JP2001152143A - Preparation process of surface-modified fluorescent body - Google Patents

Preparation process of surface-modified fluorescent body

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Publication number
JP2001152143A
JP2001152143A JP34185499A JP34185499A JP2001152143A JP 2001152143 A JP2001152143 A JP 2001152143A JP 34185499 A JP34185499 A JP 34185499A JP 34185499 A JP34185499 A JP 34185499A JP 2001152143 A JP2001152143 A JP 2001152143A
Authority
JP
Japan
Prior art keywords
phosphor
particles
producing
modified
modifying substance
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.)
Pending
Application number
JP34185499A
Other languages
Japanese (ja)
Inventor
Naoto Kijima
直人 木島
Taiichiro Miwa
泰一郎 三輪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kasei Optonix Ltd
Mitsubishi Chemical Corp
Original Assignee
Kasei Optonix Ltd
Mitsubishi Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kasei Optonix Ltd, Mitsubishi Chemical Corp filed Critical Kasei Optonix Ltd
Priority to JP34185499A priority Critical patent/JP2001152143A/en
Priority to KR1020027006938A priority patent/KR20020070297A/en
Priority to CN00818706A priority patent/CN1433454A/en
Priority to PCT/JP2000/008526 priority patent/WO2001040402A1/en
Priority to EP00978058A priority patent/EP1236784A1/en
Publication of JP2001152143A publication Critical patent/JP2001152143A/en
Pending legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To provide a preparation process of a surface-modified fluorescent body which has a fine surface-modified layer which is hardly peeled off and shows a good adhesion on the surface of a globular or nearly globular fluorescent body particle showing little coagulation. SOLUTION: In the preparation process for a surface-modified fluorescent body, a solution containing the metal element constituents of the fluorescent body is atomized into a gas atmosphere as fine droplets and dried. After attaching the surface-modifying matters onto the surface of the dried particles, the particles are introduced into a pyrolysis synthesis oven together with the associated gas and pyrolyzed.

Description

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

【０００１】[0001]

【発明の属する技術分野】本発明は、ブラウン管、蛍光
ランプ、プラズマディスプレーパネル（ＰＤＰ）などの
蛍光膜に適した表面修飾蛍光体の製造方法に関する。The present invention relates to a method for producing a surface-modified phosphor suitable for a phosphor film such as a cathode ray tube, a fluorescent lamp, and a plasma display panel (PDP).

【０００２】[0002]

【従来の技術】従来、ブラウン管、蛍光ランプやＰＤＰ
などに蛍光体を適用するときには、蛍光体を単独で用い
る場合と、蛍光体の分散性改善、蛍光体の劣化防止、蛍
光体の支持体への塗布接着性向上、反射率制御など蛍光
体の表面物性の改善を目的としてその表面に各種表面処
理物質や体色を有する顔料粒子などの表面修飾物質を被
覆することが行われている。なお、表面修飾物質にはそ
の前駆体も含まれる。2. Description of the Related Art Conventionally, cathode ray tubes, fluorescent lamps and PDPs
When applying phosphors to phosphors, etc., when using phosphors alone, it is necessary to improve the dispersibility of the phosphors, prevent the degradation of the phosphors, improve the adhesion of the phosphors to the support, and control the reflectance. For the purpose of improving the surface properties, the surface is coated with various surface treating substances or surface modifying substances such as pigment particles having a body color. In addition, the precursor is also contained in a surface modifying substance.

【０００３】この表面修飾蛍光体は、従来、蛍光体原料
粉末を混合し、坩堝などの焼成容器に充填し、高温で長
時間加熱して固相反応により焼成物を生成し、ボールミ
ルなどで微粉砕して蛍光体粒子を得た後、表面修飾物質
の水スラリー中に投入して蛍光体粒子表面に湿式法で表
面修飾物質を付着させるのが一般的であった。Conventionally, this surface-modified phosphor is prepared by mixing a raw material powder of a phosphor, filling the mixture in a firing vessel such as a crucible, heating at a high temperature for a long time to produce a fired product by a solid-phase reaction, and then using a ball mill or the like. After the phosphor particles were obtained by pulverization, it was generally put into a water slurry of a surface modifying substance, and the surface modifying substance was adhered to the surface of the phosphor particles by a wet method.

【０００４】しかし、固相反応により製造された蛍光体
粒子は、形状が不規則で一次粒子の凝集体からなってい
るため、かかる蛍光体粒子を各種用途の蛍光膜に適用す
ると、蛍光膜は不均質で充填密度が低くなり、良好な発
光特性を得ることができなかった。また、ボールミルな
どの微粉砕処理により得た蛍光体粒子は、物理的及び化
学的な衝撃を受けているため、蛍光体粒子内や表面に欠
陥が発生して発光強度を低下するという不都合があっ
た。さらに、坩堝などの焼成容器に入れて高温で長時間
加熱するときには、坩堝から不純物が混入して発光特性
の低下の要因となり、また、原料粉末の粒度によっては
固相反応が十分に進行せず、不純物相が混在して発光特
性の低下を招くことがあった。However, since the phosphor particles produced by the solid-phase reaction are irregular in shape and are composed of aggregates of primary particles, when such phosphor particles are applied to phosphor films for various uses, the phosphor film becomes It was heterogeneous and the packing density was low, so that good light emission characteristics could not be obtained. Further, since the phosphor particles obtained by the fine pulverization treatment such as a ball mill are physically and chemically shocked, there is a disadvantage that a defect is generated in the phosphor particles or on the surface and the emission intensity is reduced. Was. Furthermore, when placed in a firing vessel such as a crucible and heated at a high temperature for a long time, impurities are mixed in from the crucible and cause a decrease in light emission characteristics, and the solid-phase reaction does not sufficiently proceed depending on the particle size of the raw material powder. In some cases, a mixture of impurity phases causes deterioration of light emission characteristics.

【０００５】また、前記の不規則形状の蛍光体粒子への
表面修飾物質の付着は、不完全なものであるため、蛍光
体粒子の取り扱い中や塗布中に表面修飾物質が剥離する
ことがあり、表面修飾物質の性能を十分に発揮できない
ことがあった。また、表面修飾物質を蛍光体粒子表面に
被覆するときに、高い被覆率が要求される場合、多量の
表面修飾物質を被覆する必要があり、コスト高を招くば
かりでなく、励起線や発光光を吸収して発光効率の低下
を招いていた。しかも湿式法で表面修飾物質を付着させ
る場合、水等の液体を媒介して行うため、付着工程が煩
雑であった。[0005] Further, since the adhesion of the surface-modifying substance to the irregularly-shaped phosphor particles is incomplete, the surface-modifying substance may peel off during the handling or application of the phosphor particles. In some cases, the performance of the surface modifying substance cannot be sufficiently exhibited. In addition, when a high coverage is required when coating the surface modifying substance on the surface of the phosphor particles, it is necessary to coat a large amount of the surface modifying substance. To reduce the luminous efficiency. In addition, when the surface-modifying substance is adhered by a wet method, the adhesion is performed through a liquid such as water, so that the attaching step is complicated.

