JP2001181620A - Method for treating surface of fluorescent substance and fluorescent film - Google Patents
Method for treating surface of fluorescent substance and fluorescent filmInfo
- Publication number
- JP2001181620A JP2001181620A JP37716499A JP37716499A JP2001181620A JP 2001181620 A JP2001181620 A JP 2001181620A JP 37716499 A JP37716499 A JP 37716499A JP 37716499 A JP37716499 A JP 37716499A JP 2001181620 A JP2001181620 A JP 2001181620A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- film
- silica
- silazane
- fluorescent
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は蛍光体の表面処理方
法及び蛍光膜に関する。更に詳細には、特に、フィール
ドエミッションディスプレイ（ＦＥＤ）など、加速電圧
が数ｋＶ〜十数ｋＶであり、かつ、電流密度の高い電子
線に対して劣化の少ない蛍光体を得るための表面処理方
法及び該方法により得られた蛍光体を用いたディスプレ
イ用の蛍光膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor surface treatment method and a phosphor film. More specifically, in particular, a surface treatment method such as a field emission display (FED) for obtaining a phosphor having an acceleration voltage of several kV to several tens of kV and having little deterioration with respect to an electron beam having a high current density. And a phosphor film for a display using the phosphor obtained by the method.
【０００２】[0002]
【従来の技術】各種デイスプレイ装置の中、電子線励起
下での蛍光膜からの発光を利用した陰極線管ディスプレ
イ（ＣＲＴ）は高輝度、高精細なディスプレイとして広
く利用されているが、特にディスプレイのフラット化、
薄型化という点では限度があり、フラット化及び薄型化
を追求するディスプレイの一つとして近年来、ＦＥＤが
注目され、開発されつつある。2. Description of the Related Art Among various display devices, a cathode ray tube display (CRT) utilizing light emission from a fluorescent film under electron beam excitation is widely used as a high-brightness and high-definition display. Flattening,
There is a limit in terms of thinning, and FEDs have been attracting attention and being developed as one of displays pursuing flatness and thinning in recent years.
【０００３】ところで、ＦＥＤは真空外囲器内に電子を
放出する平面状の電界放出型カソードとアノードとをわ
ずかな間隔を持たせて対向して配置し、アノード上のカ
ソードと対向する面の所定の位置に電子線励起により各
色に発光する蛍光体からなる蛍光膜を設けておき、各カ
ソードから画像信号に対応する、加速電圧が２〜１５ｋ
Ｖ程度の中速電子線を放出させることによってアノード
上の各蛍光膜を発光させて画像を表示させる平面ディス
プレイで、消費電力が少なく、同じ平面ディスプレイで
ある液晶ディスプレイ（ＬＣＤ）よりも優位なフラット
で薄型のディスプレイとして期待されつつある。In the FED, a flat field emission cathode that emits electrons into a vacuum envelope and an anode are disposed to be opposed to each other with a slight space therebetween. A phosphor film made of a phosphor that emits light of each color by electron beam excitation is provided at a predetermined position, and an acceleration voltage corresponding to an image signal from each cathode is 2 to 15 k.
A flat display that emits light from each phosphor film on the anode by emitting a medium-speed electron beam of about V and displays an image. It consumes less power and is superior to a liquid crystal display (LCD), which is the same flat display. And is expected to be a thin display.
【０００４】しかしながら、このＦＥＤはカソードと蛍
光膜（アノード）との間の距離がＣＲＴに比較して極め
て短いことと、蛍光膜を発光させる電子線の加速電圧が
ＣＲＴよりも低く、逆にその電流密度がＣＲＴの１０〜
１０００倍の高密度であるため、ＦＥＤ用蛍光膜はＣＲ
Ｔ用蛍光膜に比べて、使用中に電子線による劣化を受け
て経時的な発光輝度の低下や発光色の変化が起こり易
く、特に、硫化物系蛍光体などの母体組成中に硫黄元素
（Ｓ）を含む蛍光体をＦＥＤ用蛍光膜として用いた場
合、高密度の電子線に長時間晒されると蛍光体自体が分
解したり、蛍光体母体の結晶性が低下して、発光輝度の
低下が顕著であるところから、ＣＲＴ用蛍光膜として用
いる従来の蛍光体をそのままＦＥＤ用蛍光膜として用い
た場合、特に、経時的な発光輝度の低下抑制という観点
から、その改良が強く望まれていた。However, in this FED, the distance between the cathode and the phosphor film (anode) is extremely shorter than that of a CRT, and the acceleration voltage of an electron beam for causing the phosphor film to emit light is lower than that of a CRT. Current density is 10 to 10
Since the density is 1000 times higher, the fluorescent film for FED is CR
Compared to the fluorescent film for T, it is more susceptible to deterioration in emission luminance and change in emission color over time due to deterioration by electron beams during use. In particular, the sulfur element ( When a phosphor containing S) is used as a phosphor film for FED, if the phosphor is exposed to a high-density electron beam for a long time, the phosphor itself is decomposed or the crystallinity of the phosphor matrix is reduced, and the emission luminance is reduced. When the conventional phosphor used as a fluorescent film for a CRT is used as it is as a fluorescent film for an FED, its improvement has been strongly desired, particularly from the viewpoint of suppressing a decrease in emission luminance over time. .
【０００５】電子線照射に対する蛍光体の劣化抑制のた
めには、蛍光体が直接電子線に晒されないよう、蛍光体
表面に何らかの被覆層を設けることが考えられ、従来か
らも特にＣＲＴ用蛍光体など、加速電圧数十数ｋＶより
大の高速電子線用蛍光体や、加速電圧数百Ｖ以下の低速
電子線用蛍光体に対し、耐熱性に優れたＳｉ、Ａｌ、Ｔ
ｉなどの酸化物の微粒子を表面に被覆した蛍光体が使用
されている。しかし、これら金属酸化物の微粒子が被覆
された蛍光体は、ＦＥＤ用蛍光膜など、高電流密度で、
加速電圧が数ｋＶ〜十数ｋＶのいわゆる中速電子線の連
続照射を受けると必ずしも劣化による発光輝度低下が抑
制されず、その改善が望まれていた。[0005] In order to suppress the deterioration of the phosphor due to electron beam irradiation, it is conceivable to provide a coating layer on the surface of the phosphor so that the phosphor is not directly exposed to the electron beam. For example, Si, Al, T, which are excellent in heat resistance, for phosphors for high-speed electron beams having an acceleration voltage of several tens of kV or more, and for low-speed electron beams having an acceleration voltage of several hundred V or less.
