JP2003193045A - Pigment-adhered fluorescent substance and method for producing the same - Google Patents

Pigment-adhered fluorescent substance and method for producing the same

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Publication number
JP2003193045A
JP2003193045A JP2001403020A JP2001403020A JP2003193045A JP 2003193045 A JP2003193045 A JP 2003193045A JP 2001403020 A JP2001403020 A JP 2001403020A JP 2001403020 A JP2001403020 A JP 2001403020A JP 2003193045 A JP2003193045 A JP 2003193045A
Authority
JP
Japan
Prior art keywords
pigment
phosphor
blue
cobalt
pigment particles
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.)
Withdrawn
Application number
JP2001403020A
Other languages
Japanese (ja)
Inventor
Kazuto Iwasaki
和人 岩崎
Shinichi Furusawa
真一 古澤
Tomohiro Miyazaki
友博 宮崎
Toshihiko Sato
稔彦 佐藤
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
Original Assignee
Kasei Optonix Ltd
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 filed Critical Kasei Optonix Ltd
Priority to JP2001403020A priority Critical patent/JP2003193045A/en
Priority to KR1020020071514A priority patent/KR20030055107A/en
Publication of JP2003193045A publication Critical patent/JP2003193045A/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cobalt-blue blue pigment-adhered fluorescent substance, which pigment has a strong adhesion force to the fluorescent substance, does not change the body color by the irradiation of electron beams, and has good electron beam resistance and heat resistance. <P>SOLUTION: The pigment-adhered fluorescent substance is prepared by adhering cobalt-blue blue pigment particles comprising an complex oxide of cobalt oxide (CoO) with aluminum oxide (Al<SB>2</SB>O<SB>3</SB>) as pigment particles to the surface of the fluorescent substance, wherein the pigment particles have an average particle diameter of 0.05 to 0.20 μm and a diffraction peak half value width of ≤0.30° at a diffraction angle (2θ) of 31.1° in a powder diffraction X-ray spectrum using Cu-Kα1 characteristic X-rays. <P>COPYRIGHT: (C)2003,JPO

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、コントラストの改
善されたカラーＴＶやコンピューターディスプレイのブ
ラウン管用蛍光膜に使用される顔料付蛍光体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigmented phosphor used for a fluorescent film for a cathode ray tube of a color TV or a computer display with improved contrast.

【０００２】[0002]

【従来の技術】カラーブラウン管の画面の明るさを出来
るだけ低下させずに、コントラストを改善するのに、そ
の蛍光面の蛍光膜として顔料付き蛍光体を用いる方法が
有効であり、特に、用いられる顔料付蛍光体として従来
の顔料付蛍光体に比べて顔料の付着量を増加させ、管面
（蛍光面）反射率をより低下させた管種のカラーブラウ
ン管が近年多く使用されるようになった。2. Description of the Related Art A method of using a pigmented phosphor as a phosphor film of a phosphor screen is effective for improving the contrast without reducing the screen brightness of a color cathode ray tube as much as possible, and is particularly used. As a pigmented phosphor, a color cathode ray tube of a tube type in which the amount of the pigment attached is increased and the reflectance of the tube surface (fluorescent surface) is further reduced compared to the conventional pigmented phosphor, has been widely used in recent years. .

【０００３】ところで、顔料付着量の多い顔料付蛍光体
を用いてカラーブラウン管の蛍光膜を形成する場合、顔
料が蛍光体に対して強固に付着していないと蛍光体をブ
ラウン管のガラス面に塗布する工程において顔料が剥離
し易く、顔料と蛍光体とが分離し、顔料付着ムラが生じ
たり、蛍光体の反射率が下がってコントラストが低下し
たりするため、顔料を蛍光体に対してより強固に付着さ
せる技術が重要になって来た。By the way, in the case of forming a fluorescent film of a color cathode ray tube using a pigmented phosphor having a large amount of attached pigment, if the pigment is not firmly attached to the phosphor, the phosphor is applied to the glass surface of the cathode ray tube. In the process of peeling the pigment, the pigment and the phosphor are separated from each other, uneven adhesion of the pigment occurs, or the reflectance of the phosphor decreases and the contrast decreases. The technology to attach to the surface has become important.

【０００４】従来、顔料を蛍光体に付着させるには、例
えばゼラチンなどの比較的親水性の良い樹脂をバインダ
ーとして使用して、蛍光体の水中での分散性を損なわな
いような条件で付着させるが、その際、顔料付着力を向
上させるための手段として、例えば顔料付蛍光体を製造
する際に使用するバインダーの量を増加させると、蛍光
体や顔料の分散性が損なわれる傾向にあり好ましくな
い。Conventionally, in order to attach the pigment to the phosphor, a resin having relatively high hydrophilicity such as gelatin is used as a binder and is attached under the condition that the dispersibility of the phosphor in water is not impaired. However, at that time, as a means for improving the pigment adhesion, for example, when the amount of the binder used in the production of the pigmented phosphor is increased, the dispersibility of the phosphor and the pigment tends to be impaired, which is preferable. Absent.