【０００６】[0006]

【発明が解決しようとする課題】本発明は、上記の問題
点を解消し、凝集の少ない球状若しくは球状に近い形状
の蛍光体粒子表面に、緻密で剥離の少ない密着性の良好
な表面修飾層を有する表面修飾蛍光体の製造方法を提供
しようとするものである。この表面修飾蛍光体は、均質
で充填密度の高い蛍光膜の形成を可能とし、優れたブラ
ウン管、蛍光ランプ、ＰＤＰなどの提供を可能にするも
のである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and provides a surface-modified layer having a dense, less peeling and good adhesion on the surface of a spherical or nearly spherical phosphor particle with less aggregation. It is an object of the present invention to provide a method for producing a surface-modified phosphor having the following. This surface-modified phosphor enables the formation of a homogeneous and high-packing-density phosphor film, and provides excellent cathode ray tubes, fluorescent lamps, PDPs, and the like.

【０００７】[0007]

【課題を解決するための手段】本発明は、下記の手段を
採用することにより、前記の課題の解決に成功した。 (1) 蛍光体の構成金属元素を含有する溶液をガス雰囲気
中に噴霧して微細な液滴となし、乾燥し、該乾燥粒子表
面に表面修飾物質を付着させてから、随伴気体と共に熱
分解合成炉に導入して前記金属塩を熱分解することを特
徴とする表面修飾蛍光体の製造方法。The present invention has succeeded in solving the above-mentioned problems by employing the following means. (1) A solution containing the metal elements constituting the phosphor is sprayed into a gas atmosphere to form fine droplets, dried, and a surface modifying substance is attached to the surface of the dried particles, and then thermally decomposed together with the accompanying gas. A method for producing a surface-modified phosphor, which is introduced into a synthesis furnace to thermally decompose the metal salt.

【０００８】(2) 蛍光体の構成金属元素を含有する溶液
をガス雰囲気中に噴霧して微細な液滴となし、乾燥して
金属塩粒子若しくは金属錯体粒子を生成し、随伴気体と
共に熱分解合成炉に導入して熱分解させた後、該熱分解
生成物粒子の表面に表面修飾物質を付着させることを特
徴とする表面修飾蛍光体の製造方法。 (3) 前記熱分解生成物粒子の表面に表面修飾物質を付着
させた後、さらに、０．５秒〜１０分間加熱処理するこ
とを特徴とする前記(1) 又は(2) 記載の表面修飾蛍光体
の製造方法。(2) A solution containing the metal elements constituting the phosphor is sprayed into a gas atmosphere to form fine droplets, which are dried to produce metal salt particles or metal complex particles, which are thermally decomposed together with the accompanying gas. A method for producing a surface-modified phosphor, comprising introducing a surface-modifying substance to the surface of the pyrolysis product particles after introducing the pyrolysis product into a synthesis furnace. (3) The surface modification according to (1) or (2), wherein after the surface modification substance is attached to the surface of the pyrolysis product particles, a heat treatment is further performed for 0.5 seconds to 10 minutes. A method for producing a phosphor.

【０００９】(4) 前記表面修飾物質を水溶液若しくは懸
濁液となし、これを随伴気体中の前記乾燥粒子又は前記
熱分解生成物粒子の表面に噴霧して付着させることを特
徴とする前記(1) 〜(3) のいずれか１つに記載の表面修
飾蛍光体の製造方法。 (5) 前記表面修飾物質の液滴、及び／又は前記乾燥粒子
若しくは前記熱分解生成物粒子に静電気を付与し、静電
力により前記粒子表面に前記液滴を付着させることを特
徴とする前記(4) 記載の表面修飾蛍光体の製造方法。 (6) 前記表面修飾物質の粉末、及び／又は前記乾燥粒子
若しくは前記熱分解生成物粒子に静電気を付与し、静電
力により前記粒子表面に前記粉末を付着させることを特
徴とする前記(1) 〜(3) のいずれか１つに記載の表面修
飾蛍光体の製造方法。(4) The surface modifying substance is formed into an aqueous solution or suspension, and this is sprayed and adhered to the surface of the dry particles or the pyrolysis product particles in the accompanying gas. 1) The method for producing a surface-modified phosphor according to any one of the above items (1) to (3). (5) applying a static electricity to the droplets of the surface modifying substance, and / or the dried particles or the pyrolysis product particles, and causing the droplets to adhere to the particle surfaces by electrostatic force. 4) The method for producing the surface-modified phosphor described above. (6) The method according to (1), wherein static electricity is applied to the powder of the surface-modifying substance, and / or the dried particles or the pyrolysis product particles, and the powder is attached to the surface of the particles by electrostatic force. The method for producing a surface-modified phosphor according to any one of (1) to (3).

【００１０】(7) 前記金属塩水溶液に溶解している金属
塩の少なくとも１０重量％が硝酸塩又は酢酸塩であるこ
とを特徴とする前記(1) 〜(6) のいずれか１つに記載の
表面修飾蛍光体の製造方法。 (8) 前記金属塩水溶液に溶解している金属塩の少なくと
も５０重量％が硝酸塩又は酢酸塩であることを特徴とす
る前記(7) 記載の表面修飾蛍光体の製造方法。(7) The method as described in any one of (1) to (6) above, wherein at least 10% by weight of the metal salt dissolved in the aqueous metal salt solution is a nitrate or an acetate. A method for producing a surface-modified phosphor. (8) The method for producing a surface-modified phosphor according to (7), wherein at least 50% by weight of the metal salt dissolved in the aqueous metal salt solution is a nitrate or an acetate.

【００１１】(9) 前記熱分解合成は、加熱温度を５００
〜１９００℃、加熱時間を０．５秒〜１０分の範囲で調
整することを特徴とする前記(1) 〜(8) のいずれか１つ
に記載の表面修飾蛍光体の製造方法。 (10)前記蛍光体が酸化物を主相とする蛍光体の場合、前
記熱分解合成は加熱温度を１２００〜１９００℃、加熱
時間を０．５秒〜１０分の範囲で調整することを特徴と
する前記(9) 記載の表面修飾蛍光体の製造方法。(9) In the thermal decomposition synthesis, the heating temperature is set to 500
The method for producing a surface-modified phosphor according to any one of the above (1) to (8), wherein the heating time is adjusted within a range of from 1 second to 1900 ° C. and from 0.5 second to 10 minutes. (10) When the phosphor is a phosphor having an oxide as a main phase, the pyrolysis synthesis is performed by adjusting a heating temperature in a range of 1200 to 1900 ° C. and a heating time in a range of 0.5 seconds to 10 minutes. (9) The method for producing a surface-modified phosphor according to the above (9).