A phosphor having a surface coated with fine particles of an oxide such as i is used. However, the phosphor coated with these metal oxide fine particles has a high current density, such as a fluorescent film for FED.
When a so-called medium-speed electron beam with an acceleration voltage of several kV to several tens of kV is continuously irradiated, a decrease in emission luminance due to deterioration is not necessarily suppressed, and improvement thereof has been desired.
【０００６】[0006]
【発明が解決しようとする課題】本発明は特に加速電圧
がおよそ数ｋＶ〜十数ｋＶであり、高電流密度の中速電
子線を継続的に照射して発光させた際に、経時的な輝度
低下の少ない蛍光体の製造方法並びに蛍光膜を提供する
ことを目的とする。SUMMARY OF THE INVENTION The present invention particularly has an accelerating voltage of about several kV to several tens of kV. It is an object of the present invention to provide a method for producing a phosphor and a phosphor film with less decrease in luminance.
【０００７】[0007]
【課題を解決するための手段】本発明者等は上記目的を
達成するため、蛍光体表面に種々の金属酸化物を被覆さ
せる表面処理方法に関し、鋭意検討した結果、特定の珪
素化合物を用いて蛍光体表面にシリカの皮膜を形成し、
これを蛍光膜として用いた場合、上記目的が達成し得る
ことを見い出した。Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on a surface treatment method for coating a phosphor surface with various metal oxides. Form a silica film on the phosphor surface,
It has been found that the above object can be achieved when this is used as a fluorescent film.
【０００８】本発明は以下の構成を採用することによっ
て上記目的を達成し得る。 （１） 表面にシラザンを付着させた蛍光体を加熱して
上記シラザンを熱分解し、シリカを生成させることによ
り上記蛍光体の表面にシリカの皮膜を被覆することを特
徴とする蛍光体の表面処理方法。 （２）上記シリカ皮膜は複数の皮膜が積層されているこ
とを特徴とする上記（１）に記載の表面処理方法。The present invention can achieve the above object by adopting the following constitution. (1) The surface of the phosphor, wherein the surface of the phosphor is coated with a silica film by heating the phosphor to which the silazane is attached on the surface to thermally decompose the silazane to form silica. Processing method. (2) The surface treatment method according to the above (1), wherein the silica film is formed by laminating a plurality of films.
【０００９】（３） 上記シラザンがポリシラザンであ
ることを特徴とする上記（１）または（２）に記載の表
面処理方法。 （４） 上記シリカの被覆量が珪素（Ｓｉ）に換算して
上記蛍光体に対して０．０２〜５重量％であることを特
徴とする上記（１）〜（３）のいずれかに記載の表面処
理方法。(3) The surface treatment method according to (1) or (2), wherein the silazane is polysilazane. (4) The coating according to any one of (1) to (3), wherein the coating amount of the silica is 0.02 to 5% by weight relative to the phosphor in terms of silicon (Si). Surface treatment method.
【００１０】（５） 上記蛍光体がその母体組成中に硫
黄元素を含むことを特徴とする上記（１）〜（４）のい
ずれかに記載の表面処理方法。 （６） 上記蛍光体が２価金属硫化物、希土類酸硫化物
及びチオガレートの中のいずれかであることを特徴とす
る上記（５）に記載の表面処理方法。(5) The surface treatment method according to any one of (1) to (4), wherein the phosphor contains a sulfur element in a matrix composition thereof. (6) The surface treatment method according to (5), wherein the phosphor is any one of divalent metal sulfides, rare earth oxysulfides, and thiogallate.
【００１１】（７） 支持体上に、上記（１）〜（６）
のいずれかに記載された表面処理方法によって得られた
蛍光体からなる蛍光体層を設けたことを特徴とする蛍光
膜。 （８） 真空外囲器内に少なくとも電界放出用カソード
と、これに対向するアノードと、該アノードの上記カソ
ード側に設けられた蛍光膜とを有し、上記カソードから
放出される加速電圧１〜１５ｋＶの電子線によって上記
蛍光膜を発光させる電界放出型ディスプレイ装置におい
て、上記蛍光膜が上記（７）に記載の蛍光膜からなるこ
とを特徴とする電界放出型ディスプレイ装置。(7) On the support, the above (1) to (6)
A phosphor film comprising a phosphor layer made of a phosphor obtained by the surface treatment method described in any one of the above. (8) A vacuum envelope having at least a field emission cathode, an anode facing the cathode, and a fluorescent film provided on the cathode side of the anode, and having an acceleration voltage of 1 to 3 emitted from the cathode. A field emission display device in which the phosphor film emits light with an electron beam of 15 kV, wherein the phosphor film comprises the phosphor film described in (7).