【０００５】また、顔料付着力を向上させるための別の
手段として、粒子径の出来るだけ小さい顔料を用いるこ
とによって、その顔料が均一に蛍光体表面に付着するた
め顔料粒子と蛍光体粒子との接触面積が大きくなり、ま
た、他の粒子との摩擦を受けにくくなるため互いに剥離
し難くなる。しかしながら、小粒子の顔料ほど結晶性が
劣り、そのため、耐熱性、耐化学薬品性、耐電子線性な
どの顔料粒子の物理的、化学的安定性が低減する。ＴＶ
やコンピューターディスプレー用ブラウン管の蛍光膜製
造プロセスにおいては、５００℃程度のベーキング工程
があるため、これらの蛍光膜に使われる蛍光体は、特に
５００℃前後の温度で熱により蛍光体が特性変化しない
だけの耐熱性を有することが重要である。更に、画像や
文字を表示するコンピューターディスプレー用ブラウン
管の蛍光膜等として使用された場合、蛍光膜中の顔料付
蛍光体が高電圧、高電流密度の電子線照射を受けるた
め、蛍光膜の一部のみが局部的に長時間電子線に晒され
て焼けを生じる場合があり、その場合、電子線照射され
た部分とそうでない部分とで蛍光体表面に付着している
顔料粒子間に焼けの程度の違いによる彩度や明度等の差
が生じる結果、顔料付蛍光体としての発光特性に局部的
な差異が生じてこれが観察者に視認され、その差が往々
にして問題になる。そのため、顔料付蛍光体の表面に付
着させる顔料粒子は、結晶性が良好で耐電子線性に優れ
る顔料粒子であることが重要である。Further, as another means for improving the pigment adhering power, by using a pigment having a particle size as small as possible, the pigment is evenly adhered to the surface of the phosphor, so that the pigment particles and the phosphor particles are separated from each other. The contact area becomes large, and it becomes difficult to be rubbed with other particles, so that it becomes difficult to separate from each other. However, the smaller the particle size of the pigment is, the poorer the crystallinity is, and thus the physical and chemical stability of the pigment particle such as heat resistance, chemical resistance, and electron beam resistance is reduced. TV
In the fluorescent screen manufacturing process for cathode ray tubes for computer displays, there is a baking step at about 500 ° C, so the phosphors used for these fluorescent screens do not change their characteristics due to heat especially at temperatures of around 500 ° C. It is important to have heat resistance of. Furthermore, when it is used as a fluorescent film for cathode ray tubes for computer displays that display images and characters, the fluorescent substance with pigment in the fluorescent film is exposed to electron beam irradiation of high voltage and high current density. There is a case where only one is locally exposed to the electron beam for a long time to cause burning, and in that case, the degree of burning between the pigment particles adhering to the surface of the phosphor between the part irradiated with the electron beam and the part not irradiated with the electron beam. As a result of a difference in saturation, brightness, etc. due to the difference between the two, a local difference occurs in the light emission characteristics of the pigmented phosphor, which is visually recognized by the observer, and the difference is often a problem. Therefore, it is important that the pigment particles attached to the surface of the pigmented phosphor have good crystallinity and electron beam resistance.

【０００６】コバルトブルー青色顔料の場合にも、付着
力を高めるために通常用いられている顔料よりも極端に
小さい粒子径を有するコバルトブルー青色顔料粒子を用
いて顔料付蛍光体を製造すると、顔料粒子の結晶性が十
分でないため、電子線や熱による焼けのために顔料粒子
の彩度や明度が変化する結果、これらの顔料粒子を付着
させた顔料付蛍光体を使用して蛍光膜を形成したブラウ
ン管を作動させていると、経時的に蛍光膜の局部的な焼
けの違いによる輝度や発光色等の局部的な経時変化が生
じて、３色の蛍光膜に電子線を照射して発光させて白色
画面とした時に画面上に特定のパターンが視認されるよ
うになったり、また、電子線未照射時（未発光時）にお
いても、局部的な蛍光膜の焼けの程度の違いにより生じ
る蛍光膜の局部的な体色差によるパターンが作動してい
ない画面上に視認されるようになったりする弊害が生じ
た。Also in the case of cobalt blue blue pigments, when a pigmented phosphor is produced using cobalt blue blue pigment particles having a particle size extremely smaller than the pigments usually used for enhancing the adhesion, Since the crystallinity of the particles is not sufficient, the saturation and brightness of the pigment particles change due to burning due to electron beam or heat, and as a result, the fluorescent film is formed using the pigmented phosphor with these pigment particles attached. When the cathode ray tube is operated, a temporal change in brightness, emission color, etc. occurs due to the difference in the local burning of the fluorescent film over time, and the fluorescent film of three colors is irradiated with an electron beam to emit light. When a white screen is displayed, a specific pattern will be visible on the screen, and even when the electron beam is not irradiated (when no light is emitted), it occurs due to the degree of local burning of the fluorescent film. Local of fluorescent film Adverse effects pattern by the body color difference or adapted to be visually recognized on the screen is not operating has occurred.

【０００７】[0007]

【発明が解決しようとする課題】本発明は上述のような
弊害を防止するため、蛍光体に対する付着力が強く、し
かも耐電子線性や耐熱性の良好な、コバルトブルー青色
顔料付着蛍光体及びその製造方法を提供することを目的
とする。SUMMARY OF THE INVENTION In order to prevent the above-mentioned problems, the present invention provides a cobalt blue blue pigment-adhered phosphor having a strong adhesion to the phosphor and good electron beam resistance and heat resistance, and the same. It is intended to provide a manufacturing method.

【０００８】[0008]

【課題を解決するための手段】本発明者らは上記目的を
達成するため、蛍光体の表面に付着させるコバルトブル
ー青色顔料粒子の種類やその粉砕手段等の異なる種々物
性のコバルトブルー青色顔料粒子を用いて、顔料付蛍光
体を製造し、その顔料付蛍光体の顔料剥離、耐電子線
性、耐熱性等について詳細に検討した結果、ある程度以
上の結晶性を有し、しかもその粒子径が一定の粒径以下
であるコバルトブルー青色顔料粒子を用いてこれを蛍光
体表面に付着させた顔料付蛍光体は顔料剥離の程度が少
なく、しかも、耐電子線性並びに耐熱性にも優れること
を見出し、本発明に至った。In order to achieve the above object, the inventors of the present invention have achieved various objects such as cobalt blue blue pigment particles having different physical properties such as types of cobalt blue blue pigment particles to be attached to the surface of a phosphor and crushing means thereof. Was used to produce a pigmented phosphor, and as a result of a detailed examination of the pigment peeling, electron beam resistance, heat resistance, etc. of the pigmented phosphor, it has a certain degree of crystallinity and its particle size is constant. It is found that the pigmented phosphor with the cobalt blue blue pigment particles having a particle size of less than or equal to this adhered to the phosphor surface has a small degree of pigment peeling, and is also excellent in electron beam resistance and heat resistance, The present invention has been completed.

