このため次の段階で大気中低温熱処理し、蛍光体表
面を適度に酸化して表面エネルギーを緩和させ、かつ蛍
光体表面近傍の結晶の格子不整を再結晶させる。Next, the phosphor after firing is subjected to an etching process which is generally performed to remove lattice irregularities and excessive Cu x S (X = 1 to 2) of crystals contained in the phosphor surface layer. However, the surface of the phosphor after the treatment is broken, the bond of Zn-S is broken, and the surface energy is high and the phosphor is in an extremely unstable state. In addition, the lattice damage of the crystal occurs again near the phosphor surface due to the etching damage, which affects the life characteristics. Therefore, in the next stage, a low-temperature heat treatment in the air is performed to moderately oxidize the phosphor surface to reduce the surface energy and recrystallize the lattice irregularity of the crystal near the phosphor surface.

【００１７】上記低温熱処理温度は９０〜１６０℃、好
ましくは１００〜１５０℃が適当であり、処理時間は２
０〜２５０時間が適当である。処理温度が９０℃より低
いと蛍光体表面に存在する結晶格子不整の再結晶が不充
分であるため効果がなく、１６０℃よりも高いと逆に酸
化の進行により蛍光体表面近傍の結晶のダメージが大き
くなるため効果がない。処理時間については、２０時間
よりも短い場合でも２５０時間より長い場合でも、いず
れもそれぞれ前記理由と同様に効果がなく好ましくな
い。The above low temperature heat treatment temperature is 90 to 160 ° C., preferably 100 to 150 ° C.
0-250 hours is appropriate. When the treatment temperature is lower than 90 ° C., recrystallization of the crystal lattice irregularity existing on the phosphor surface is insufficient, so that there is no effect. Has no effect because it increases. Regarding the processing time, whether the processing time is shorter than 20 hours or longer than 250 hours, each has the same effect as described above, which is not preferable.

【００１８】[0018]

【実施例】以下、本発明を具体的実施例に基づいて詳述
する。硫化亜鉛１ｋｇと酢酸銅２水和物１.５５ｇをイ
オン交換水で湿式混合して １２５℃で２０時間乾燥し
た。次にこの混合物２００ｇに融剤として塩化バリウム
２水和物を８ｇ、塩化マグネシウム６水和物を１０ｇ、
塩化ナトリウム６ｇを混合してアルミナ製２８０ｃｃの
坩堝中に入れてフタをして１２００℃で４時間大気中焼
成した。焼成後、この焼成物をイオン交換水２リットル
を用いて５回洗浄して融剤を溶解除去し、濾過して１３
０℃で１５時間乾燥した。次にこの蛍光体１５０ｇを１
リットルのポリエチレン製ポットに入れ、アルミナボー
ルφ１０ｍｍを１５０ｇ入れてフタをし、ボールミル回
転台上６００回転／分、１２０分回転させた。この蛍光
体はＸ線回折では立方晶形ＺnＳに変換されていた。次
にこの蛍光体１００ｇと硫酸塩として硫酸亜鉛１５ｇ、
硫酸バリウム５ｇ、硫酸ストロンチウム５ｇを混合し、
この混合物をアルミナ製１５０ｃｃの坩堝中に入れてフ
タをし、８００℃で５時間大気中再焼成した。次に焼成
後、この蛍光体を坩堝からとりだして２０％酢酸水溶液
に入れ８０℃の温度で１時間撹拌洗浄したのち、イオン
交換水２リットルで７回洗浄した。濾過後、蛍光体を１
１０℃の温度で１００時間熱処理した結果、収率９１％
の蛍光体が得られた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on specific embodiments. 1 kg of zinc sulfide and 1.55 g of copper acetate dihydrate were wet-mixed with ion-exchanged water and dried at 125 ° C. for 20 hours. Next, 8 g of barium chloride dihydrate and 10 g of magnesium chloride hexahydrate were used as fluxes in 200 g of this mixture.
6 g of sodium chloride was mixed, put into a 280 cc crucible made of alumina, covered with a lid, and fired in the air at 1200 ° C. for 4 hours. After firing, the fired material was washed five times with 2 liters of ion-exchanged water to dissolve and remove the flux, and filtered to remove 13%.
Dry at 0 ° C. for 15 hours. Next, 150 g of this phosphor was
Then, 150 g of an alumina ball φ10 mm was put in a polyethylene liter pot, and a lid was put thereon. The lid was rotated on a ball mill rotating table at 600 rpm for 120 minutes. This phosphor was converted to cubic ZnS by X-ray diffraction. Next, 100 g of this phosphor and 15 g of zinc sulfate as a sulfate,
5 g of barium sulfate and 5 g of strontium sulfate are mixed,
The mixture was placed in a 150 cc crucible made of alumina, capped, and refired in the air at 800 ° C. for 5 hours. Next, after firing, the phosphor was taken out of the crucible, placed in a 20% acetic acid aqueous solution, washed with stirring at a temperature of 80 ° C. for 1 hour, and then washed 7 times with 2 liters of ion-exchanged water. After filtration, remove 1 phosphor
As a result of heat treatment at a temperature of 10 ° C. for 100 hours, the yield was 91%.
Was obtained.