【００１２】[0012]
【発明の実施の態様】以下、本発明を更に詳細に説明す
る。本発明の表面処理蛍光体を製造するには、先ず、シ
ラザンを溶解し得るがこれと反応しない有機溶媒中に所
定量の蛍光体を懸濁させて蛍光体の有機溶媒懸濁液を調
製し、この中に所定量のシラザンを添加して十分に攪拌
し、次いで濾過またはデカンテーションにより蛍光体を
有機溶媒から分離して、乾燥させた後、空気中で熱処理
して蛍光体に付着しているシラザンを加熱分することに
よって、蛍光体の表面には粒状のシリカではなく、皮膜
状のシリカが生成される。なお、この時、蛍光体表面に
複数のシリカ皮膜を積層すると、同一量のシリカ皮膜を
被覆する場合には、その被覆効果が単層のシリカ皮膜を
被覆する場合に比べてより向上するので好ましい。蛍光
体表面に複数層のシリカ皮膜を積層して被覆するには、
上記方法により得られた、シリカ皮膜被覆蛍光体を用い
て、上記操作を反復することにより、既に形成されたシ
リカ皮膜の表面に更にシリカ皮膜を被覆すればよい。即
ち、蛍光体の表面に付着すべき所定量のシラザンを分割
して別々に準備し、先ず、上述のようにして予め所定量
よりも少ない量のシラザンを蛍光体の有機溶媒懸濁液中
に投入して蛍光体表面に付着させ、これを加熱分解して
シリカ皮膜を蛍光体表面に被覆させた蛍光体を製造し、
この蛍光体の表面に更に残りのシラザンを付着させて同
様にしてこれを熱分解し、既に被覆されているシリカ膜
の上に、更にシリカの皮膜を形成する操作を反復するこ
とにより、蛍光体の表面に複数層のシリカ膜を積層すれ
ばよい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. To produce the surface-treated phosphor of the present invention, first, a predetermined amount of the phosphor is suspended in an organic solvent capable of dissolving silazane but not reacting with the silazane to prepare an organic solvent suspension of the phosphor. A predetermined amount of silazane was added thereto, and the mixture was sufficiently stirred. Then, the phosphor was separated from the organic solvent by filtration or decantation, dried, and then heat-treated in air to adhere to the phosphor. By heating the silazane that is present, film-like silica is generated on the surface of the phosphor instead of granular silica. Note that, at this time, it is preferable to laminate a plurality of silica films on the phosphor surface, since when the same amount of silica film is coated, the coating effect is more improved than when a single layer of silica film is coated. . To laminate and coat multiple layers of silica coating on the phosphor surface,
The above operation is repeated using the phosphor coated with the silica film obtained by the above method, so that the surface of the already formed silica film may be further coated with the silica film. That is, a predetermined amount of silazane to be attached to the surface of the phosphor is divided and separately prepared. First, as described above, an amount of silazane smaller than the predetermined amount is previously added to the suspension of the phosphor in the organic solvent. The phosphor is put on and adhered to the phosphor surface, which is thermally decomposed to produce a phosphor having a silica film coated on the phosphor surface,
The remaining silazane is further adhered to the surface of the phosphor, pyrolyzed in the same manner, and an operation of forming a silica film on the already-coated silica film is repeated, thereby obtaining the phosphor. A plurality of layers of silica films may be stacked on the surface.
【００１３】本発明において用いられるシラザンは、Ｓ
ｉ−Ｎ（珪素ー窒素）結合を有する化合物であって、そ
の組成がＨ３Ｓｉ［ＮＨＳｉＨ２］ｎＮＨＳｉＨ３（但
しｎは０または正数）で表される、有機溶媒に可溶な無
機ポリマーであって、その組成中に含有する珪素原子数
の異なるジシラザン、トリシラザン、ポリシラザンの外
に、シラザンの水素（Ｈ）が有機酸で置換されたオルガ
ノシラザン等が使用できるが、特に珪素原子数ｎが１０
以上のポリシラザンを用いるのがより好ましい。その理
由は、珪素原子数ｎが小さい、即ちシラザンの分子量が
小さいと蒸気圧が大きくなり、溶媒蒸発処理中にシラザ
ンの蒸発ロスが発生し、また安全衛生上も好ましくな
い。The silazane used in the present invention is S
i-N is a compound having a (silicon over nitrogen) bonds, the composition H 3 Si [NHSiH 2] n NHSiH 3 ( where n is 0 or a positive number) represented by soluble inorganic to organic solvents In addition to disilazane, trisilazane, and polysilazane, which are different in the number of silicon atoms contained in the composition, organosilazane in which hydrogen (H) of silazane is substituted with an organic acid can be used. n is 10
It is more preferable to use the above polysilazane. The reason is that, when the number n of silicon atoms is small, that is, when the molecular weight of silazane is small, the vapor pressure increases, and the evaporation loss of silazane occurs during the solvent evaporation treatment, which is not preferable in terms of safety and health.
【００１４】蛍光体表面に被覆されるシリカの量はＳｉ
に換算して蛍光体に対して０．０２〜５重量％とするの
が好ましく、特に、０．１〜２．５重量％とするのがよ
り好ましい。シリカの被覆量がＳｉに換算して蛍光体に
対して０．０２重量％より少ないと得られる蛍光体の経
時的な輝度低下が改善されず、また、この被覆量が５重
量％より多いと得られる蛍光体の発光輝度が低下してし
まうので実用上好ましくない。The amount of silica coated on the phosphor surface is Si
Preferably, the content is 0.02 to 5% by weight, particularly 0.1 to 2.5% by weight, based on the phosphor. If the coating amount of silica is less than 0.02% by weight relative to the phosphor in terms of Si, the decrease in luminance over time of the obtained phosphor is not improved, and if the coating amount is more than 5% by weight. It is not practically preferable because the emission luminance of the obtained phosphor is reduced.
【００１５】蛍光体表面に被覆されるシリカの量は蛍光
体の有機溶媒懸濁液中でのシラザンの濃度、蛍光体量、
蛍光体の平均粒径（比表面積；ｍ２／ｇ）、その有機溶
媒の粘度や温度等により変化する。従って予めシリカの
被覆量と各要因との関係を確認しておく必要がある。The amount of silica coated on the phosphor surface depends on the concentration of silazane in the suspension of the phosphor in the organic solvent, the amount of the phosphor,
The average particle size (specific surface area; m 2 / g) of the phosphor, and the viscosity and temperature of the organic solvent change. Therefore, it is necessary to confirm in advance the relationship between the silica coating amount and each factor.