【０００９】本発明の顔料付蛍光体及びその製造方法は
以下の構成を有する。 （１） 蛍光体表面に酸化コバルト（ＣｏＯ）と酸化ア
ルミニウム（Ａｌ２Ｏ３）との複合酸化物からなるコバ
ルトブルー青色顔料粒子を付着させた顔料付蛍光体であ
って、前記コバルトブルー青色顔料粒子の平均粒子径が
０．０５〜０．２０μｍであり、かつ、該コバルトブル
ー青色顔料粒子のＣｕ−Ｋα１特性Ｘ線による粉末回折
Ｘ線スペクトルにおいて、該スペクトルの３１．１°の
回折角（２θ）における回折ピークの半値幅が０．３０
°以下であることを特徴とする顔料付蛍光体。 （２） 前記コバルトブルー青色顔料粒子の付着量が蛍
光体に対して０．３〜１５重量％であることを特徴とす
る前記（１）記載の顔料付蛍光体。The pigmented phosphor of the present invention and the method for producing the same have the following constitutions. (1) A pigmented phosphor in which cobalt blue blue pigment particles made of a composite oxide of cobalt oxide (CoO) and aluminum oxide (Al 2 O 3 ) are attached to the surface of the phosphor, the cobalt blue blue pigment The average particle size of the particles is 0.05 to 0.20 μm, and in the powder diffraction X-ray spectrum by the Cu-Kα1 characteristic X-ray of the cobalt blue blue pigment particles, the diffraction angle of 31.1 ° of the spectrum ( The half width of the diffraction peak in 2θ) is 0.30
A fluorescent substance with a pigment characterized by being at most °. (2) The pigmented phosphor according to (1), wherein the amount of the cobalt blue blue pigment particles attached is 0.3 to 15% by weight based on the phosphor.

【００１０】（３） 顔料粒子を使用して、該顔料粒子
を蛍光体粒子の表面に付着させた顔料付蛍光体を製造す
る方法において、前記顔料粒子が酸化コバルト（Ｃｏ
Ｏ）と酸化アルミニウム（Ａｌ２Ｏ３）との複合酸化物
からなるコバルトブルー青色顔料粒子であって、前記コ
バルトブルー青色顔料粒子の平均粒子径が０．０５〜
０．２０μｍであり、かつ、前記コバルトブルー青色顔
料粒子のＣｕ−Ｋα１特性Ｘ線による粉末回折Ｘ線スペ
クトルにおいて、該スペクトルの３１．１°の回折角
（２θ）における回折ピークの半値幅が０．３０°以下
であることを特徴とする顔料付蛍光体の製造方法。(3) In the method for producing a pigmented phosphor in which the pigment particles are attached to the surface of the phosphor particles, the pigment particles are cobalt oxide (Co).
O) and aluminum oxide (Al 2 O 3 ), which is a cobalt blue blue pigment particle having an average particle diameter of 0.05 to 0.5.
0.20 μm, and in the powder diffraction X-ray spectrum by the Cu-Kα1 characteristic X-ray of the cobalt blue blue pigment particles, the half value width of the diffraction peak at a diffraction angle (2θ) of 31.1 ° of the spectrum was 0. 30 ° or less, a method for producing a pigmented phosphor.

【００１１】[0011]

【発明の実施の形態】本発明の顔料付蛍光体は、蛍光体
の表面に付着させるコバルトブルー青色顔料粒子として
特定の範囲の粒子径を有し、しかも、従来のものよりそ
の粉末Ｘ線スペクトルの半値幅が特定値以下であって、
結晶性の程度が大である、コバルトブルー青色顔料粒子
を使用する以外は従来のコバルトブルー青色顔料付蛍光
体と同様にして製造することが出来る。BEST MODE FOR CARRYING OUT THE INVENTION The pigmented phosphor of the present invention has a particle diameter in a specific range as cobalt blue blue pigment particles to be attached to the surface of the phosphor, and its powder X-ray spectrum is more than that of the conventional one. The half-width of is less than the specified value,
It can be manufactured in the same manner as a conventional phosphor with a cobalt blue blue pigment except that cobalt blue blue pigment particles having a high degree of crystallinity are used.

【００１２】即ち、特定の粒子径と結晶性をもった、所
定量の粉末状のコバルトブルー青色顔料をポリビニルア
ルコール等の分散剤と共に水または温水中に懸濁、分散
させた顔料スラリーを、同じく所定量の蛍光体を分散さ
せた蛍光体スラリー中に混合し、この中に更に、例えば
ゼラチンとアラビアゴムなどからなるバインダーを添加
して撹拌し、顔料−蛍光体混合スラリーのｐＨがおよそ
４の酸性となるまで該スラリー中に希硫酸、酢酸等の酸
を添加してそのまま静置することによってスラリー中の
蛍光体粒子の表面にコバルトブルー青色顔料を付着さ
せ、脱水して本発明の顔料付蛍光体を得る。この時に添
加されるゼラチン、アラビアゴム等のバインダーの総添
加量は、従来の顔料付蛍光体を製造する場合と同様に蛍
光体に対して０．０１〜１．０重量％が好ましい。That is, a pigment slurry prepared by suspending and dispersing a predetermined amount of powdery cobalt blue blue pigment having a specific particle size and crystallinity in water or warm water together with a dispersant such as polyvinyl alcohol is also prepared. A predetermined amount of phosphor is mixed in a phosphor slurry, and a binder made of, for example, gelatin and gum arabic is added to the slurry and stirred, and the pH of the pigment-phosphor mixed slurry is adjusted to about 4 The cobalt blue blue pigment is attached to the surface of the phosphor particles in the slurry by adding an acid such as dilute sulfuric acid or acetic acid to the slurry until it becomes acidic, and dehydrating the pigment with the pigment of the present invention. Obtain a phosphor. The total amount of binders such as gelatin and gum arabic added at this time is preferably 0.01 to 1.0% by weight based on the phosphor, as in the case of producing a conventional pigmented phosphor.

【００１３】本発明の顔料付蛍光体の製造に際して蛍光
体の表面に付着させるコバルトブルー青色顔料は、組成
がＣｏＯ・ｎＡｌ２Ｏ３（但し、ｎは２〜３の範囲の
数）で表される、酸化コバルト（ＣｏＯ）と酸化アルミ
ニウム（Ａｌ２Ｏ３）との複合酸化物からなり、その平
均粒子径がおよそ０．０５〜０．２０μｍであるものを
用いる。平均粒子径がおよそ０．０５μｍより小である
コバルトブルー青色顔料粒子を用いると、耐電子線性や
耐熱性が悪くなる上に、取り扱い性も悪くなるので好ま
しくなく、また、平均粒子径がおよそ０．２０より大で
あるコバルトブルー青色顔料粒子を用いると蛍光体に対
する付着力が低下するので共に実用上好ましくない。The cobalt blue blue pigment to be attached to the surface of the phosphor in the production of the pigmented phosphor of the present invention is represented by CoO.nAl 2 O 3 (where n is a number in the range of 2 to 3). A composite oxide of cobalt oxide (CoO) and aluminum oxide (Al 2 O 3 ) having an average particle diameter of about 0.05 to 0.20 μm is used. The use of cobalt blue blue pigment particles having an average particle size of less than about 0.05 μm is not preferable because the electron beam resistance and heat resistance are poor, and the handleability is poor, and the average particle size is about 0. If cobalt blue blue pigment particles having a size of more than 0.20 are used, the adhesion to the phosphor is lowered, and both are not preferable in practical use.