【００１２】(11)前記蛍光体が酸化物を主相とする蛍光
体の場合、前記随伴気体として酸化性ガス又は還元性ガ
スを用いることを特徴とする前記(9) 又は(10)記載の表
面修飾蛍光体の製造方法。 (12)前記酸化性ガスとして空気を用いることを特徴とす
る前記(11)記載の表面修飾蛍光体の製造方法。 (13)前記還元性ガスとして水素又は一酸化炭素を含有す
る窒素を用いることを特徴とする前記(11)記載の表面修
飾蛍光体の製造方法。(11) In the case where the phosphor is a phosphor having an oxide as a main phase, an oxidizing gas or a reducing gas is used as the accompanying gas. A method for producing a surface-modified phosphor. (12) The method for producing a surface-modified phosphor according to the above (11), wherein air is used as the oxidizing gas. (13) The method for producing a surface-modified phosphor according to the above (11), wherein hydrogen or nitrogen containing carbon monoxide is used as the reducing gas.

【００１３】(14)前記蛍光体が硫化物を主相とする蛍光
体の場合、前記熱分解合成は加熱温度を５００〜１１０
０℃、加熱時間を０．５秒〜１０分の範囲で調整するこ
とを特徴とする前記(9) 記載の表面修飾蛍光体の製造方
法。 (15)前記蛍光体が酸硫化物を主相とする蛍光体の場合、
前記熱分解合成は加熱温度を７００〜１３００℃、加熱
時間を０．５秒〜１０分の範囲で調整することを特徴と
する前記(9) 記載の表面修飾蛍光体の製造方法。(14) In the case where the phosphor is a phosphor having a sulfide as a main phase, the pyrolysis synthesis requires a heating temperature of 500 to 110.
(9) The method for producing a surface-modified phosphor according to the above (9), wherein the heating time is adjusted within a range of 0.5 seconds to 10 minutes at 0 ° C. (15) When the phosphor is a phosphor having an oxysulfide as a main phase,
The method for producing a surface-modified phosphor according to (9), wherein the pyrolysis synthesis is performed by adjusting the heating temperature to 700 to 1300 ° C. and the heating time to 0.5 seconds to 10 minutes.

【００１４】(16)前記蛍光体が硫化物又は酸硫化物を主
相とする蛍光体の場合、前記随伴気体として還元性ガス
又は不活性ガスを用いることを特徴とする前記(14)又は
(15)記載の表面修飾蛍光体の製造方法。 (17)前記還元性ガスとして水素又は一酸化炭素を含有す
る窒素を用いることを特徴とする前記(16)記載の表面修
飾蛍光体の製造方法。(16) When the phosphor is a phosphor having sulfide or oxysulfide as a main phase, a reducing gas or an inert gas is used as the accompanying gas.
(15) The method for producing a surface-modified phosphor according to (15). (17) The method for producing a surface-modified phosphor according to the above (16), wherein hydrogen or nitrogen containing carbon monoxide is used as the reducing gas.

【００１５】(18)前記不活性ガスとして窒素を用いるこ
とを特徴とする前記(16)記載の表面修飾蛍光体の製造方
法。 (19)前記蛍光体が硫化物又は酸硫化物を主相とする蛍光
体の場合、前記随伴気体として硫黄をその構成元素とし
て含むガスを使用することを特徴とする前記(14)〜(17)
のいずれか１つに記載の表面修飾蛍光体の製造方法。 (20)硫黄をその構成元素として含むガスとして、硫化水
素又は二硫化炭素を用いることを特徴とする前記(19)記
載の表面修飾蛍光体の製造方法。(18) The method for producing a surface-modified phosphor according to the above (16), wherein nitrogen is used as the inert gas. (19) When the phosphor is a phosphor having a sulfide or an oxysulfide as a main phase, a gas containing sulfur as a constituent element thereof is used as the accompanying gas, wherein (14) to (17). )
The method for producing a surface-modified phosphor according to any one of the above. (20) The method for producing a surface-modified phosphor according to the above (19), wherein hydrogen sulfide or carbon disulfide is used as the gas containing sulfur as a constituent element.

【００１６】[0016]

【発明の実施の形態】本発明は、蛍光体原料溶液をガス
雰囲気中に噴霧して微細な液滴となし、乾燥し、該乾燥
粒子表面に表面修飾物質を付着させてから、随伴気体と
共に熱分解合成炉に導入するか、乾燥粒子を熱分解合成
炉で処理した後に、熱分解生成物粒子の表面に表面修飾
物質を付着して表面修飾蛍光体を製造する方法である。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a phosphor raw material solution is sprayed into a gas atmosphere to form fine droplets, dried, and a surface-modifying substance is attached to the surface of the dried particles. This is a method of producing a surface-modified phosphor by introducing the particles into a pyrolysis synthesis furnace or treating the dried particles in the pyrolysis synthesis furnace, and then attaching a surface modifying substance to the surface of the pyrolysis product particles.

【００１７】本発明において蛍光体粒子に表面修飾層を
形成するには、前記乾燥粒子表面に表面修飾物質を付
着させた後、熱分解合成炉に導入して表面修飾蛍光体を
得る方法（図１）、及び前記乾燥粒子を随伴気体と共
に熱分解合成炉に導入して蛍光体粒子を形成した後、そ
の表面に表面修飾物質を付着させて表面修飾蛍光体を得
る方法（図２）がある。In the present invention, in order to form a surface-modifying layer on the phosphor particles, a method of obtaining a surface-modified phosphor by attaching a surface-modifying substance to the surface of the dried particles and introducing the surface-modified substance into a pyrolysis synthesis furnace (FIG. 1) and a method in which the dried particles are introduced into a pyrolysis synthesis furnace together with the accompanying gas to form phosphor particles, and a surface-modifying substance is attached to the surface of the particles to obtain a surface-modified phosphor (FIG. 2). .