【００１６】本発明の蛍光体の表面処理方法において使
用される有機溶媒としては、ベンゼン、トルエン、キシ
レン、ジブチルエーテル、シクロヘキサン等の、水を溶
解し難く、かつ、安定であって、ポリシラザンとは反応
しないが、ポリシラザンを溶解する溶媒が良い。特に、
ポリシラザンは、水酸基（ＯＨ）を持つ物質と容易に反
応し、加水分解されるため、水、アルコール類は使用出
来ない。また、ケトンやエステル類、エーテル類も水を
溶解するため好ましくない。The organic solvent used in the phosphor surface treatment method of the present invention, such as benzene, toluene, xylene, dibutyl ether and cyclohexane, is hardly soluble in water and is stable. A solvent that does not react but dissolves polysilazane is preferred. In particular,
Polysilazane easily reacts with a substance having a hydroxyl group (OH) and is hydrolyzed, so that water and alcohols cannot be used. Further, ketones, esters, and ethers are also not preferable because they dissolve water.
【００１７】また、ポリシラザンの有機溶媒中の濃度と
しては、０．０１〜２０重量％程度が推奨出来る。蛍光
体表面に付着させたシラザンを加熱分解してシリカを生
成させる際の加熱処理は、空気中、２５０℃以上の温度
で行う。２５０℃以上の温度で加熱処理することによっ
て、空気中の水分や酸素とシラザンとの反応によりシリ
カが生成すると同時に、熱によるシリカ膜の緻密化が同
時に起る。この時、シリカの緻密な薄膜を得るために
は、一般に熱処理温度が高い方が好ましいが、組成中に
硫黄元素（Ｓ）を含む蛍光体の場合、空気中で５００℃
以上の高温にさらされると、その表面で分解や酸化が生
ずるという弊害があり、一方、蛍光体表面に付着してい
るシラザンはその全量がシリカになっていなくても、そ
の過半量がシリカである皮膜を形成していれば本発明の
効果である、経時的な発光輝度低下の抑制は充分得られ
るので、熱処理温度としては、２５０℃〜５００℃の範
囲で行うことが推奨される。The concentration of polysilazane in the organic solvent is preferably about 0.01 to 20% by weight. The heat treatment for generating silica by thermally decomposing silazane attached to the phosphor surface is performed in air at a temperature of 250 ° C. or higher. By performing the heat treatment at a temperature of 250 ° C. or more, silica is generated by a reaction between water and oxygen and silazane in the air, and the silica film is densified by heat at the same time. At this time, in order to obtain a dense silica thin film, it is generally preferable that the heat treatment temperature is higher. However, in the case of a phosphor containing a sulfur element (S) in the composition, the phosphor is heated to 500 ° C. in air.
When exposed to the above high temperatures, there is a problem that decomposition or oxidation occurs on the surface, while the majority of the silazane adhering to the phosphor surface is not silica but the majority thereof is silica. If a certain film is formed, the effect of the present invention, that is, the suppression of the decrease in emission luminance over time can be sufficiently obtained. Therefore, it is recommended to perform the heat treatment at a temperature in the range of 250 to 500 ° C.
【００１８】本発明において表面処理用として用いられ
る蛍光体としては、ＣＲＴ用の赤色蛍光体であるＹ２０
２Ｓ：Ｅｕ、緑色蛍光体であるＺｎＳ：Ｃｕ，Ａｌ、青
色蛍光体であるＺｎＳ：Ａｇ，Ｃｌ、ＺｎＳ：Ａｇ，Ａ
ｌ等、電子線で励起した時、高効率の発光を呈し、電子
線を画像表示のための励起源とするディスプレイの蛍光
膜として用いられる蛍光体であれば特に制限はないが、
本発明の表面処理に用いられる蛍光体は、特にＺｎＳ系
蛍光体、（Ｚｎ、Ｃｄ）Ｓ系蛍光体（Ｓｒ、Ｃａ）Ｓ系
等の硫化物を母体とする蛍光体、Ｌｎ２Ｏ２Ｓ（Ｌｎは
Ｙ，Ｇｄ及びＬａの少なくとも１種）で表される希土類
酸硫化物系蛍光体を母体とする蛍光体、ＭＧａ２Ｓ
４（ＭはＳｒ、Ｃａ，Ｂａ及びＭｇの中の少なくとも１
種）で表されるチオガレート系蛍光体等、蛍光体の母体
組成中にＳ元素を含む蛍光体に対して特に経時的な発光
輝度低下の抑制効果を発揮する。The phosphor used for surface treatment in the present invention is Y 20, which is a red phosphor for CRT.
2 S: Eu, ZnS: Cu, Al which is a green phosphor, ZnS: Ag, Cl, ZnS: Ag, A which is a blue phosphor
l, etc., is not particularly limited as long as it emits highly efficient light when excited by an electron beam and is used as a phosphor film of a display using an electron beam as an excitation source for image display.
Phosphors used in the surface treatment of the present invention are, in particular, ZnS-based phosphors, (Zn, Cd) S-based phosphors (Sr, Ca) S-based phosphors, etc., which are based on sulfides, Ln 2 O 2 S (Ln is at least one of Y, Gd and La), a phosphor mainly composed of a rare earth oxysulfide-based phosphor, MGa 2 S
4 (M is at least one of Sr, Ca, Ba and Mg
Particularly, it exerts an effect of suppressing a decrease in emission luminance over time with respect to a phosphor containing the S element in the base composition of the phosphor, such as a thiogallate-based phosphor represented by the following formula:
【００１９】以上のようにして得られた蛍光体は、特
に、ＦＥＤ等、加速電圧が数ｋＶ〜十数ｋＶで、電流密
度が数μＡ〜十数ｍＡの中速電子線で継続的に照射され
る環境下において使用した時、経時的な発光輝度の低下
を抑制する効果が顕著であるが、本発明の製造方法によ
り得られた蛍光体は、継続的に真空紫外線の照射を受け
る環境下で使用されるプラズマディスプレイ（ＰＤＰ）
や、紫外線励起下で使用される蛍光ランプの蛍光膜とし
て使用した場合にも同様に蛍光体の劣化による発光輝度
の低下が抑制される外、加速電圧が数１００Ｖの低速電
子線や加速電圧が２０ｋＶ以上の高速電子線用蛍光体と
しても利用できる。The phosphor obtained as described above is continuously irradiated with a medium-speed electron beam having an acceleration voltage of several kV to several tens of kV and a current density of several μA to tens of mA in particular, such as an FED. When used in an environment where it is used, the effect of suppressing a decrease in emission luminance over time is remarkable, but the phosphor obtained by the production method of the present invention can be used in an environment that is continuously irradiated with vacuum ultraviolet rays. Plasma Display (PDP) used in Japan
Similarly, when used as a fluorescent film of a fluorescent lamp used under ultraviolet excitation, a decrease in emission luminance due to deterioration of the phosphor is similarly suppressed, and a low-speed electron beam with an acceleration voltage of several hundred volts or an acceleration voltage It can also be used as a high-speed electron beam phosphor of 20 kV or more.