【００１４】また、本発明の顔料付蛍光体の製造に際し
て蛍光体の表面に付着させるコバルトブルー青色顔料は
従来のものよりも結晶性の高い顔料を使用することが必
要である。ある結晶粒子の結晶性の程度の大小の一つの
評価方法としては、その結晶粒子の粉末回折Ｘ線スペク
トルにおけるピークの半値幅を比較することによって行
うことが出来るが、本発明の顔料付蛍光体の製造のため
に用いられるコバルトブルー青色顔料粒子においてもこ
の方法により評価した時の結晶性と、その顔料の耐電子
線性や耐熱性との間に相関が認められ、本発明者らの検
討によると、コバルトブルー青色顔料粒子の粉末回折Ｘ
線スペクトルにおいて、特に該スペクトルの３１．１°
の回折角（２θ）における回折ピークの半値幅の大小と
その顔料の耐電子線性や耐熱性との間の相関が顕著であ
ることが判明した。即ち、該スペクトルの３１．１°の
回折角（２θ）における回折ピークの半値幅が０．３０
°以下であるコバルトブルー青色顔料を付着させた顔料
付蛍光体の耐電子線性や耐熱性発光特性が向上し、電子
線照射を受けたことによる顔料の焼けによる体色、輝
度、発光色などの変化が少ないことが分かった。用いら
れるコバルトブルー青色顔料粒子の粉末回折Ｘ線スペク
トルにおける、３１．１°の回折角（２θ）での回折ピ
ークの半値幅が０．３０°より大である顔料を用いる
と、結晶性が低いことにより電子線、熱等の外的刺激に
より変化し易くなる。Further, in the production of the pigmented phosphor of the present invention, it is necessary to use a cobalt blue blue pigment having a higher crystallinity than the conventional one, which is attached to the surface of the phosphor. One method for evaluating the degree of crystallinity of a certain crystal grain can be carried out by comparing the half-value widths of the peaks in the powder diffraction X-ray spectrum of that crystal grain. Also in the cobalt blue blue pigment particles used for the production of the crystallinity when evaluated by this method, a correlation was observed between the electron beam resistance and heat resistance of the pigment, And powder diffraction X of cobalt blue blue pigment particles
In the line spectrum, especially 31.1 ° of the spectrum
It was found that the correlation between the magnitude of the full width at half maximum of the diffraction peak at the diffraction angle (2θ) and the electron beam resistance and heat resistance of the pigment is remarkable. That is, the full width at half maximum of the diffraction peak at a diffraction angle (2θ) of 31.1 ° of the spectrum is 0.30.
Electron beam resistance and heat resistant luminescence properties of the pigmented phosphor with a cobalt blue blue pigment below ° are improved, and body color, brightness, emission color etc. due to burning of the pigment due to electron beam irradiation It turned out that there was little change. In the powder X-ray powder diffraction spectrum of the cobalt blue blue pigment particles used, the crystallinity is low when a pigment having a full width at half maximum of the diffraction peak at a diffraction angle (2θ) of 31.1 ° is larger than 0.30 ° is used. This makes it easy to change due to external stimuli such as electron beam and heat.

【００１５】本発明の顔料付蛍光体を製造するために用
いられる、平均粒子径がおよそ０．０５〜０．２０μｍ
であり、その粉末回折Ｘ線スペクトルにおいて、回折角
（２θ）が３１．１°での回折ピークの半値幅が０．３
０°以下である、コバルトブルー青色顔料は沈殿条件、
焼成条件などを調整して結晶性良く合成された、比較的
結晶性の良好な従来のコバルトブルー青色顔料をポリビ
ニルアルコール等の分散剤と共に、例えばアルミナボー
ル、ガラスボール等、セラミックス製やガラス製やプラ
スチックス製のメディアを用いて湿式ミリングし、ミリ
ング処理に供される顔料スラリーの濃度、ミリング処理
時のメディアの種類とその粒子径、ミリング処理時間、
ミルの回転数等、いくつかの分散化処理条件の中から所
望の粒子径や結晶性の顔料が粒子相互の凝集を起こさせ
ることなく得られる条件を逐次選択しながら分散処理す
ることによって得ることが出来る。The average particle size used for producing the pigmented phosphor of the present invention is about 0.05 to 0.20 μm.
In the powder diffraction X-ray spectrum, the full width at half maximum of the diffraction peak at a diffraction angle (2θ) of 31.1 ° is 0.3.
Cobalt blue blue pigment, which is 0 ° or less, has precipitation conditions,
A conventional cobalt blue blue pigment with relatively good crystallinity, which was synthesized with good crystallinity by adjusting firing conditions and the like, together with a dispersant such as polyvinyl alcohol, for example, alumina balls, glass balls, etc., made of ceramics or glass, Wet milling using a plastics medium, the concentration of the pigment slurry to be used in the milling treatment, the type of media during the milling treatment and its particle size, the milling treatment time,
Obtained by performing dispersion treatment by sequentially selecting the conditions under which a desired pigment size or crystalline pigment can be obtained without causing mutual aggregation of the particles from among several dispersion treatment conditions such as the rotation speed of the mill. Can be done.

【００１６】本発明の顔料付蛍光体に付着させるコバル
トブルー青色顔料の付着量が、蛍光体に対しておよそ
０．３重量％より少ないと顔料付着によるコントラスト
効果が微力であり、顔料の付着量がおよそ１５重量％よ
り大であると蛍光体自体の発光を顔料によって吸収され
る度合いが増して、発光輝度を実用上好ましくない程度
にまで低下させるため、蛍光体に付着させるコバルトブ
ルー青色顔料の付着量は、蛍光体に対して０．３〜１５
重量％が適当である。If the amount of the cobalt blue blue pigment attached to the pigmented phosphor of the present invention is less than about 0.3% by weight of the phosphor, the contrast effect due to the pigment attachment will be weak, and the amount of the pigment attached will be small. Is greater than about 15% by weight, the luminescence of the phosphor itself is more likely to be absorbed by the pigment, and the luminescence brightness is reduced to a level not practically desirable. The adhesion amount is 0.3 to 15 with respect to the phosphor.
Weight percent is suitable.