【００１８】本発明で用いる蛍光体の構成金属元素を含
有する水溶液は、金属元素を含有する無機の塩や金属錯
体等の有機金属化合物など、水に可溶であり、高温に加
熱するときに、酸化物、硫化物、酸硫化物に分解反応す
るものであればその種類を問わず使用することができ
る。金属元素の酸化物を酸に溶解した金属塩水溶液も含
む。以下、蛍光体の構成金属元素を含有する無機金属
塩、金属錯体等の有機金属化合物を総称して「金属塩」
といい、この水溶液を「金属塩水溶液」という。その中
でも、硝酸塩水溶液若しくは酢酸塩水溶液は蛍光体の合
成が容易であるため好適である。本発明では、金属塩水
溶液に溶解されている金属塩の少なくとも１０重量％、
より好ましくは少なくとも５０重量％が硝酸塩若しくは
酢酸塩であることが特に好ましい。The aqueous solution containing the metal element constituting the phosphor used in the present invention is soluble in water, such as an inorganic salt containing the metal element and an organometallic compound such as a metal complex. Any substance can be used as long as it decomposes into oxides, sulfides, and oxysulfides. A metal salt aqueous solution in which an oxide of a metal element is dissolved in an acid is also included. Hereinafter, an inorganic metal salt containing a metal element constituting the phosphor, and an organic metal compound such as a metal complex are collectively referred to as “metal salt”.
This aqueous solution is called “metal salt aqueous solution”. Among them, an aqueous solution of a nitrate or an aqueous solution of an acetate is preferable because the phosphor can be easily synthesized. In the present invention, at least 10% by weight of the metal salt dissolved in the aqueous metal salt solution,
More preferably, at least 50% by weight is a nitrate or an acetate.

【００１９】原料溶液には、種々の目的で、蛍光体の構
成金属元素以外の金属元素や添加物を添加することがで
きる。硫化物や酸硫化物を主相とする蛍光体を製造する
ときには、チオ尿素やチオアセトアミドなどの硫黄を含
有する化合物を含有させることが好ましい。To the raw material solution, metal elements other than the constituent metal elements of the phosphor and additives can be added for various purposes. When producing a phosphor having sulfide or oxysulfide as a main phase, it is preferable to include a sulfur-containing compound such as thiourea or thioacetamide.

【００２０】前記表面修飾層は、表面修飾物質を溶解し
た水溶液、表面修飾物質を懸濁させた懸濁液、又は、前
記水溶液若しくは懸濁液を乾燥させた粉末を、前記乾燥
粒子又は蛍光体粒子の表面に付着して形成する。その際
に、前記水溶液若しくは懸濁液を噴霧して形成した液滴
若しくはその粉末を帯電するか、前記乾燥粒子若しくは
蛍光体粒子を帯電するか、両者を逆極性に帯電させるこ
とにより、静電力で前記乾燥粒子若しくは蛍光体粒子表
面に前記液滴若しくは粉末を付着することが好ましい。The surface-modifying layer is formed by coating an aqueous solution in which the surface-modifying substance is dissolved, a suspension in which the surface-modifying substance is suspended, or a powder in which the aqueous solution or the suspension is dried with the dried particles or the phosphor. It forms on the surface of the particles. At this time, by electrostatically charging the droplet formed by spraying the aqueous solution or the suspension or the powder thereof, charging the dry particles or the phosphor particles, or charging both of them with opposite polarities. Preferably, the droplets or powders are attached to the surfaces of the dried particles or phosphor particles.

【００２１】また、水溶液中に少量のフラックスを添加
すると、熱分解反応を比較的低温で短時間で結晶性の高
い蛍光体球状粒子を生成できる利点がある。フラックス
の具体例としては、ハロゲン化アルカリ金属塩、ハロゲ
ン化アルカリ土類金属塩、ハロゲン化アンモニウム塩、
ホウ酸などを挙げることができる。なお、良好な発光特
性を得るためには、キラーセンターとなる鉄やニッケル
などの不純物元素の含有量の少ない原料溶液を使用する
ことが好ましい。Further, when a small amount of flux is added to the aqueous solution, there is an advantage that the thermal decomposition reaction can be performed at a relatively low temperature in a short time to form phosphor spherical particles having high crystallinity. Specific examples of the flux include alkali metal halide salts, alkali earth metal halide salts, ammonium halide salts,
Boric acid and the like can be mentioned. Note that in order to obtain good emission characteristics, it is preferable to use a raw material solution containing a small amount of an impurity element such as iron or nickel which serves as a killer center.

【００２２】蛍光体原料である各金属塩は水や酸に投入
して攪拌して完全に溶解させることが望ましい。溶液中
の各元素濃度は、蛍光体粒子の直径に対する微細な液滴
の直径にしたがって調整される。即ち、蛍光体粒子直径
に対する液滴直径の比が大きければ、溶液中の溶質濃度
を低くし、その比が小さければ溶質濃度を高く調整する
のがよい。良好な蛍光体を合成するためには、水溶液中
の金属元素の溶質濃度Ｃ（重量モル濃度で、水溶液１ｋ
ｇ中に含有される全ての金属元素の合計モル数）は０．
０１≦Ｃ≦５．０の範囲が適当である。It is desirable that each metal salt, which is a raw material of a phosphor, is put into water or an acid and stirred to be completely dissolved. The concentration of each element in the solution is adjusted according to the diameter of the fine droplet relative to the diameter of the phosphor particles. That is, if the ratio of the droplet diameter to the phosphor particle diameter is large, the solute concentration in the solution should be lowered, and if the ratio is small, the solute concentration should be adjusted high. In order to synthesize a good phosphor, the solute concentration C of the metal element in the aqueous solution (molar concentration, 1 k
(total mole number of all metal elements contained in g) is 0.
The range of 01 ≦ C ≦ 5.0 is appropriate.

【００２３】金属塩水溶液から微細な液滴を形成する方
法としては、例えば、加圧空気で液体を吸い上げなが
ら噴霧して平均粒径１〜５０μｍの液滴を形成する方
法、圧電結晶からの２ＭＨｚ程度の超音波を加えて平
均粒径４〜１０μｍの液滴を形成する方法、孔径が１
０〜２０μｍのオリフィスを振動子により振動させて平
均粒径５〜５０μｍの液滴を形成する方法、回転円板
上に溶液を一定速度で落下させて遠心力によって平均粒
径２０〜１００μｍの液滴を形成する方法、液体表面
に高い電圧を印加して平均粒径０．５〜１０μｍの液滴
を発生する方法、ピエゾ素子ヘッド方式やバブルジェ
ット方式、サーマルヘッド方式などのヘッドを用いた液
滴形成方法、高圧気体を平滑面上に噴射して原料溶液
を薄膜流となし、液滴を形成する方法などを採用するこ
とができる。As a method of forming fine droplets from a metal salt aqueous solution, for example, a method of forming droplets having an average particle diameter of 1 to 50 μm by spraying while sucking up a liquid with pressurized air, a method of forming 2 MHz from a piezoelectric crystal, To form droplets having an average particle size of 4 to 10 μm by applying ultrasonic waves of about
A method in which an orifice of 0 to 20 μm is vibrated by a vibrator to form a droplet having an average particle size of 5 to 50 μm. A solution having an average particle size of 20 to 100 μm is dropped on a rotating disk at a constant speed and centrifugal force is applied. A method for forming a droplet, a method for applying a high voltage to the surface of a liquid to generate a droplet having an average particle size of 0.5 to 10 μm, a liquid using a piezo element head system, a bubble jet system, a thermal head system, etc. A droplet forming method, a method of injecting a high-pressure gas onto a smooth surface to form a raw material solution into a thin film flow, and form a droplet can be employed.

