JP2959817B2 - Phosphor with pigment - Google Patents
Phosphor with pigmentInfo
- Publication number
- JP2959817B2 JP2959817B2 JP20637790A JP20637790A JP2959817B2 JP 2959817 B2 JP2959817 B2 JP 2959817B2 JP 20637790 A JP20637790 A JP 20637790A JP 20637790 A JP20637790 A JP 20637790A JP 2959817 B2 JP2959817 B2 JP 2959817B2
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- JP
- Japan
- Prior art keywords
- phosphor
- pigment
- conductive
- screen
- blue
- 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.)
- Expired - Lifetime
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、カラーテレビジョンに用いられる顔料付き
蛍光体に係り、特に導電性を有する顔料付き蛍光体に関
する。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor with a pigment used for a color television, and more particularly to a phosphor with a pigment having conductivity.
［従来の技術］ 一般に、カラーテレビジョン用蛍光体として、カラー
テレビジョンの画面のコントラストを向上させる目的
で、蛍光体からの好ましい発光色を透過し、他の可視光
を吸収する顔料を蛍光体表面に付着させた顔料付き蛍光
体を使用することが知られている。通常、このような顔
料としては、赤色発光蛍光体には赤色顔料、青色発光蛍
光体には青色顔料というように、付着される蛍光体の発
光色と同様のものが用いられる。[Prior Art] In general, as a phosphor for color television, a pigment that transmits a preferred emission color from the phosphor and absorbs other visible light is used for the purpose of improving the contrast of the screen of the color television. It is known to use pigmented phosphors attached to the surface. Usually, as such a pigment, the same color as the luminescent color of the attached phosphor is used, such as a red pigment for the red light emitting phosphor and a blue pigment for the blue light emitting phosphor.
近年にいたっては、カラーテレビジョンも24インチ以
上の大画面のものが好まれるようになっている。大画面
のカラーテレビジョンでは、その蛍光面を構成する蛍光
体ドット、ストライプの幅が、小画面のそれに比べて大
きいため、高輝度を得る目的で、高電圧（通常約30〜35
kV）、高電流密度（カソード電流／スポット面積）（通
常、約２〜５μA/cm2）の電子線を用いて、顔料付き蛍
光体が励起される。そのような状況で長期間顔料付き蛍
光体を励起すると、蛍光体及び顔料は電子線による熱還
元のため、その化合物組成が次第に金属イオンと陰イオ
ンとに分解され、蛍光体の体色が茶色〜黒色に変化す
る、一般に「焼け」といわれる現象が生じてくる。In recent years, color televisions having a large screen of 24 inches or more have been preferred. In a large-screen color television, the width of the phosphor dots and stripes constituting the phosphor screen is larger than that of a small screen, so that a high voltage (usually about 30 to 35
kV) and a high current density (cathode current / spot area) (usually about 2 to 5 μA / cm 2 ) is used to excite the pigmented phosphor. In such a situation, when the phosphor with pigment is excited for a long time, the phosphor and the pigment are thermally reduced by an electron beam, so that the compound composition is gradually decomposed into metal ions and anions, and the color of the phosphor is brown. A phenomenon called "burn", which changes to black, occurs.
また前述の電子線で蛍光面を励起し続けると、蛍光体
表面に負電荷がたまることによって、蛍光体の輝度が次
第に低下してくる「チャージアップ」と呼ばれる現象が
生じてくる。通常このようなチャージアップを防ぐた
め、カラーテレビジョンの蛍光面は、Al等の金属を蒸着
したメタルバック層を蛍光面の上に形成することによ
り、たまった負電荷を逃がすようにしている。Further, when the phosphor screen is continuously excited by the above-mentioned electron beam, a phenomenon called "charge-up" occurs in which the luminance of the phosphor gradually decreases due to accumulation of negative charges on the phosphor surface. Normally, in order to prevent such charge-up, the phosphor screen of the color television is formed with a metal back layer on which a metal such as Al is deposited on the phosphor screen to release accumulated negative charges.
しかし、近年、特に大画面のテレビジョン例えばハイ
ビジョン（HDTV）において、高コントラストの映像を得
るために、蛍光体に付着される顔料の量が通常の小画面
のものに比べて２倍以上多くなる傾向がある。このよう
な顔料として通常のテレビジョンの場合、例えばべんが
ら0.1重量％、コバルトブルー1.0重量％であるのに対
し、ハイビジョンの場合、べんがら0.2重量％、コバル
トブルー3.0重量％が付着されている。そのような多量
の顔料を有する顔料付き蛍光体においては、前記メタル
バックのみでは、焼け及びチャージアップを防ぐには不
十分であった。However, in recent years, particularly in a large-screen television such as a high-definition television (HDTV), in order to obtain a high-contrast image, the amount of the pigment attached to the phosphor is more than twice as large as that of an ordinary small-screen. Tend. In the case of ordinary television, such pigments are, for example, 0.1% by weight of red wax and 1.0% by weight of cobalt blue, whereas in the case of Hi-Vision, 0.2% by weight of red iron and 3.0% by weight of cobalt blue are adhered. In the pigmented phosphor having such a large amount of pigment, the metal back alone was insufficient to prevent burning and charge-up.