【００１７】本発明の顔料付蛍光体に用いられる蛍光体
としては、銀付活硫化亜鉛蛍光体（ＺｎＳ：Ａｇ）、銀
及びアルミニウム共付活硫化亜鉛蛍光体（ＺｎＳ：Ａ
ｇ，Ａｌ）、銀及びハロゲン共付活硫化亜鉛蛍光体（Ｚ
ｎＳ：Ａｇ，Ｘ）等をはじめとする、電子線励起により
高輝度の青色発光を呈する蛍光体が用いられる。The phosphors used in the pigmented phosphor of the present invention include silver-activated zinc sulfide phosphor (ZnS: Ag), silver and aluminum co-activated zinc sulfide phosphor (ZnS: A).
g, Al), silver and halogen co-activated zinc sulfide phosphor (Z
A fluorescent substance such as nS: Ag, X) which emits blue light with high brightness by electron beam excitation is used.

【００１８】[0018]

【実施例】〔実施例１〕銀付活硫化亜鉛青色発光蛍光体
（中央粒径７μｍ）１００重量部に対し、５０℃の脱イ
オン水１００重量部を加えて撹拌し、蛍光体スラリーを
調製した。これとは別に、Ｃｕ−Ｋα１特性Ｘ線による
粉末回折Ｘ線スペクトルにおいて、該スペクトルの３
１．１°の回折角（２θ）における回折ピークの半値幅
が０．２７°であって、水中に分散させた時のスラリー
粒度の中央値が０．１μｍであるコバルトブルー青色顔
料１重量部を０．０５重量部のポリビニルアルコール
（重合度５５０、ケン化度８８）と共におよそ６重量部
の脱イオン水中に投入して十分に顔料粒子を分散させて
実施例１のコバルトブルー青色顔料分散スラリーを調製
した。Example 1 100 parts by weight of silver-activated zinc sulfide blue light emitting phosphor (median particle size 7 μm) was added with 100 parts by weight of deionized water at 50 ° C. and stirred to prepare a phosphor slurry. did. Separately from this, in the powder diffraction X-ray spectrum by Cu-Kα1 characteristic X-ray,
1 part by weight of cobalt blue blue pigment having a half value width of the diffraction peak at a diffraction angle (2θ) of 1.1 ° of 0.27 ° and a median slurry particle size of 0.1 μm when dispersed in water. Was added to 0.05 parts by weight of polyvinyl alcohol (polymerization degree: 550, saponification degree: 88) in about 6 parts by weight of deionized water to sufficiently disperse the pigment particles, and the cobalt blue blue pigment dispersion slurry of Example 1 was obtained. Was prepared.

【００１９】次いで、先に調製した上記蛍光体スラリー
中に含有顔料量として４重量部に相当する、実施例１の
コバルトブルー青色顔料分散スラリーを添加し、さらに
０．３重量部のゼラチンと０．３重量部のアラビアゴム
を加温溶解した混合溶液を添加してから、酢酸を徐々に
加えてそのスラリーのｐＨを４．０に調整した。次いで
そのスラリー中にゼラチン硬化剤として５０％濃度のグ
ルタルアルデヒドを１ｍｌ加えて１５時間攪拌した後に
濾過し、１２０℃で乾燥してから、４００メッシュステ
インレス網がセットされた篩い機を使用して粉砕し、実
施例１のコバルトブルー青色顔料付蛍光体を製造した。Next, the cobalt blue blue pigment dispersion slurry of Example 1 corresponding to 4 parts by weight as the pigment content was added to the above prepared phosphor slurry, and 0.3 parts by weight of gelatin and 0 parts were added. After adding a mixed solution in which 3 parts by weight of gum arabic was heated and dissolved, acetic acid was gradually added to adjust the pH of the slurry to 4.0. Next, 1 ml of 50% glutaraldehyde as a gelatin hardening agent was added to the slurry, and the mixture was stirred for 15 hours, filtered, dried at 120 ° C., and then sieved using a 400 mesh stainless mesh. The powder was pulverized to produce a phosphor with cobalt blue blue pigment of Example 1.

【００２０】なお、ここで用いたコバルトブルー青色顔
料の粉末回折Ｘ線スペクトルは、日本電子（株）製、Ｊ
ＤＸ−３５３０型を用いて測定した。また、この顔料の
スラリー粒度は、上記実施例１の顔料スラリーと同様に
して顔料を水中に分散させてその１部を分取し、この顔
料を比重を４．２として、島津製作所製レーザー式粒度
測定器ＳＡ−ＣＰ３で測定した。The powder diffraction X-ray spectrum of the cobalt blue blue pigment used here is J.
It measured using DX-3530 type. The particle size of the pigment slurry was the same as in the pigment slurry of Example 1 except that the pigment was dispersed in water and a part thereof was fractionated. The specific gravity of this pigment was 4.2, and the laser type manufactured by Shimadzu Corporation was used. The particle size was measured by SA-CP3.

【００２１】〔比較例１〕コバルトブルー青色顔料とし
て、Ｃｕ−Ｋα１特性Ｘ線による粉末回折Ｘ線スペクト
ルにおいて、該スペクトルの３１．１°の回折角（２
θ）における回折ピークの半値幅が０．２７°である
が、水中に分散させた時のスラリー粒度の中央値が０．
１０μｍではなく０．２８μｍあるコバルトブルー青色
顔料を用いた以外は実施例１のコバルトブルー青色顔料
分散スラリーと同様にして比較例１のコバルトブルー青
色顔料分散スラリーを調製し、実施例１のコバルトブル
ー青色顔料分散スラリーに代えて比較例１のコバルトブ
ルー青色顔料分散スラリーを用いた以外は実施例１のコ
バルトブルー青色顔料付蛍光体と同様にして比較例１の
コバルトブルー青色顔料付蛍光体を製造した。なお、こ
こで用いたコバルトブルー青色顔料の粉末回折Ｘ線スペ
クトル及びスラリー粒度は実施例１と同様にして測定し
た。[Comparative Example 1] As a cobalt blue blue pigment, in the powder diffraction X-ray spectrum by Cu-Kα1 characteristic X-ray, the diffraction angle (2
The half value width of the diffraction peak in θ) is 0.27 °, but the median value of the slurry particle size when dispersed in water is 0.
A cobalt blue blue pigment dispersion slurry of Comparative Example 1 was prepared in the same manner as the cobalt blue blue pigment dispersion slurry of Example 1 except that a cobalt blue blue pigment having a size of 0.28 μm was used instead of 10 μm. A cobalt blue blue pigment-containing phosphor of Comparative Example 1 was produced in the same manner as the cobalt blue blue pigment-containing phosphor of Example 1 except that the cobalt blue blue pigment-dispersing slurry of Comparative Example 1 was used instead of the blue pigment dispersion slurry. did. The powder diffraction X-ray spectrum and the slurry particle size of the cobalt blue blue pigment used here were measured in the same manner as in Example 1.