【００２４】本発明の微細な液滴の形成時の雰囲気ガス
としては、空気、酸素、窒素、水素、少量の水素や一酸
化炭素を含む窒素やアルゴンなどを使用できる。良好な
発光特性を得るためには、発光に関与する付活剤イオン
の種類により気体を選択することが重要である。例え
ば、酸化雰囲気で原子価を保ちやすいＥｕ3+等を付活イ
オンとする場合は、空気や酸素などの酸化性ガスが好ま
しく、また、還元雰囲気で原子価を保ちやすいＥｕ2+等
を付活イオンとする場合は、水素や、少量の水素や一酸
化炭素を含む窒素やアルゴンなどの還元性ガスが好まし
い。硫化物や酸硫化物を母体の主相とする蛍光体を製造
する場合は、硫化水素ガス、二硫化炭素ガス、又は、硫
黄をその構成元素として含む気体を使用することが好ま
しい。As the atmosphere gas for forming fine droplets of the present invention, air, oxygen, nitrogen, hydrogen, nitrogen or argon containing a small amount of hydrogen or carbon monoxide, or the like can be used. In order to obtain good light emission characteristics, it is important to select a gas according to the type of activator ions involved in light emission. For example, in the case where Eu 3+ or the like that easily maintains a valence in an oxidizing atmosphere is used as the activation ion, an oxidizing gas such as air or oxygen is preferable, and Eu 2+ or the like that easily maintains a valence in a reducing atmosphere is used. In the case where active ions are used, hydrogen or a reducing gas such as nitrogen or argon containing a small amount of hydrogen or carbon monoxide is preferable. In the case of producing a phosphor having sulfide or oxysulfide as a parent main phase, it is preferable to use hydrogen sulfide gas, carbon disulfide gas, or a gas containing sulfur as a constituent element.

【００２５】液滴を乾燥して金属塩粒子を形成する前に
液滴を分級して、重量平均粒子径を２〜４０μｍに調整
することが望ましい。液滴の重量平均粒子径が２μｍよ
り小さな液滴が増えると、得られる蛍光体が極度に小さ
くなり、蛍光体スラリーを調製するときに、粘度が高く
なって蛍光膜の塗布特性が低下する。４０μｍより大き
な液滴が増えると、得られる蛍光体が極度に大きくなっ
て、緻密で高精細の蛍光膜を形成し難くなる。Before the droplets are dried to form metal salt particles, the droplets are preferably classified to adjust the weight average particle diameter to 2 to 40 μm. When the number of droplets having a weight average particle diameter of less than 2 μm increases, the obtained phosphor becomes extremely small, and when a phosphor slurry is prepared, the viscosity becomes high and the coating characteristics of the phosphor film deteriorate. When the number of droplets larger than 40 μm increases, the obtained phosphor becomes extremely large, and it becomes difficult to form a dense and high-definition phosphor film.

【００２６】熱分解合成炉における蛍光体の生産効率を
上げるために、分級時に液滴随伴気体の単位体積当たり
の液滴体積を２倍以上に濃縮することが好ましい。分級
器としては、重力分級器、遠心分級器、慣性分級器など
を使用できるが、その中でも慣性分級器が好適である。
慣性分級器は、随伴する気体の一部と共に、粒径範囲の
下限値未満の液滴を除去するのに適している。In order to increase the production efficiency of the phosphor in the pyrolysis synthesis furnace, it is preferable to concentrate the droplet volume per unit volume of the gas accompanying droplets at least twice during classification. As a classifier, a gravity classifier, a centrifugal classifier, an inertial classifier and the like can be used, and among them, the inertial classifier is preferable.
The inertial classifier is suitable for removing droplets below the lower limit of the particle size range, along with some of the entrained gas.

【００２７】微細な液滴の乾燥方法としては、凍結乾燥
や減圧乾燥なども可能であるが、加熱乾燥が好適であ
る。例えば、前記の微細な液滴の形成手段を円筒容器の
上方に配置し、下方に乾燥用の加熱帯を設け、下方に流
れる随伴気体中に微細な液滴を放出し、降下する間に乾
燥させることができる。As a method for drying the fine droplets, freeze drying, drying under reduced pressure, etc. are possible, but drying by heating is preferred. For example, the above-mentioned means for forming fine droplets is arranged above a cylindrical container, a heating zone for drying is provided below, and fine droplets are discharged into accompanying gas flowing downward, and drying is performed while descending. Can be done.

【００２８】加熱乾燥された金属塩粒子は、１００℃以
上に保温された状態で熱分解合成炉に移行することが望
ましい。１００℃を下回ると、乾燥時に発生した水蒸気
が凝縮して前記粒子を部分的に溶解して凝集し、所望の
形状や粒径の蛍光体粒子を得ることができないおそれが
ある。The heat-dried metal salt particles are desirably transferred to a pyrolysis synthesis furnace while keeping the temperature at 100 ° C. or higher. If the temperature is lower than 100 ° C., water vapor generated during drying may condense, partially dissolve and aggregate the particles, and may not be able to obtain phosphor particles having a desired shape and particle size.

【００２９】本発明の熱分解合成では、熱分解合成炉内
で加熱温度を５００〜１９００℃、加熱時間を０．５秒
〜１０分の範囲に調整することが好ましい。本発明の蛍
光体が酸化物を主相とする蛍光体の場合、熱分解合成
は、加熱温度を１２００〜１９００℃、加熱時間を０．
５秒〜１０分の範囲で調整することにより発光特性の良
好な蛍光体を得ることができる。本発明の蛍光体が硫化
物を主相とする蛍光体の場合、熱分解合成は、加熱温度
を５００〜１１００℃、加熱時間を０．５秒〜１０分の
範囲で調整することにより発光特性の良好な蛍光体を得
ることができる。 本発明の蛍光体が酸硫化物を主相と
する蛍光体の場合、熱分解合成の加熱温度を７００〜１
３００℃、加熱時間を０．５秒〜１０分の範囲で調整す
ることにより発光特性の良好な蛍光体を得ることができ
る。In the pyrolysis synthesis of the present invention, it is preferable to adjust the heating temperature in the pyrolysis synthesis furnace to 500 to 1900 ° C. and the heating time to 0.5 seconds to 10 minutes. When the phosphor of the present invention is a phosphor having an oxide as a main phase, in the thermal decomposition synthesis, the heating temperature is 1200 to 1900 ° C., and the heating time is 0.1 minute.
By adjusting the time in the range of 5 seconds to 10 minutes, a phosphor having good emission characteristics can be obtained. When the phosphor of the present invention is a phosphor having a sulfide as a main phase, the pyrolysis synthesis is carried out by adjusting the heating temperature in the range of 500 to 1100 ° C. and the heating time in the range of 0.5 seconds to 10 minutes. And a phosphor having a good value can be obtained. When the phosphor of the present invention is a phosphor having an oxysulfide as a main phase, the heating temperature of the thermal decomposition synthesis is set to 700 to 1
By adjusting the heating time at 300 ° C. in the range of 0.5 seconds to 10 minutes, a phosphor having good emission characteristics can be obtained.