【００２０】次に本発明の蛍光膜について述べる。上述
のようにして得られた、表面にシリカ皮膜が被覆された
蛍光体は、デバイス中の蛍光膜が形成されるべき所定の
場所に設けられたガラス等の支持体上に塗布して蛍光体
層を形成し、蛍光膜として利用される。例えば、これを
ＦＥＤ用の蛍光膜とする場合には、一対のガラス基板
Ａ、Ｂをおよそ２ｍｍ程度の間隙でもって対向配置し、
一方のガラス基板Ａの片面（もう一方のガラス基板Ｂと
対面する側）にＩＴＯ等の透明導電性薄膜を介して透明
なカソード電極と、これに通ずるカソードを所定の位置
に点在させて設けるとともに、ガラス基板Ｂの片面（ガ
ラス基板Ａと対面する側）にはアノード電極を設け、こ
のアノード電極の上に本発明の方法により得られた表面
処理蛍光体からなる蛍光膜を形成した後、これらガラス
基板Ａ、Ｂを対面させて真空外囲器内に封入しＦＥＤを
製造する。Next, the fluorescent film of the present invention will be described. The phosphor obtained as described above, the surface of which is coated with a silica film, is coated on a support such as glass provided at a predetermined place in the device where the fluorescent film is to be formed, and is then coated with the phosphor. A layer is formed and used as a fluorescent film. For example, when this is used as a fluorescent film for FED, a pair of glass substrates A and B are arranged to face each other with a gap of about 2 mm,
On one surface of one glass substrate A (the side facing the other glass substrate B), a transparent cathode electrode is provided via a transparent conductive thin film such as ITO, and cathodes passing therethrough are provided at predetermined positions. At the same time, an anode electrode is provided on one side of the glass substrate B (the side facing the glass substrate A), and after forming a phosphor film made of the surface-treated phosphor obtained by the method of the present invention on the anode electrode, The glass substrates A and B are opposed to each other and sealed in a vacuum envelope to manufacture an FED.
【００２１】支持体上に本発明の表面処理方法によって
得られた蛍光体を用いて蛍光体層を形成するには、例え
ば、水ガラス等のバインダーを含む水の入った容器の器
底に支持体となる基板を沈めておき、この中に上述のよ
うにして得られた所定量の蛍光体を投入して攪拌し、器
底の基板上に沈積させる、いわゆる、沈降塗布法による
方法、得られた蛍光体と水溶性の感光性樹脂バインダー
とを水等の溶媒中に懸濁させて感光性樹脂スラリーを調
製し、これを基板上の全面に塗布した後、所定のパター
ンに露光してから、未露光部を洗い流す、いわゆるホト
リソ法による方法、更にまた、得られた蛍光体をバイン
ダー樹脂と共に混練して蛍光体ペーストとし、これを基
板上の所定の位置に印刷塗布する、いわゆるスクリーン
印刷法などの従来から知られている方法により形成す
る。In order to form a phosphor layer on a support using the phosphor obtained by the surface treatment method of the present invention, for example, the support is placed on the bottom of a container containing water containing a binder such as water glass. The body substrate is submerged, and a predetermined amount of the phosphor obtained as described above is put therein, stirred, and deposited on the substrate at the bottom of the vessel. The phosphor and the water-soluble photosensitive resin binder were suspended in a solvent such as water to prepare a photosensitive resin slurry, which was applied to the entire surface of the substrate, and then exposed to a predetermined pattern. Then, the unexposed part is washed away, a method by the so-called photolithographic method, and further, the obtained phosphor is kneaded with a binder resin to form a phosphor paste, and this is printed and applied to a predetermined position on a substrate, so-called screen printing. Conventional as law Formed by methods known al.
【００２２】[0022]
【実施例】次に実施例により本発明を説明する。 〔実施例１〕市販のポリシラザン溶液（東燃社製”Ｄ８
２０”；ポリシラザン濃度２０ｗｔ％、ジブチルエーテ
ル溶媒。分子量７００。）３ｍｌを２９７ｍｌのトルエ
ンに溶解させたシラザンの有機溶媒液に、ＺｎＳ：Ｃ
ｕ，Ａｌ緑色蛍光体１００ｇ投入した。そして、十分に
混合接触させた蛍光体スラリーを密閉加圧濾過（計装用
空気：３．５ｋｇ／ｃｍ２Ｇ）した。Next, the present invention will be described by way of examples. [Example 1] A commercially available polysilazane solution ("D8" manufactured by Tonen Corporation)
20 ″; polysilazane concentration 20 wt%, dibutyl ether solvent; molecular weight 700.) ZnS: C was added to an organic solvent solution of silazane in which 3 ml was dissolved in 297 ml of toluene.
100 g of u, Al green phosphor was charged. Then, the phosphor slurry sufficiently mixed and contacted was subjected to closed pressure filtration (instrument air: 3.5 kg / cm 2 G).