【００２２】〔比較例２〕コバルトブルー青色顔料とし
て、Ｃｕ−Ｋα１特性Ｘ線による粉末回折Ｘ線スペクト
ルにおいて、該スペクトルの３１．１°の回折角（２
θ）における回折ピークの半値幅が０．２７°ではなく
０．３５°であり、水中に分散させた時のスラリー粒度
の中央値が０．１０μｍではなく０．１４μｍあるコバ
ルトブルー青色顔料を用いた以外は実施例１のコバルト
ブルー青色顔料分散スラリーと同様にして比較例２のコ
バルトブルー青色顔料分散スラリーを調製し、実施例１
のコバルトブルー青色顔料分散スラリーに代えて比較例
２のコバルトブルー青色顔料分散スラリーを用いた以外
は実施例１のコバルトブルー青色顔料付蛍光体と同様に
して比較例２のコバルトブルー青色顔料付蛍光体を製造
した。なお、ここで用いたコバルトブルー青色顔料の粉
末回折Ｘ線スペクトル及びスラリー粒度は実施例１と同
様にして測定した。[Comparative Example 2] As a cobalt blue blue pigment, in the powder diffraction X-ray spectrum by Cu-Kα1 characteristic X-ray, the diffraction angle (2
The cobalt blue blue pigment whose half value width of the diffraction peak in θ) is 0.35 ° instead of 0.27 ° and the median particle size of the slurry when dispersed in water is 0.14 μm instead of 0.10 μm is used. A cobalt blue blue pigment dispersion slurry of Comparative Example 2 was prepared in the same manner as the cobalt blue blue pigment dispersion slurry of Example 1 except that
The cobalt blue blue pigment dispersion slurry of Comparative Example 2 was used in the same manner as the cobalt blue blue pigment dispersion slurry of Example 1 except that the cobalt blue blue pigment dispersion slurry of Comparative Example 2 was used. Manufactured body. The powder diffraction X-ray spectrum and the slurry particle size of the cobalt blue blue pigment used here were measured in the same manner as in Example 1.

【００２３】〔比較例３〕コバルトブルー青色顔料とし
て、Ｃｕ−Ｋα１特性Ｘ線による粉末回折Ｘ線スペクト
ルにおいて、該スペクトルの３１．１°の回折角（２
θ）における回折ピークの半値幅が０．２７°ではなく
０．６０°であり、水中に分散させた時のスラリー粒度
の中央値が同じく０．１０μｍであるコバルトブルー青
色顔料を用いた以外は実施例１のコバルトブルー青色顔
料分散スラリーと同様にして比較例３のコバルトブルー
青色顔料分散スラリーを調製し、実施例１のコバルトブ
ルー青色顔料分散スラリーに代えて比較例３のコバルト
ブルー青色顔料分散スラリーを用いた以外は実施例１の
コバルトブルー青色顔料付蛍光体と同様にして比較例３
のコバルトブルー青色顔料付蛍光体を製造した。[Comparative Example 3] As a cobalt blue blue pigment, in the powder diffraction X-ray spectrum by Cu-Kα1 characteristic X-ray, the diffraction angle (2
The half value width of the diffraction peak in θ) is 0.60 ° instead of 0.27 °, and the cobalt blue blue pigment whose median particle size of the slurry when dispersed in water is also 0.10 μm is used. A cobalt blue blue pigment dispersion slurry of Comparative Example 3 was prepared in the same manner as the cobalt blue blue pigment dispersion slurry of Example 1, and the cobalt blue blue pigment dispersion slurry of Comparative Example 3 was replaced with the cobalt blue blue pigment dispersion slurry of Example 1. Comparative Example 3 as in the phosphor with cobalt blue blue pigment of Example 1 except that a slurry was used.
A phosphor with cobalt blue blue pigment was manufactured.

【００２４】なお、ここで用いたコバルトブルー青色顔
料の粉末回折Ｘ線スペクトル及びスラリー粒度は実施例
１と同様にして測定した。上述の実施例並びに各比較例
の顔料付蛍光体について、用いられたコバルトブルー青
色顔料粒子のボールミルによる分散処理後における各顔
料の分散スラリー中での顔料粉末の粒子径（スラリー粒
径）と顔料分散スラリーを脱水、乾燥して得た各顔料粒
子の結晶性及び得られた各顔料付蛍光体の耐電子線性、
顔料剥離度、粉体の反射率をそれぞれ表１に示す。な
お、本明細書において、顔料粒子並びに顔料付蛍光体の
各特性値はそれぞれ全て下記の方法で測定した時の値を
いう。The powder diffraction X-ray spectrum and slurry particle size of the cobalt blue blue pigment used here were measured in the same manner as in Example 1. Regarding the pigmented phosphors of the above Examples and Comparative Examples, the particle diameter (slurry particle diameter) of the pigment powder in the dispersion slurry of each pigment after the dispersion treatment of the cobalt blue blue pigment particles by the ball mill and the pigment Dehydration of the dispersion slurry, the crystallinity of each pigment particle obtained by drying and the electron beam resistance of each pigmented phosphor obtained,
Table 1 shows the degree of peeling of the pigment and the reflectance of the powder. In the present specification, all the characteristic values of the pigment particles and the pigmented phosphor are the values measured by the following methods.