【００３０】本発明で使用する表面修飾物質としては、
シリカ、アルミナ、アルミナゾル、チタニア、酸化亜鉛
などの無機金属酸化物や、高温に加熱されて無機金属酸
化物を生成する前記無機金属酸化物の前駆体、具体的に
は前記金属化合物、水酸化亜鉛、弁柄、アルミン酸コバ
ルト、群青などの顔料粒子を挙げることができる。これ
らの表面修飾物質は、蛍光体の分散性や蛍光体スラリー
の塗布特性などを改善するのに有効である。The surface modifying substance used in the present invention includes:
Inorganic metal oxides such as silica, alumina, alumina sol, titania, and zinc oxide, and precursors of the inorganic metal oxides that generate inorganic metal oxides when heated to a high temperature, specifically, the metal compound, zinc hydroxide , Red iron oxide, cobalt aluminate, ultramarine blue and the like. These surface modifiers are effective in improving the dispersibility of the phosphor and the coating properties of the phosphor slurry.

【００３１】[0031]

【実施例】（実施例１）蛍光体の化学組成が（Ｙ0.97Ｅ
ｕ0.03）2 Ｏ3 となるように硝酸イットリウム及び硝酸
ユーロピウムを水に溶解し、少量の硝酸を添加して溶質
濃度Ｃ（金属元素の合計モル数／水溶液１ｋｇ）が０．
３の金属塩水溶液を作成した。１ＭＰａに加圧された空
気でこの金属塩水溶液を吸い上げて微細な液滴に噴霧し
た。この微細な液滴を慣性分級器を使用して分級して、
液滴の重量平均粒子径が５μｍで９０重量％の微液滴が
１０μｍ以下の粒径の液滴とした。この分級された液滴
を２００℃で加熱乾燥して金属塩粒子を得た。EXAMPLES (Example 1) The chemical composition of the phosphor was (Y 0.97 E
u 0.03 ) 2 O 3 , yttrium nitrate and europium nitrate are dissolved in water, and a small amount of nitric acid is added to adjust the solute concentration C (total mole number of metal elements / 1 kg of aqueous solution) to 0.1.
A metal salt aqueous solution of No. 3 was prepared. This metal salt aqueous solution was sucked up by air pressurized to 1 MPa and sprayed into fine droplets. This fine droplet is classified using an inertial classifier,
Fine droplets having a weight average particle diameter of 5 μm and 90% by weight of the droplets were formed as droplets having a particle diameter of 10 μm or less. The classified droplets were dried by heating at 200 ° C. to obtain metal salt particles.

【００３２】得られた金属塩粒子を２００℃に保持しな
がら空気流で熱分解合成炉に搬送して、最高温度が１６
００℃の電気炉内で１０秒間の滞留時間だけ熱分解合成
して蛍光体を得た。この蛍光体を一旦捕集してから、該
蛍光体を負に帯電させて空気流中に浮遊させ、他方、平
均粒子径が０．２μｍの弁柄を水に懸濁させて０．５重
量％の水スラリーを調整し、このスラリーを空気流中に
浮遊している前記蛍光体粒子の表面に噴霧して正に帯電
させた弁柄含有液滴と、前記の負に帯電した蛍光体粒子
を静電的に吸引して弁柄を付着させた状態で加熱炉に導
入し、１０００℃で１０秒間加熱処理を行った。The obtained metal salt particles are conveyed to the pyrolysis synthesis furnace by airflow while maintaining the temperature at 200 ° C.
A phosphor was obtained by pyrolysis synthesis in a 00 ° C. electric furnace for a residence time of 10 seconds. Once the phosphor is collected, the phosphor is negatively charged and floated in an air stream, while a petiole having an average particle diameter of 0.2 μm is suspended in water to obtain 0.5 wt. % Water slurry is prepared, and the slurry is sprayed onto the surface of the phosphor particles floating in the air stream to form a positively charged petiole-containing droplet; and the negatively charged phosphor particles Was introduced into a heating furnace in a state where the stem was adhered by electrostatically sucking, and a heat treatment was performed at 1000 ° C. for 10 seconds.

【００３３】得られた蛍光体は、その表面が滑らかで粒
子径が揃った略球状の粒子であり、その平均粒径は１μ
ｍだった。この蛍光体の弁柄剥離の程度は、従来の湿式
法で付着させた場合より少なかった。なお、弁柄の剥離
の程度は、蛍光体を試験管に投入し、さらに一定量の水
を加えて蛍光体スラリーとし、この試験管を一定時間振
とうしてから、一定時間放置し、試験管の上澄み液の光
透過率を測定して弁柄の剥離の程度を相対的に調べた。
この蛍光体について波長２５４ｎｍ紫外線照射下での発
光スペクトルを測定したところ、良好な赤色発光を示し
た。The obtained phosphor is a substantially spherical particle having a smooth surface and a uniform particle diameter, and has an average particle diameter of 1 μm.
m. The degree of peeling off of the fluorescent material was smaller than in the case where the fluorescent material was attached by a conventional wet method. In addition, the degree of peeling of the petiole was measured by putting the phosphor into a test tube, adding a certain amount of water to make a phosphor slurry, shaking the test tube for a certain period of time, and leaving it to stand for a certain period of time. The light transmittance of the supernatant of the tube was measured to relatively examine the degree of peeling of the petiole.
The emission spectrum of this phosphor under irradiation of ultraviolet light with a wavelength of 254 nm was measured.

【００３４】（実施例２）蛍光体の化学組成が（Ｂａ
0.9 Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 となるように
硝酸バリウム、硝酸ユーロピウム、硝酸マグネシウム、
硝酸アルミニウムをそれぞれ水に溶解し、少量の硝酸を
添加して溶質濃度Ｃが０．３の均質な金属塩水溶液を作
成した。随伴気体として水素を２体積％含有する窒素を
使用し、この金属塩水溶液を１．７ＭＨｚの振動子を有
する超音波噴霧器に入れて微細な液滴を形成した。次
に、この液滴を慣性分級器を使用して分級して、液滴の
重量平均粒子径が５μｍで９０重量％の微液滴が１０μ
ｍ以下の粒径の液滴とすると共に、液滴随伴気体の単位
体積当たりの液滴体積を５倍に濃縮した。Example 2 The chemical composition of the phosphor was (Ba)
0.9 Eu 0.1) barium nitrate so that O · MgO · 5Al 2 O 3 , europium nitrate, magnesium nitrate,
Aluminum nitrate was dissolved in water, and a small amount of nitric acid was added to prepare a homogeneous metal salt aqueous solution having a solute concentration C of 0.3. Nitrogen containing 2% by volume of hydrogen was used as an accompanying gas, and the aqueous metal salt solution was put into an ultrasonic atomizer having a 1.7 MHz vibrator to form fine droplets. Next, the droplets were classified using an inertial classifier, and fine droplets having a weight average particle diameter of 5 μm and 90% by weight of 10 μm were obtained.
m and a droplet volume per unit volume of the gas accompanying the droplet was concentrated 5 times.