［発明が解決しようとする課題］ 本発明は上記事情を鑑みてなされたものであり、高電
圧、高電流密度域の電子線の照射下においても、チャー
ジアップ及び焼けの少ない顔料付き蛍光体を提供するこ
とを課題とするものである。[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and has been developed to provide a pigmented phosphor with less charge-up and burn even under irradiation of an electron beam in a high voltage and high current density region. The task is to provide.
［課題を解決するための手段］ 本発明者らは、本来絶縁体である顔料粒子を導電性を
有する顔料に変え、これを蛍光体に付着させ、顔料付き
蛍光体に導電性を付与することにより、上記課題を解決
できることを見出だし、本発明をなすに至った。[Means for Solving the Problems] The present inventors changed pigment particles, which are originally insulators, into conductive pigments, adhered them to phosphors, and imparted conductivity to pigmented phosphors. As a result, the inventors have found that the above problems can be solved, and have accomplished the present invention.
本発明の顔料付き蛍光体は、導電性を有する顔料粒子
が表面に付着した蛍光体を包含するものである。The pigmented phosphor of the present invention includes a phosphor having pigment particles having conductivity attached to the surface.
導電性顔料粒子は、表面が導電性物質で被覆された顔
料粒子であるか、または導電性物質を成分として含有す
る顔料粒子であることが好ましい。The conductive pigment particles are preferably pigment particles whose surface is coated with a conductive substance, or pigment particles containing a conductive substance as a component.
本発明において、顔料に導電性を付与するために使用
される導電性物質は、主としてIn2O3、ITO（酸化インジ
ウムスズ）及びAZO（アルミ付活酸化亜鉛）からなる第
１群から選ばれた少なくとも１種の酸化物であるか、ま
たは前記第１群の酸化物を主成分としてSnO、SnO2、Sb2
O3、Sb付活SnO2（SSO）、TiO2、WO3、ZnO、MoO、V2O5、
Li2O、K2O、及びNa2Oからなる第２群から選ばれた少な
くとも１種の酸化物を含んでなる複合化合物であっても
よいが、導電性が優れているという点では、第１群の酸
化物を用いることが好ましい。In the present invention, the conductive substance used for imparting conductivity to the pigment is selected from the first group consisting mainly of In 2 O 3 , ITO (indium tin oxide) and AZO (aluminum activated zinc oxide). Or at least one kind of oxide, or SnO, SnO 2 , Sb 2
O 3 , Sb activated SnO 2 (SSO), TiO 2 , WO 3 , ZnO, MoO, V 2 O 5 ,
It may be a composite compound containing at least one oxide selected from the second group consisting of Li 2 O, K 2 O, and Na 2 O, but in terms of excellent conductivity, It is preferable to use the first group of oxides.
顔料は、通常顔料付き蛍光体に用いられるものを使用
できる。例えば、赤色顔料としてべんがら（Fe2O3）、
鉛丹（Pb3O4）等、黄色顔料として黄色酸化鉄（FeOO
H）、青色顔料として群青（２（Al2Na2Si3O10）Na
2S4）、コバルトブルー（Co・nAl2O3）等、緑色顔料と
してコバルトグリーン（CoO・nZnO2）、チタングリーン
（TiO2・NiO・ZnCoO）、酸化クロム（Cr2O3）等を好ま
しく用いることができる。また、顔料は、通常0.1〜0.5
μｍの粒径を有するものが好ましい。As the pigment, those usually used for a phosphor with a pigment can be used. For example, red pigment (Fe 2 O 3 ),
Yellow iron oxide (FeOO) as a yellow pigment such as lead tin (Pb 3 O 4 )
H), ultramarine (2 (Al 2 Na 2 Si 3 O 10 ) Na as a blue pigment
2 S 4), such as cobalt blue (Co · nAl 2 O 3) , cobalt green (CoO · nZnO 2 as a green pigment), titanium green (TiO 2 · NiO · ZnCoO) , chromium oxide (Cr 2 O 3), etc. It can be preferably used. The pigment is usually 0.1 to 0.5
Those having a particle size of μm are preferred.