【００２３】濾過して得られた蛍光体を防爆型循環乾燥
機を用いて１２０℃で３０分間乾燥させた。その後、電
気炉で、大気中３００℃の温度で３０分加熱処理し、表
面にシリカ皮膜が被覆された実施例１の蛍光体（Ｚｎ
Ｓ：Ｃｕ，Ａｌ緑色蛍光体）を得た。The phosphor obtained by filtration was dried at 120 ° C. for 30 minutes using an explosion-proof circulating dryer. Then, the phosphor (Zn) of Example 1 having a surface coated with a silica film was heated in an electric furnace at a temperature of 300 ° C. for 30 minutes in the atmosphere.
S: Cu, Al green phosphor).
【００２４】この蛍光体表面のシリカ成分を定量分析し
たところ、シリカが珪素に換算してＺｎＳ：Ｃｕ，Ａｌ
蛍光体に対して０．１５ｗｔ％被覆されていた。When the silica component on the phosphor surface was quantitatively analyzed, the silica was converted to silicon and ZnS: Cu, Al
The phosphor was coated at 0.15 wt%.
【００２５】次に、上述のようにして得られた実施例１
の蛍光体をエチルセルロース（バインダー樹脂）及びブ
チルカルビトールアセテート（溶媒）と共に混合して混
練して蛍光体ペーストを調製し、この蛍光体ペーストを
スクリーン印刷法で表面に透明導電（ＩＴＯ）膜が形成
されているガラス基板上の全面に印刷塗布後、電気炉で
大気中、４３０℃で加熱処理を行って有機物成分を除去
し、蛍光体層の膜厚が２０μｍの実施例１の蛍光膜を得
た。 次いでこの実施例１の蛍光膜に加速電圧６ｋＶ、
電流密度１５０μＡ／ｃｍ２の電子線を１０時間連続照
射して発光させ続け、その時の電子線照射開始直後の発
光輝度｛初期輝度（ａ）｝、照射開始から１０時間後に
おける発光輝度｛経時後の発光輝度（ｂ）｝及び輝度維
持率｛（ｂ／ａ）×１００｝をそれぞれ求め、その結果
を、この蛍光体の表面に被覆されているシリカ被覆量
（シリカ中におけるＳｉの量の蛍光体に対すると重量百
分率）と共に表１に示した。Next, Example 1 obtained as described above was used.
Is mixed with ethyl cellulose (binder resin) and butyl carbitol acetate (solvent) and kneaded to prepare a phosphor paste, and this phosphor paste is screen-printed to form a transparent conductive (ITO) film on the surface. After printing and coating on the entire surface of the glass substrate, heat treatment was performed at 430 ° C. in the air in an electric furnace to remove organic components, thereby obtaining a phosphor film of Example 1 having a phosphor layer thickness of 20 μm. Was. Next, an acceleration voltage of 6 kV was applied to the fluorescent film of the first embodiment.
An electron beam having a current density of 150 μA / cm 2 is continuously irradiated for 10 hours to continuously emit light. At that time, the emission luminance immediately after the start of the electron beam irradiation {initial luminance (a)}, the emission luminance 10 hours after the start of the irradiation {after lapse of time} And the luminance maintenance rate {(b / a) × 100}, respectively, and the results are shown as the amount of silica covering the surface of this phosphor (the fluorescence of the amount of Si in silica). The results are shown in Table 1 together with the weight percentage based on the body.
【００２６】なお、前記の初期輝度（ａ）はこれと同様
にして測定した、下記の比較例１の蛍光膜の初期輝度
（ａ）を１００とした時の相対値で全て示してある（以
下、各実施例並びに比較例においても同様）。The above-mentioned initial luminance (a) was measured in the same manner, and all values are shown as relative values when the initial luminance (a) of the phosphor film of Comparative Example 1 described below is set to 100 (hereinafter, referred to as the initial luminance (a)). The same applies to each of Examples and Comparative Examples).
【００２７】〔比較例１〕実施例１の蛍光体を製造する
ために用いた、表面に何ら被覆処理をしていないＺｎ
Ｓ：Ｃｕ，Ａｌ緑色蛍光体を比較例１の蛍光体とした。Comparative Example 1 Zn used for producing the phosphor of Example 1 and having no surface coating treatment was used.
S: Cu, Al green phosphor was used as the phosphor of Comparative Example 1.
【００２８】次に蛍光体として実施例１の蛍光体に代え
て比較例１の蛍光体を用いた以外は、実施例１の蛍光膜
と同様にして比較例１の蛍光膜を製造し、実施例１の蛍
光膜の測定と同一の測定条件により測定して比較例１の
蛍光膜の初期輝度（ａ）、経時後の発光輝度（ｂ）及び
輝度維持率｛（ｂ／ａ）×１００｝をそれぞれ測定並び
に算出し、その結果を、この蛍光体の表面に被覆されて
いるシリカ被覆量と共に表１に示した。Next, a phosphor film of Comparative Example 1 was manufactured in the same manner as the phosphor film of Example 1 except that the phosphor of Example 1 was used instead of the phosphor of Example 1. The initial luminance (a), the emission luminance after lapse of time (b), and the luminance maintenance ratio {(b / a) × 100} of the fluorescent film of Comparative Example 1 were measured under the same measurement conditions as the measurement of the fluorescent film of Example 1. Was measured and calculated, and the results are shown in Table 1 together with the amount of silica coating on the surface of the phosphor.
【００２９】〔実施例２〕シラザンの有機溶媒液とし
て、ポリシラザン溶液３ｍｌを２９７ｍｌのトルエンに
溶解する代わりに、ポリシラザン溶液１５ｍｌを２８５
ｍｌのトルエンに溶解したシラザンの有機溶媒液を用い
た以外は実施例１の蛍光体と同様にして表面にシリカ皮
膜が被覆された実施例２の蛍光体（ＺｎＳ：Ｃｕ，Ａｌ
緑色蛍光体）を得た。Example 2 Instead of dissolving 3 ml of a polysilazane solution in 297 ml of toluene as an organic solvent liquid of silazane, 15 ml of a polysilazane solution was used instead of 285 ml.