【００３５】この分級された液滴を２００℃で加熱乾燥
して金属塩粒子を得た。この金属塩粒子を２００℃に保
持して熱分解合成炉に搬送して、最高温度が１６００℃
の電気炉内で１０秒間の滞留時間だけ熱分解合成して酸
化物粒子を得た。次に硝酸アルミニウムを水に溶解し、
少量の硝酸を添加し溶質濃度Ｃが０．３の金属塩水溶液
を作成した。この硝酸アルミニウム水溶液を先に製造し
た酸化物粒子に対して２重量％となるように酸化物粒子
に噴霧した。その際、酸化物粒子を負に帯電させ、硝酸
アルミニウムの液滴を正に帯電させて、酸化物粒子の表
面に硝酸アルミニウムを付着させ、これを、水素を２体
積％含有する窒素ガス気流と共に加熱炉に導入して１０
００℃で１０秒間加熱して酸化物粒子の表面に酸加アル
ミニウムを被覆して（Ｂａ0.9 Ｅｕ0.1 ）Ｏ・ＭｇＯ・
５Ａｌ2 Ｏ3 蛍光体を得た。The classified droplets were dried by heating at 200 ° C. to obtain metal salt particles. The metal salt particles are held at 200 ° C. and transported to a pyrolysis synthesis furnace, where the maximum temperature is 1600 ° C.
Was thermally decomposed and synthesized in an electric furnace for a residence time of 10 seconds to obtain oxide particles. Next, dissolve aluminum nitrate in water,
A small amount of nitric acid was added to prepare a metal salt aqueous solution having a solute concentration C of 0.3. The aluminum nitrate aqueous solution was sprayed on the oxide particles so as to be 2% by weight with respect to the oxide particles prepared above. At this time, the oxide particles are negatively charged, the droplets of aluminum nitrate are positively charged, and aluminum nitrate is adhered to the surface of the oxide particles. This is mixed with a nitrogen gas stream containing 2% by volume of hydrogen. 10 in the heating furnace
The surface of the oxide particles was coated with acidified aluminum by heating at 00 ° C. for 10 seconds to form (Ba 0.9 Eu 0.1 ) O.MgO.
5Al 2 O 3 phosphor was obtained.

【００３６】得られた蛍光体は、その表面が滑らかで粒
子径が揃った略球状の粒子であり、その平均粒径は１μ
ｍだった。蛍光体表面は酸化アルミニウムの皮膜で覆わ
れていた。この蛍光体について波長２５４ｎｍ紫外線照
射下での発光スペクトルを測定したところ、良好な青色
発光を示した。The obtained phosphor is a substantially spherical particle having a smooth surface and a uniform particle diameter, and has an average particle diameter of 1 μm.
m. The phosphor surface was covered with a film of aluminum oxide. The emission spectrum of this phosphor under irradiation of ultraviolet light with a wavelength of 254 nm was measured, and it was found that the phosphor emitted good blue light.

【００３７】[0037]

【発明の効果】本発明は、上記の構成を採用することに
より、凝集の少ない球状若しくは球状に近い形状の蛍光
体粒子表面に、緻密で剥離の少ない密着性の良好な表面
修飾層を有する表面修飾蛍光体を効率的に安価に得るこ
とが可能になった。また、この表面修飾蛍光体は、ブラ
ウン管、蛍光ランプやＰＤＰなどの蛍光膜とした時、均
質で緻密な高輝度蛍光膜を形成することが可能となる。According to the present invention, by adopting the above constitution, a surface having a dense, less peeling and good adhesion surface modification layer on a spherical or nearly spherical phosphor particle surface with less aggregation. The modified phosphor can be obtained efficiently and inexpensively. In addition, when the surface-modified phosphor is used as a phosphor film for a cathode ray tube, a fluorescent lamp, a PDP, or the like, it becomes possible to form a uniform and dense high-luminance phosphor film.

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

【図１】表面修飾物質又はその前駆体を乾燥工程の後に
導入して表面修飾蛍光体を製造する手順を示した図であ
る。FIG. 1 is a view showing a procedure for producing a surface-modified phosphor by introducing a surface-modifying substance or a precursor thereof after a drying step.

【図２】表面修飾物質又はその前駆体を熱分解工程の後
に導入する表面修飾蛍光体を製造する手順を示した図で
ある。FIG. 2 is a view showing a procedure for producing a surface-modified phosphor in which a surface-modifying substance or a precursor thereof is introduced after a thermal decomposition step.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 三輪 泰一郎 神奈川県小田原市成田1060番地 化成オプ トニクス株式会社内 Ｆターム(参考） 4H001 CA06 CA07 CC02 CC04 CC05 CF02 XA08 XA12 XA13 XA16 XA39 XA56 XA63  ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Taiichiro Miwa 1060 Narita, Odawara-shi, Kanagawa F-term in Kasei Optonics Co., Ltd. (Reference) 4H001 CA06 CA07 CC02 CC04 CC05 CF02 XA08 XA12 XA13 XA16 XA39 XA56 XA63

Claims (12)