【００１９】蛍光体の輝度、寿命特性の評価は蛍光体を
シアノエチルセルローズに混練して、ＩＴＯ（スズドー
プ酸化インジウム）を蒸着した透明ポリエチレンフィル
ム電極上にスクリーン印刷して５０μｍの発光層を形成
し、つづいてその上にチタン酸バリウムを混練したシア
ノエチルセルローズをスクリーン印刷して２０μｍの絶
縁層を形成し、最後にこの上に銀ペーストを塗布して裏
面電極を形成した。次に１００℃で３時間乾燥してから
更に８５℃で１５時間真空乾燥し、電極に端子を取りつ
け三フッ化塩化エチレン製の防湿フィルムを挟んで真空
熱圧着してＥＬ発光素子を形成した。特性評価は、室温
で、１２０Ｖ、１ｋＨzの交流電圧をこのＥＬ発光素子の
電極間に印加した結果、従来の硫酸塩を加えないで開放
坩堝中、大気中で焼成する方法の蛍光体に比べて、発光
輝度が２５１ｃｄ/ｍ2、輝度半減寿命が３１８０時間の
特性を発現し、本発明の方法では従来の方法で作製した
蛍光体に比べて、発光輝度が２５％、輝度半減寿命が８
０％向上した特性を発現した。Evaluation of the luminance and life characteristics of the phosphor was carried out by kneading the phosphor with cyanoethyl cellulose and screen-printing it on a transparent polyethylene film electrode on which ITO (tin-doped indium oxide) was deposited to form a 50 μm light-emitting layer. Subsequently, cyanoethyl cellulose kneaded with barium titanate was screen-printed thereon to form a 20 μm insulating layer, and finally a silver paste was applied thereon to form a back electrode. Next, drying was performed at 100 ° C. for 3 hours, and further vacuum drying was performed at 85 ° C. for 15 hours. Terminals were attached to electrodes, and vacuum thermocompression bonding was performed using a moisture-proof film made of ethylene trifluoride chloride to form an EL light emitting device. Characterization, at room temperature, 120V, a result of applying an AC voltage of 1 kH z between the electrodes of the EL light emitting element, in an open crucible without adding a conventional sulfate, compared to phosphor and calcining in air As a result, a light emission luminance of 251 cd / m 2 and a luminance half life of 3180 hours are exhibited. In the method of the present invention, the light emission luminance is 25% and the luminance half life is 8% as compared with the phosphor prepared by the conventional method.
The properties improved by 0% were exhibited.

【００２０】[0020]

【比較例】低温熱処理温度を変えたほかは上記実施例と
全く同様にして製造した蛍光体について特性評価した結
果、熱処理温度が９０℃より低いか、または１６０℃よ
りも高い場合は、輝度、寿命特性の向上はほとんど認め
られなかった。[Comparative Example] As a result of characteristic evaluation of a phosphor manufactured in exactly the same manner as in the above example except that the low-temperature heat treatment temperature was changed, when the heat treatment temperature was lower than 90 ° C or higher than 160 ° C, the brightness and Little improvement in life characteristics was observed.

【００２１】さらに本発明の方法において、熱処理温度
がそれぞれ１００℃、１５０℃に対して１〜４００時間
処理したときの輝度、寿命特性の挙動関係を図１および
図２のグラフで示した。図の寿命曲線(Ａ)、輝度曲線
(Ｂ)に示したように大気中熱処理の条件が２０〜２５０
時間で特性は著しく向上する。また比較例として上記方
法において、硫酸塩を加えないでフタを開けた坩堝中で
ＺｎＳ：Ｃｕ、Ｃｌ蛍光体を大気中再焼成した場合（従
来法）の特性を図３及び図４にグラフで示した。明らか
に輝度、寿命特性が向上する効果は認められなかった。
尚、この実験結果から本発明の方法は従来法と比べて焼
成時に蛍光体が酸化分解されず、したがって大量に毒性
の ＳＯ2酸性ガスの発生がなく、また蛍光体の最終収率
は常時８８〜９２％の高収率で得られたが、比較例で示
した従来法では焼成時にフタを開いた坩堝中でＺｎＳ：
Ｃｕ、Ｃｌ蛍光体を大気中再焼成するため酸化分解し、
大量の毒性のＳＯ2酸性ガスが発生して常時６２〜６８
％の低収率であった。Further, in the method of the present invention, the behavioral relationship of the luminance and the life characteristics when the heat treatment temperature is 100 ° C. and 150 ° C., respectively, for 1 to 400 hours is shown in the graphs of FIG. 1 and FIG. Life curve (A) and brightness curve
As shown in (B), the condition of the heat treatment in the air is 20 to 250.
The properties improve significantly with time. In addition, as a comparative example, in the above method, the characteristics of the case where ZnS: Cu, Cl phosphor was refired in the air in a crucible in which the lid was opened without adding a sulfate (conventional method) are shown in graphs in FIGS. Indicated. Clearly, the effect of improving the luminance and life characteristics was not recognized.
From this experimental result, it can be seen from the experimental results that the phosphor of the present invention is not oxidized and decomposed at the time of calcination as compared with the conventional method, so that a large amount of toxic SO 2 acidic gas is not generated, and the final yield of the phosphor is always 88. In the conventional method shown in the comparative example, ZnS was obtained in a crucible whose lid was opened at the time of firing.
Cu and Cl phosphors are oxidatively decomposed to refire in the air,
A large amount of toxic SO 2 acid gas is generated and is constantly 62-68
% Low yield.