The phosphor of Example 2 (ZnS: Cu, Al) having a silica coating on the surface in the same manner as the phosphor of Example 1 except that an organic solvent solution of silazane dissolved in
Green phosphor).
【００３０】この蛍光体表面のシリカ成分を定量分析し
たところ、シリカが珪素に換算してＺｎＳ：Ｃｕ，Ａｌ
蛍光体に対して０．２ｗｔ％被覆されていた。次に蛍光
体として実施例１の蛍光体に代えて実施例２の蛍光体を
用いた以外は、実施例１の蛍光膜と同様にして実施例２
の蛍光膜を製造し、実施例１の蛍光膜の測定と同一の測
定条件により測定して実施例２の蛍光膜の初期輝度
（ａ）、経時後の発光輝度（ｂ）及び輝度維持率｛（ｂ
／ａ）×１００｝をそれぞれ測定並びに算出し、その結
果を、この蛍光体の表面に被覆されているシリカ被覆量
（シリカ中におけるＳｉの量の蛍光体に対すると重量百
分率）と共に表１に示した。When the silica component on the phosphor surface was quantitatively analyzed, the silica was converted to silicon and ZnS: Cu, Al
The phosphor was coated at 0.2 wt%. Next, the same procedure as in the phosphor film of Example 1 was repeated except that the phosphor of Example 2 was used instead of the phosphor of Example 1 as the phosphor.
The initial luminance (a), the emission luminance (b) after lapse of time, and the luminance retention rate of the phosphor film of Example 2 were measured under the same measurement conditions as those of the phosphor film of Example 1. (B
/ A) × 100 ° were measured and calculated respectively, and the results are shown in Table 1 together with the amount of silica coating on the surface of the phosphor (the weight percentage of the amount of Si in the silica relative to the phosphor). Was.
【００３１】〔実施例３〕蛍光体としてＺｎＳ：Ｃｕ，
Ａｌ緑色蛍光体に代えて、実施例１の蛍光体を用いた以
外は同様にして（即ち、実施例１の蛍光体の製造プロセ
スを２回反復する）実施例３の蛍光体を得た。Example 3 ZnS: Cu,
A phosphor of Example 3 was obtained in the same manner except that the phosphor of Example 1 was used instead of the Al green phosphor (that is, the manufacturing process of the phosphor of Example 1 was repeated twice).
【００３２】次に蛍光体として実施例１の蛍光体に代え
て実施例３の蛍光体を用いた以外は、実施例１の蛍光膜
と同様にして実施例３の蛍光膜を製造し、実施例１の蛍
光膜の測定と同一の測定条件により測定して実施例３の
蛍光膜の初期輝度（ａ）、経時後の発光輝度（ｂ）及び
輝度維持率｛（ｂ／ａ）×１００｝をそれぞれ測定並び
に算出し、その結果を、この蛍光体の表面に被覆されて
いるシリカ被覆量（シリカ中におけるＳｉの量の蛍光体
に対すると重量百分率）と共に表１に示した。Next, a phosphor film of the third embodiment was manufactured in the same manner as the phosphor film of the first embodiment except that the phosphor of the third embodiment was used instead of the phosphor of the first embodiment. The initial luminance (a), the emission luminance after aging (b), and the luminance maintenance rate {(b / a) × 100} of the fluorescent film of Example 3 were measured under the same measurement conditions as those of the fluorescent film of Example 1. Was measured and calculated, and the results are shown in Table 1 together with the amount of silica coating on the surface of the phosphor (the weight percentage of the amount of Si in the silica relative to the phosphor).
【００３３】〔比較例２〕ＺｎＳ：Ｃｕ，Ａｌ緑色蛍光
体１００ｇと純水１００ｇをビーカーに入れ、マグネチ
ックスタラーで良く攪拌して蛍光体スラリーを調製し、
このスラリーをさらに攪拌しながら蛍光体に対して０．
１５重量％のＳｉを含有する市販のコロイダルシリカ
（日産化学社製、“スノーテッツクス”ＳＴ−２０Ｌ）
を添加した。Comparative Example 2 100 g of ZnS: Cu, Al green phosphor and 100 g of pure water were placed in a beaker and stirred well with a magnetic stirrer to prepare a phosphor slurry.
While the slurry is being further stirred, the slurry is added to the phosphor in a volume of 0.1%.
Commercially available colloidal silica containing 15% by weight of Si ("Snowtecs" ST-20L, manufactured by Nissan Chemical Industries, Ltd.)
Was added.
【００３４】次に硫酸亜鉛（ＺｎＳＯ４・７Ｈ２Ｏ）の
２０％水溶液を９ｍｌ添加してから希釈した苛性ソーダ
を添加してスラリーのＰＨを８．５に調整し、蛍光体表
面にシリカゾルを付着させた。次いで、この蛍光体をデ
カンテーションにより水洗してから濾過し、乾燥を行っ
て蛍光体表面にシリカ粒子を付着させたＺｎＳ：Ｃｕ，
Ａｌ緑色蛍光体を得た。この蛍光体表面に付着している
シリカを定量分析したところ、シリカが珪素に換算して
ＺｎＳ：Ｃｕ，Ａｌ蛍光体に対して０．１５ｗｔ％被覆
されていた。この時蛍光体表面に付着しているシリカは
膜状ではなくほぼ粒状であり、断続的に付着していた。[0034] Then 20% aqueous solution of zinc sulfate (ZnSO 4 · 7H 2 O) was added to sodium hydroxide, diluted from the addition 9ml adjust the PH of the slurry to 8.5, depositing a silica sol to the phosphor surface I let it. Next, the phosphor was washed with water by decantation, filtered, and dried to obtain ZnS: Cu, having silica particles adhered to the phosphor surface.
An Al green phosphor was obtained. Quantitative analysis of the silica adhering to the phosphor surface revealed that the silica was coated on the ZnS: Cu, Al phosphor in 0.15 wt% in terms of silicon. At this time, the silica adhering to the phosphor surface was not granular but substantially granular, and intermittently adhered.