【００２５】表１において、各特性値は以下のようにし
て測定した。 （１）各顔料粒子の粒子径：容量がおよそ５０ｍｌの円
錐型ビーカー中に分散剤を含んだ脱イオン水３ｍｌと被
測定顔料スラリーを加えて超音波分散機（海上電機社製
Ａｕｔｏ Ｃｈａｓｅｒ３００）によって出力２５Ｗで
１分間分散処理した後、島津製作所製レーザー式粒度測
定器ＳＡ−ＣＰ３を用いて、各顔料粒子の比重を４．２
としてそれぞれの顔料粒子の中央粒度を求めた。In Table 1, each characteristic value was measured as follows. (1) Particle size of each pigment particle: 3 ml of deionized water containing a dispersant and a pigment slurry to be measured were added to a conical beaker having a capacity of about 50 ml, and the mixture was subjected to an ultrasonic disperser (Auto Chaser 300 manufactured by Marine Electric Co., Ltd.). After performing a dispersion treatment at an output of 25 W for 1 minute, the specific gravity of each pigment particle is 4.2 using a Shimadzu laser particle size analyzer SA-CP3.
The median particle size of each pigment particle was determined as

【００２６】（２）結晶性：被測定顔料スラリーを脱
水、乾燥して得た顔料粉末粒子をＸ線回折装置（日本電
子（株）製、ＪＤＸ−３５３０）により粉末回折Ｘ線ス
ペクトルを測定し、そのスペクトルの回折角（２θ）が
３１．１°である時の回折ピークの半値幅を実測し、こ
の半値幅が小さい程、その顔料粒子の結晶性が良好であ
ると判断した。(2) Crystallinity: Pigment powder particles obtained by dehydrating and drying the pigment slurry to be measured were measured for powder diffraction X-ray spectrum with an X-ray diffractometer (JDX-3530, manufactured by JEOL Ltd.). The half-value width of the diffraction peak when the diffraction angle (2θ) of the spectrum was 31.1 ° was measured, and it was determined that the smaller the half-value width, the better the crystallinity of the pigment particles.

【００２７】（３）耐電子線性：２０ｘ２０ｍｍ２のス
テンレス板の試験片を器底に静置したビーカー内に顔料
付蛍光体を投入して懸濁させてからそのまま静置し、顔
料付蛍光体を沈降塗布した試験片をビーカーから取り出
し、乾燥後、試験片の蛍光体塗布面に加速電圧が２７Ｋ
Ｖ、電流密度が１００μＡ／ｃｍ２である電子線を一定
時間照射し、電子線照射前後における蛍光体塗布面（蛍
光膜）の体色、即ち、電子線照射前後における蛍光膜の
体色の変化量（Δｘ、Δｙ）を求め、この蛍光膜の体色
の変化量（Δｘ、Δｙ）から体色の色度点の移動距離
｛（Δｘ２＋Δｙ２）１／２｝値を算出した。(3) Electron ray resistance: A pigmented phosphor is placed in a beaker in which a test piece of a stainless steel plate of 20 × 20 mm 2 is allowed to stand on the bottom of the vessel, and the suspension is allowed to stand and then the pigmented phosphor is allowed to stand. After removing the test piece coated by sedimentation from the beaker and drying, the accelerating voltage was 27K on the phosphor-coated surface of the test piece.
V, an electron beam having a current density of 100 μA / cm 2 is irradiated for a certain period of time, and the body color of the phosphor-coated surface (phosphor film) before and after the electron beam irradiation, that is, the body color of the phosphor film before and after the electron beam irradiation is changed. The amount (Δx, Δy) was obtained, and the moving distance {(Δx 2 + Δy 2 ) 1/2 } value of the chromaticity point of the body color was calculated from the amount of change (Δx, Δy) in the body color of the fluorescent film.

【００２８】なお、ＣＩＥ表色系で表した電子線照射前
後の蛍光膜の体色の色度座標値をそれぞれ（ｘ１、
ｙ１）、（ｘ２、ｙ２）とした時、Δｘは（ｘ１−
ｘ２）値であり、Δｙは（ｙ１−ｙ２）値である。コバ
ルトブルー青色顔料は熱や電子線で劣化すると焼けによ
り彩度が悪くなる方向、即ち、体色のｘ値、ｙ値共に、
中心（０．３３３／０．３３３）に近づく方向に移動す
るが、この体色の色度点の移動距離を表す｛（Δｘ２＋
Δｙ２）１／２｝値が小さい程、電子線の照射を受けた
時の焼けによる彩度の変化が少なく、耐電子線性並びに
耐熱性が良好であると判断した。The chromaticity coordinate values of the body color of the phosphor film before and after the electron beam irradiation represented by the CIE color system are respectively (x 1 ,
When y 1 ) and (x 2 , y 2 ), Δx is (x 1 −
x 2 ) value and Δy is a (y 1 -y 2 ) value. Cobalt blue blue pigment is deteriorated by heat or electron beam, so that the saturation is deteriorated due to burning, that is, both x and y values of body color are
Although it moves toward the center (0.333 / 0.333), it represents the moving distance of the chromaticity point of this body color {(Δx 2 +
It was judged that the smaller the Δy 2 ) 1/2 } value was, the less the change in saturation due to burning upon irradiation with an electron beam was, and the better the electron beam resistance and the heat resistance were.

【００２９】（４）顔料剥離度合：２ｇの顔料付蛍光体
と３０ｍｌの０．１％水ガラス溶液を容積がほぼ３０ｍ
ｌの沈降試験管に入れて１分間、手で震盪し、１時間静
置した後、上澄液を１ｃｍ平方の石英セルに分取し、分
光光度計を用いて各上澄液に６００ｎｍの光を入射させ
てその透過率を測定し、その時の上澄液の光透過率が高
いほど顔料剥離度合い顔料の剥離度合いが低いと評価し
た。なお、各上澄液の透過率は、参照試料として各上澄
液の透過率測定と同一条件で測定した脱イオン水の透過
率を１００とした時の相対百分率で示した。(4) Detachment degree of pigment: 2 g of the pigmented phosphor and 30 ml of 0.1% water glass solution were added to a volume of about 30 m.
It was shaken by hand for 1 minute in a settling test tube of 1 l and allowed to stand for 1 hour, then, the supernatant was collected in a 1 cm square quartz cell, and 600 nm was applied to each supernatant using a spectrophotometer. The transmittance was measured by making light incident, and it was evaluated that the higher the light transmittance of the supernatant liquid at that time was, the lower the pigment peeling degree was. The transmittance of each supernatant was shown as a relative percentage when the transmittance of deionized water measured as the reference sample under the same conditions as the transmittance measurement of each supernatant was 100.

【００３０】（５）粉体反射率：得られたそれぞれの顔
料付蛍光体の拡散反射率を積分球付分光光度計により測
定し、波長６００ｎｍにおける粉体の拡散反射率を示し
た。(5) Powder reflectance: The diffuse reflectance of each of the obtained pigmented phosphors was measured by a spectrophotometer with an integrating sphere, and the diffuse reflectance of the powder at a wavelength of 600 nm was shown.