表面が導電性物質で被覆または付着された顔料組成物
を得るためには、例えば以下の方法を用いることができ
る。第１はスパッタ、蒸着により顔料に前記導電性物質
を直接被覆する方法、第２は加熱酸化によって前記導電
性物質となり得る化合物（水酸化物、有機化合物、硫化
物等）を顔料に被覆し、その後加熱酸化することによ
り、当該化合物を導電性物質に転化する方法が挙げられ
る。In order to obtain a pigment composition whose surface is coated or adhered with a conductive substance, for example, the following method can be used. The first is a method in which the conductive material is directly coated on the pigment by sputtering or vapor deposition. The second is a method in which the pigment is coated with a compound (hydroxide, organic compound, sulfide, or the like) that can become the conductive material by thermal oxidation, After that, a method of converting the compound into a conductive substance by heat oxidation is used.
また、導電性物質を成分として含有する顔料（導電性
顔料）を得るためには、例えば以下の方法を用いること
ができる。これは、まず加熱酸化によって顔料となる顔
料原料の溶液と、同じく加熱酸化によって導電性物質と
なる化合物の溶液とを混合し、次にそれらを水酸化物、
シュウ酸塩または炭酸塩等として共沈させた後、その共
沈物を焼成し、酸化物とする方法または顔料と導電性物
質とを混合し、適当な融剤を添加して焼成する方法であ
る。In order to obtain a pigment containing a conductive substance as a component (conductive pigment), for example, the following method can be used. This is done by first mixing a solution of a pigment raw material that becomes a pigment by thermal oxidation and a solution of a compound that becomes a conductive substance by thermal oxidation, and then mixing them with a hydroxide,
After coprecipitation as oxalate or carbonate, the coprecipitate is calcined, or a method of forming an oxide or a method of mixing a pigment and a conductive substance, adding a suitable flux, and calcining. is there.
このようにして得た導電性顔料において、導電性物質
の顔料に対する割合は、0.1〜40重量％の範囲であるこ
とが好ましい。さらに好ましくは５〜30重量％である。
なぜなら0.1重量％以下であると顔料付き蛍光体に十分
な導電性が付与できず、40重量％以上であると導電性物
質の存在により顔料色が薄くなり、コントラストが低下
する傾向があるためである。In the conductive pigment thus obtained, the ratio of the conductive substance to the pigment is preferably in the range of 0.1 to 40% by weight. More preferably, it is 5 to 30% by weight.
If the content is less than 0.1% by weight, sufficient conductivity cannot be imparted to the phosphor with the pigment, and if the content is more than 40% by weight, the pigment color becomes thinner due to the presence of the conductive substance, and the contrast tends to decrease. is there.
このようにして得られた導電性顔料を蛍光体に付着さ
せることによって、本発明の顔料付き蛍光体を得ること
ができる。顔料付き蛍光体を得るためには、有機バイン
ダーまたは無機バインダーを用いて顔料を蛍光体に付着
させる方法を使用することができる。蛍光体に付着させ
る導電性顔料の量は、蛍光体の種類、設計事項によって
異なるが、通常蛍光体に対し、0.05〜20重量％以下、好
ましくは0.1〜10重量％以下の範囲で付着させることが
できる。有機バインダーとしては、通常顔料付き蛍光体
に用いられるものを使用することができる。例えばアク
リル系樹脂、ゼラチンまたはその組み合わせ、ポリビニ
ルピロリドン、ポリビニルアセタール等が好ましく用い
られ、またZnO、Al2O3、SiO2等の無機化合物も有機バイ
ンダーと共に使用するか、もしくは単独でバインダーと
して用いられる。By attaching the conductive pigment thus obtained to the phosphor, the phosphor with a pigment of the present invention can be obtained. In order to obtain a phosphor with a pigment, a method of attaching a pigment to the phosphor using an organic binder or an inorganic binder can be used. The amount of the conductive pigment to be attached to the phosphor varies depending on the type of phosphor and design items, but is usually 0.05 to 20% by weight or less, preferably 0.1 to 10% by weight or less based on the phosphor. Can be. As the organic binder, those usually used for a phosphor with a pigment can be used. For example, an acrylic resin, gelatin or a combination thereof, polyvinyl pyrrolidone, polyvinyl acetal, and the like are preferably used, and inorganic compounds such as ZnO, Al 2 O 3 , and SiO 2 are also used together with an organic binder, or used alone as a binder. .