【００３５】次に蛍光体として実施例１の蛍光体に代え
て比較例２の蛍光体を用いた以外は、実施例１の蛍光膜
と同様にして比較例２の蛍光膜を製造し、実施例１の蛍
光膜の測定と同一の測定条件により測定して比較例２の
蛍光膜の初期輝度（ａ）、経時後の発光輝度（ｂ）及び
輝度維持率｛（ｂ／ａ）×１００｝をそれぞれ測定並び
に算出し、その結果をに表１に示した。Next, a phosphor film of Comparative Example 2 was manufactured in the same manner as the phosphor film of Example 1 except that the phosphor of Example 1 was used instead of the phosphor of Example 1. The initial luminance (a), the emission luminance after lapse of time (b), and the luminance maintenance ratio {(b / a) × 100} of the fluorescent film of Comparative Example 2 were measured under the same measurement conditions as the measurement of the fluorescent film of Example 1. Was measured and calculated, and the results are shown in Table 1.
【００３６】[0036]
【表１】 [Table 1]
【００３７】表１からわかるように、ポリシラザンを蛍
光体表面に付着させてこれを熱分解することによってシ
リカを被覆した実施例１〜３の本発明の蛍光膜は、表面
に何ら被覆処理が施されていない蛍光体からなる比較例
１の蛍光膜に比べて、１０時間連続して発光させた場合
（経時後の発光輝度）においても、発光輝度の低下が少
なく、輝度維持率が著しく改善されていた。特に比較的
低濃度のシリカ皮膜を複数回に分けて被覆させた実施例
３の蛍光膜では経時的な発光輝度低下の抑制効果的はよ
り顕著であった。これは蛍光体表面のシリカの被覆がよ
り強固になったためであろうと思われる。As can be seen from Table 1, the phosphor films of Examples 1 to 3 of the present invention, in which polysilazane was adhered to the phosphor surface and thermally decomposed to coat silica, were not subjected to any coating treatment on the surface. In the case of emitting light continuously for 10 hours (emission luminance after lapse of time), the decrease in emission luminance is small, and the luminance retention rate is remarkably improved, as compared with the phosphor film of Comparative Example 1 made of a phosphor not subjected to phosphor. I was In particular, in the fluorescent film of Example 3 in which a relatively low-concentration silica film was coated a plurality of times, the effect of suppressing the decrease in emission luminance over time was more remarkable. This is probably because the silica coating on the phosphor surface became stronger.
【００３８】なお、上記各実施例において蛍光体として
ＺｎＳ：Ｃｕ，Ａｌ緑色蛍光体を用いた場合についての
み例示したが、その他の例えば、ＺｎＳ：Ａｇ，Ｃｌ青
色蛍光体、Ｙ２Ｏ２Ｓ：Ｅｕ赤色蛍光体も同様に発光輝
度低下の抑制効果が確認された。In each of the above embodiments, only the case where ZnS: Cu, Al green phosphor is used as the phosphor has been exemplified. However, for example, ZnS: Ag, Cl blue phosphor, Y 2 O 2 S: The effect of suppressing the decrease in emission luminance was also confirmed for the Eu red phosphor.
【００３９】[0039]
【発明の効果】本発明の表面処理方法によれば上述のよ
うな構成としたので、特に中速電子線により継続発光さ
せた際の輝度維持率が改善され、長時間の使用によって
も発光輝度の低下の程度が小さく、高輝度の発光を呈す
る蛍光体並びに蛍光膜が得られる。According to the surface treatment method of the present invention, since the above-described structure is employed, the luminance maintenance ratio is improved particularly when the medium-speed electron beam continuously emits light, and the light emission luminance is maintained even after long use. Thus, a phosphor and a phosphor film which exhibit a small degree of decrease and emit light of high luminance can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三浦 典夫 神奈川県小田原市成田1060番地 化成オプ トニクス株式会社小田原工場内 Ｆターム(参考） 4H001 CA01 CA06 CC11 XA16 XA30 YA13 YA29 5C036 EE01 EF01 EF06 EF09 EG36 EH12 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Norio Miura, Inventor No. 1060 Narita, Odawara-shi, Kanagawa F-term in the Odawara Plant of Kasei Optonics Co., Ltd. 4H001 CA01 CA01 CC06
Claims (6)
熱して上記シラザンを熱分解し、シリカを生成させるこ
とにより上記蛍光体の表面にシリカの皮膜を被覆するこ
とを特徴とする蛍光体の表面処理方法。1. A phosphor characterized in that the surface of the phosphor is coated with a silica film by heating a phosphor having silazane adhered to the surface to thermally decompose the silazane to generate silica. Surface treatment method.
ていることを特徴とする請求項１に記載の蛍光体の表面
処理方法。2. The method according to claim 1, wherein a plurality of the silica coatings are laminated.
を特徴とする請求項１または２に記載の蛍光体の表面処
理方法。3. The method according to claim 1, wherein the silazane is polysilazane.
算して上記蛍光体に対して０．０２〜５重量％であるこ
とを特徴とする請求項１〜３に記載の蛍光体の表面処理
方法。4. The phosphor according to claim 1, wherein a coating amount of the silica is 0.02 to 5% by weight based on the phosphor in terms of silicon (Si). Surface treatment method.
（Ｓ）を含むことを特徴とする請求項１〜４のいずれか
一項に記載の蛍光体の表面処理方法。5. The method for surface treatment of a phosphor according to claim 1, wherein the phosphor contains a sulfur element (S) in a matrix composition thereof.
項に記載された表面処理方法によって得られた蛍光体か
らなる蛍光体層を設けたことを特徴とする蛍光膜。6. A phosphor film comprising a support and a phosphor layer made of the phosphor obtained by the surface treatment method according to claim 1.
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| JP37716499A JP4157243B2 (en) | 1999-12-27 | 1999-12-27 | Phosphor surface treatment method and phosphor film |
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