【特許請求の範囲】[Claims] 【請求項１】 蛍光体の構成金属元素を含有する溶液を
ガス雰囲気中に噴霧して微細な液滴となし、乾燥し、該
乾燥粒子の表面に表面修飾物質を付着させてから、随伴
気体と共に熱分解合成炉に導入して熱分解することを特
徴とする表面修飾蛍光体の製造方法。1. A solution containing a metal element constituting a phosphor is sprayed into a gas atmosphere to form fine droplets, dried, and a surface modifying substance is attached to the surface of the dried particles. A method for producing a surface-modified phosphor, wherein the phosphor is introduced into a pyrolysis synthesis furnace for thermal decomposition. 【請求項２】 蛍光体の構成金属元素を含有する溶液を
ガス雰囲気中に噴霧して微細な液滴となし、乾燥し、随
伴気体と共に熱分解合成炉に導入して熱分解させた後、
該熱分解生成物粒子の表面に表面修飾物質を付着させる
ことを特徴とする表面修飾蛍光体の製造方法。2. A solution containing a metal element constituting the phosphor is sprayed into a gas atmosphere to form fine droplets, dried, introduced into a pyrolysis synthesis furnace together with accompanying gas, and thermally decomposed.
A method for producing a surface-modified phosphor, comprising attaching a surface-modifying substance to the surface of the thermal decomposition product particles. 【請求項３】 前記熱分解生成物粒子の表面に表面修飾
物質を付着させた後、さらに０．５秒〜１０分間加熱処
理することを特徴とする請求項１又は２記載の表面修飾
蛍光体の製造方法。3. The surface-modified phosphor according to claim 1, wherein a heat treatment is further performed for 0.5 second to 10 minutes after a surface-modifying substance is attached to the surface of the thermal decomposition product particles. Manufacturing method. 【請求項４】 前記表面修飾物質を水溶液若しくは懸濁
液となし、これを随伴気体中の前記乾燥粒子又は前記熱
分解生成物粒子の表面に噴霧して付着させることを特徴
とする請求項１〜３のいずれか１項に記載の表面修飾蛍
光体の製造方法。4. The method according to claim 1, wherein the surface modifying substance is an aqueous solution or suspension, which is sprayed and adhered to the surface of the dried particles or the pyrolysis product particles in the accompanying gas. 4. The method for producing a surface-modified phosphor according to any one of items 1 to 3. 【請求項５】 前記表面修飾物質の液滴、及び／又は前
記乾燥粒子若しくは前記熱分解生成物粒子に静電気を付
与し、静電力により前記粒子表面に前記液滴を付着させ
ることを特徴とする請求項４記載の表面修飾蛍光体の製
造方法。5. The method according to claim 1, wherein static electricity is applied to the droplets of the surface modifying substance and / or the dried particles or the pyrolysis product particles, and the droplets adhere to the surface of the particles by electrostatic force. A method for producing a surface-modified phosphor according to claim 4. 【請求項６】 前記表面修飾物質の粉末、及び／又は前
記乾燥粒子若しくは前記熱分解生成物粒子に静電気を付
与し、静電力により前記粒子表面に前記粉末を付着させ
ることを特徴とする請求項１〜３のいずれか１項に記載
の表面修飾蛍光体の製造方法。6. The method according to claim 1, wherein static electricity is applied to the powder of the surface modifying substance and / or the dry particles or the thermal decomposition product particles, and the powder is attached to the surface of the particles by electrostatic force. The method for producing a surface-modified phosphor according to any one of claims 1 to 3. 【請求項７】 前記金属塩水溶液に溶解している金属塩
の少なくとも１０重量％が硝酸塩又は酢酸塩であること
を特徴とする請求項１〜６のいずれか１項に記載の表面
修飾蛍光体の製造方法。7. The surface-modified phosphor according to claim 1, wherein at least 10% by weight of the metal salt dissolved in the aqueous metal salt solution is nitrate or acetate. Manufacturing method. 【請求項８】 前記蛍光体が硫化物又は酸硫化物を主相
とする蛍光体の場合、前記随伴気体が硫黄をその構成元
素として含む気体からなることを特徴とする請求項１〜
７のいずれか１項に記載の表面修飾蛍光体の製造方法。8. When the phosphor is a phosphor having sulfide or oxysulfide as a main phase, the accompanying gas is a gas containing sulfur as a constituent element thereof.
8. The method for producing a surface-modified phosphor according to any one of items 7 to 7. 【請求項９】 前記熱分解合成は、加熱温度を５００〜
１９００℃、加熱時間を０．５秒〜１０分の範囲で調整
することを特徴とする請求項１〜８のいずれか１項に記
載の表面修飾蛍光体の製造方法。9. The thermal decomposition synthesis according to claim 1, wherein the heating temperature is 500 to
The method for producing a surface-modified phosphor according to any one of claims 1 to 8, wherein the heating time is adjusted at 1900 ° C and the heating time is within a range of 0.5 seconds to 10 minutes. 【請求項１０】 前記蛍光体が酸化物を主相とする蛍光
体の場合、前記熱分解合成は加熱温度を１２００〜１９
００℃、加熱時間を０．５秒〜１０分の範囲で調整する
ことを特徴とする請求項９記載の表面修飾蛍光体の製造
方法。10. In the case where the phosphor is a phosphor having an oxide as a main phase, the pyrolysis synthesis requires a heating temperature of 1200 to 19.
The method for producing a surface-modified phosphor according to claim 9, wherein the heating time is adjusted within a range of 0.5 seconds to 10 minutes at 00C. 【請求項１１】 前記蛍光体が硫化物を主相とする蛍光
体の場合、前記熱分解合成は加熱温度を５００〜１１０
０℃、加熱時間を０．５秒〜１０分の範囲で調整するこ
とを特徴とする請求項９記載の表面修飾蛍光体の製造方
法。11. In the case where the phosphor is a phosphor having a sulfide as a main phase, the pyrolysis synthesis may be performed at a heating temperature of 500 to 110.
The method for producing a surface-modified phosphor according to claim 9, wherein the heating time is adjusted within a range of 0.5 seconds to 10 minutes at 0 ° C. 【請求項１２】 前記蛍光体が酸硫化物を主相とする蛍
光体の場合、前記熱分解合成は加熱温度を７００〜１３
００℃、加熱時間を０．５秒〜１０分の範囲で調整する
ことを特徴とする請求項９記載の表面修飾蛍光体の製造
方法。12. When the phosphor is a phosphor having an oxysulfide as a main phase, the pyrolysis synthesis may be performed at a heating temperature of 700 to 13.
The method for producing a surface-modified phosphor according to claim 9, wherein the heating time is adjusted within a range of 0.5 seconds to 10 minutes at 00C.
JP34185499A 1999-12-01 1999-12-01 Preparation process of surface-modified fluorescent body Pending JP2001152143A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP34185499A JP2001152143A (en) 1999-12-01 1999-12-01 Preparation process of surface-modified fluorescent body
KR1020027006938A KR20020070297A (en) 1999-12-01 2000-12-01 Method for producing phosphor
CN00818706A CN1433454A (en) 1999-12-01 2000-12-01 Method for producing phosphor
PCT/JP2000/008526 WO2001040402A1 (en) 1999-12-01 2000-12-01 Method for producing phosphor
EP00978058A EP1236784A1 (en) 1999-12-01 2000-12-01 Method for producing phosphor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP34185499A JP2001152143A (en) 1999-12-01 1999-12-01 Preparation process of surface-modified fluorescent body

Publications (1)

Publication Number Publication Date
JP2001152143A true JP2001152143A (en) 2001-06-05

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Country Link
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100431458B1 (en) * 2001-08-13 2004-05-12 주식회사 엘지화학 Blue phosphor of a high performance according to site selectively chemical reaction and method for preparing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100431458B1 (en) * 2001-08-13 2004-05-12 주식회사 엘지화학 Blue phosphor of a high performance according to site selectively chemical reaction and method for preparing the same

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