【００２２】[0022]

【発明の効果】本発明の方法は従来の方法で作製した蛍
光体に比べて、発光輝度が２５％、輝度半減寿命が８０
％向上した特性を発現する。また本方法は特性のばらつ
きが極めて小さく、収率、歩留りが高いため製造コスト
も軽減され、しかも焼成時に腐食性ガス、有毒ガスが発
生しない優れた製造方法を提供する。According to the method of the present invention, the emission luminance is 25% and the luminance half-life is 80% as compared with the phosphor prepared by the conventional method.
%. Further, the present method provides an excellent production method in which the variation in characteristics is extremely small, the yield and the yield are high, the production cost is reduced, and no corrosive gas or toxic gas is generated during firing.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 本発明の方法により製造された蛍光体(熱処
理温度１５０℃)の熱処理時間(ｈ)に対する相対輝度
(Ｂ)および相対輝度半減期(Ａ)を示すグラフ。FIG. 1 shows the relative luminance of a phosphor (heat treatment temperature of 150 ° C.) manufactured by the method of the present invention with respect to the heat treatment time (h).
Graph showing (B) and relative luminance half-life (A).

【図２】 本発明の方法により製造された蛍光体(熱処
理温度１００℃)の熱処理時間(ｈ)に対する相対輝度
(Ｂ)および相対輝度半減期(Ａ)を示すグラフ。FIG. 2 shows the relative luminance of the phosphor (heat treatment temperature: 100 ° C.) manufactured by the method of the present invention with respect to the heat treatment time (h).
Graph showing (B) and relative luminance half-life (A).

【図３】 従来法により製造された蛍光体(熱処理温度
１５０℃)の相対輝度(Ｄ)および半減期(Ｃ)のグラフ。FIG. 3 is a graph of relative luminance (D) and half-life (C) of a phosphor (heat treatment temperature: 150 ° C.) manufactured by a conventional method.

【図４】 従来法により製造された蛍光体(熱処理温度
１００℃)の相対輝度(Ｄ)および半減期(Ｃ)のグラフ。FIG. 4 is a graph of relative luminance (D) and half-life (C) of a phosphor (heat treatment temperature: 100 ° C.) manufactured by a conventional method.

フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C09K 11/56 CPC C09K 11/08 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C09K 11/56 CPC C09K 11/08

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 硫化亜鉛、銅化合物および塩化物を含む
混合物を焼成して中間蛍光体を製造する工程と、この中
間蛍光体に機械的応力を加えた後再焼成する工程とを具
備する蛍光体の製造方法であって、前記再焼成工程が硫
酸塩を混合し、大気をしゃ断して５５０〜９００℃で行
われ、さらに、再焼成工程の後に、得られた蛍光体の表
面層をエッチング処理した後、大気中、９０〜１６０℃
で２０〜２５０時間熱処理する工程を有することからな
るエレクトロルミネッセンス蛍光体の製造方法。1. A fluorescent light comprising a step of firing a mixture containing zinc sulfide, a copper compound, and a chloride to produce an intermediate phosphor, and a step of applying a mechanical stress to the intermediate phosphor and then refiring the intermediate phosphor. The method of manufacturing a body, wherein the refiring step is performed at 550 to 900 ° C. by mixing sulfate and shutting off the air, and further, after the refiring step, etching the surface layer of the obtained phosphor. After treatment, in air, 90-160 ° C
A method for producing an electroluminescent phosphor, comprising a step of performing a heat treatment for 20 to 250 hours. 【請求項２】 硫酸塩が、硫酸亜鉛、硫酸バリウム、硫
酸ストロンチウムのうちの一種または二種以上の混合物
である請求項１のエレクトロルミネッセンス蛍光体の製
造方法。2. The method for producing an electroluminescent phosphor according to claim 1, wherein the sulfate is one or a mixture of two or more of zinc sulfate, barium sulfate, and strontium sulfate.
JP21364992A 1992-07-17 1992-07-17 Manufacturing method of EL fluorescent material Expired - Lifetime JP2936902B2 (en)

Priority Applications (1)

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JP21364992A JP2936902B2 (en) 1992-07-17 1992-07-17 Manufacturing method of EL fluorescent material

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Application Number Priority Date Filing Date Title
JP21364992A JP2936902B2 (en) 1992-07-17 1992-07-17 Manufacturing method of EL fluorescent material

Publications (2)

Publication Number Publication Date
JPH0633053A JPH0633053A (en) 1994-02-08
JP2936902B2 true JP2936902B2 (en) 1999-08-23

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CN103930518B (en) * 2011-11-24 2015-09-16 圣戈本陶瓷及塑料股份有限公司 luminescent material and forming method thereof

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