【００３１】[0031]

【表１】 [Table 1]

【００３２】表１から分かるように粒子径（中央粒径）
が０．２０μｍより小さく、かつ、その粉末回折Ｘ線ス
ペクトルの回折角（２θ）３１．１°での半値幅が０．
３０°より小さいコバルトブルー青色顔料粒子を蛍光体
表面に付着させた顔料付蛍光体（実施例１）は電子線照
射を受けたときの体色の変化（体色移動距離）がほとん
どなく、耐電子線性が良好であり、しかも顔料剥離度が
極めて小さかったのに対して、粒子径が０．２０μｍよ
り大である（比較例１）か、もしくはその粉末回折Ｘ線
スペクトルの回折角（２θ）３１．１°での半値幅が
０．３０°より大であって結晶性の比較的低いコバルト
ブルー青色顔料粒子を蛍光体表面に付着させた顔料付蛍
光体（比較例２、３）は顔料剥離度が高いか、電子線照
射を受けたときの体色の変化（体色移動距離）が比較的
大きく、耐電子線性が悪かったAs can be seen from Table 1, particle size (median particle size)
Is less than 0.20 μm, and the powder diffraction X-ray spectrum has a half value width of 0. 1 at a diffraction angle (2θ) of 31.1 °.
The pigmented phosphor (Example 1) having cobalt blue blue pigment particles smaller than 30 ° adhered to the phosphor surface (Example 1) shows almost no change in body color (body color movement distance) when exposed to electron beams, The electron beam property was good and the degree of peeling of the pigment was extremely small, whereas the particle size was larger than 0.20 μm (Comparative Example 1) or the diffraction angle (2θ) of the powder diffraction X-ray spectrum thereof. The pigmented phosphors (Comparative Examples 2 and 3) in which cobalt blue blue pigment particles having a half-value width at 31.1 ° of more than 0.30 ° and relatively low crystallinity were attached to the phosphor surface (Comparative Examples 2 and 3) were pigments. The degree of peeling was high, or the change in body color when exposed to electron beams (body color moving distance) was relatively large, and electron beam resistance was poor.

【００３３】[0033]

【発明の効果】本発明の顔料付蛍光体は上述のような構
成としたので、顔料剥離が少なく、しかも耐電子線性や
耐熱性が良好で、高加速電圧、高電流の電子線照射を受
けても従来の顔料付蛍光体に比べて電子線や熱による焼
けによる発光色の変化や、発光輝度の低下等が起こり難
い。EFFECTS OF THE INVENTION Since the pigmented phosphor of the present invention has the above-mentioned constitution, it is less likely to cause pigment peeling, has good electron beam resistance and heat resistance, and is irradiated with electron beams of high accelerating voltage and high current. However, as compared with the conventional pigmented phosphor, it is less likely that a change in emission color due to burning due to an electron beam or heat or a decrease in emission brightness occurs.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 稔彦 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 CA06 CC15 XA16 XA30 YA47   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshihiko Sato             1060 Narita, Odawara-shi, Kanagawa Kasei Op             Tonics Co., Ltd. Odawara factory F-term (reference) 4H001 CA06 CC15 XA16 XA30 YA47

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 蛍光体表面に酸化コバルト（ＣｏＯ）と
酸化アルミニウム（Ａｌ２Ｏ３）との複合酸化物からな
るコバルトブルー青色顔料粒子を付着させた顔料付蛍光
体であって、前記コバルトブルー青色顔料粒子の平均粒
子径が０．０５〜０．２０μｍであり、かつ、該コバル
トブルー青色顔料粒子のＣｕ−Ｋα１特性Ｘ線による粉
末回折Ｘ線スペクトルにおいて、該スペクトルの３１．
１°の回折角（２θ）における回折ピークの半値幅が
０．３０°以下であることを特徴とする顔料付蛍光体。1. A pigmented phosphor in which cobalt blue blue pigment particles composed of a complex oxide of cobalt oxide (CoO) and aluminum oxide (Al 2 O 3 ) are attached to the surface of the phosphor, wherein the cobalt blue The average particle diameter of the blue pigment particles is 0.05 to 0.20 μm, and in the powder diffraction X-ray spectrum by the Cu-Kα1 characteristic X-ray of the cobalt blue blue pigment particles, 31.
A pigment-containing phosphor, wherein a half-value width of a diffraction peak at a diffraction angle (2θ) of 1 ° is 0.30 ° or less. 【請求項２】 前記コバルトブルー青色顔料粒子の付着
量が蛍光体に対して０．３〜１５重量％であることを特
徴とする請求項１記載の顔料付蛍光体。2. The pigmented phosphor according to claim 1, wherein the amount of the cobalt blue blue pigment particles attached is 0.3 to 15% by weight based on the phosphor. 【請求項３】 顔料粒子を使用して、該顔料粒子を蛍光
体粒子の表面に付着させた顔料付蛍光体を製造する方法
において、前記顔料粒子が酸化コバルト（ＣｏＯ）と酸
化アルミニウム（Ａｌ２Ｏ３）との複合酸化物からなる
コバルトブルー青色顔料粒子であって、前記コバルトブ
ルー青色顔料粒子の平均粒子径が０．０５〜０．２０μ
ｍであり、かつ、前記コバルトブルー青色顔料粒子のＣ
ｕ−Ｋα１特性Ｘ線による粉末回折Ｘ線スペクトルにお
いて、該スペクトルの３１．１°の回折角（２θ）にお
ける回折ピークの半値幅が０．３０°以下であることを
特徴とする顔料付蛍光体の製造方法。3. A method for producing a pigmented phosphor in which the pigment particles are attached to the surface of the phosphor particles by using the pigment particles, wherein the pigment particles are cobalt oxide (CoO) and aluminum oxide (Al 2 Cobalt blue blue pigment particles composed of a composite oxide with O 3 ), wherein the cobalt blue blue pigment particles have an average particle diameter of 0.05 to 0.20 μm.
m and C of the cobalt blue blue pigment particles
In the powder diffraction X-ray spectrum by u-Kα1 characteristic X-ray, the full width at half maximum of the diffraction peak at a diffraction angle (2θ) of 31.1 ° of the spectrum is 0.30 ° or less, and the pigment-containing phosphor. Manufacturing method.
JP2001403020A 2001-12-25 2001-12-25 Pigment-adhered fluorescent substance and method for producing the same Withdrawn JP2003193045A (en)

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