本発明に用いられる蛍光体としては、例えばZnS:Ag,A
l蛍光体、ZnS:Ag,Cl蛍光体、ZnS:Cu・Au・Al蛍光体、Zn
S:Cu・Al蛍光体、Y2O2S:Eu蛍光体、Y2O3:Eu蛍光体、Zn3
（PO4）2:Mn蛍光体、Zn2SiO4:Mn蛍光体、ZnSiO4:Mn,A
s、Y2O2S:Tb蛍光体、Y2SiO5:Tb、Y3（Al,Ga）5O12:Tb蛍
光体、InBO3:Eu蛍光体等の一般に陰極線管に用いられる
蛍光体を使用することができる。As the phosphor used in the present invention, for example, ZnS: Ag, A
l Phosphor, ZnS: Ag, Cl phosphor, ZnS: Cu, Au, Al phosphor, Zn
S: Cu ・ Al phosphor, Y 2 O 2 S: Eu phosphor, Y 2 O 3 : Eu phosphor, Zn 3
(PO 4 ) 2 : Mn phosphor, Zn 2 SiO 4 : Mn phosphor, ZnSiO 4 : Mn, A
s, Y 2 O 2 S: Tb phosphor, Y 2 SiO 5 : Tb, Y 3 (Al, Ga) 5 O 12 : Tb phosphor, InBO 3 : Eu phosphor, etc., which are generally used for cathode ray tubes. Can be used.
［作用］ 第１図に本発明の顔料付き蛍光体の一例の模式断面図
を示す。第１図から明らかなように、蛍光体３の表面に
付着している顔料２は均一な導電性物質膜１で覆われて
いる。この均一な導電性物質膜１が電子線が顔料２に到
達する仲介の役目をしている。従って、高電圧、高電流
により顔料２が電子線によって侵され、焼け等の変質を
発生することが少ないため、長期間にわたりコントラス
トを維持することができる。また、第１図は導電性物質
を被覆した顔料の一例を示すものであるが、導電性物質
を含有する顔料についても同様である。また、Ｂ、Ti、
Ce、Ge、Si及びＰからなる群から選択された少なくとも
１種の元素を、導電性物質に対し数ppm〜数％含有させ
ることにより、第１群の酸化物中の金属イオンと陰イオ
ンとの結合力に向上することができる。このことは、顔
料及び蛍光体の焼けの防止に効果的である。[Operation] FIG. 1 is a schematic cross-sectional view of an example of the pigmented phosphor of the present invention. As is clear from FIG. 1, the pigment 2 adhering to the surface of the phosphor 3 is covered with a uniform conductive material film 1. The uniform conductive material film 1 serves as an intermediary for the electron beam to reach the pigment 2. Therefore, since the pigment 2 is hardly affected by the electron beam due to the high voltage and the high current and the deterioration such as burning occurs, the contrast can be maintained for a long time. FIG. 1 shows an example of a pigment coated with a conductive substance. The same applies to a pigment containing a conductive substance. Also, B, Ti,
By containing at least one element selected from the group consisting of Ce, Ge, Si, and P with respect to the conductive material by several ppm to several percent, the metal ions and the anions in the first group of oxides are reduced. Can be improved. This is effective for preventing burning of the pigment and the phosphor.
［実施例］ 以下、実施例を示し、本発明を具体的に説明する。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
実施例１ 青色顔料としてコバルトブルー（CoO・nAl2O3）15gを
エタノール100ml中に分散させた。この分散液にITO換算
含量５重量％のアトロンＮ−In（日本曹達（株）製 商
品名）のエタノール溶液30gを添加し、十分攪拌した
後、液温を50℃に上げてエタノールを揮散させた。その
後青色顔料を取り出し、450℃で１時間の焼成を行なう
ことにより、青色顔料に対し10重量％のITOを被覆した
導電性青色顔料を得た。Cobalt blue (CoO · nAl 2 O 3) 15g was dispersed in ethanol 100ml as in Example 1 blue pigment. To this dispersion was added 30 g of an ethanol solution of Atron N-In (trade name, manufactured by Nippon Soda Co., Ltd.) having a content of 5% by weight in terms of ITO, and the mixture was sufficiently stirred. Was. Thereafter, the blue pigment was taken out and baked at 450 ° C. for 1 hour to obtain a conductive blue pigment coated with 10% by weight of ITO based on the blue pigment.
次に、青色発光蛍光体（ZnS:Ag,Al）1kgを１中に懸
濁させ、この懸濁液に前述の導電性青色顔料を添加し、
十分攪拌した。攪拌を続けながらゼラチン1.5g、ポリビ
ニルピロリドン2.0gを添加し、十分懸濁させた後、酢酸
で懸濁液のpHを5.0に調整した。蛍光体に導電性青色顔
料が十分付着し、沈降するのを待って、上澄を捨て、水
で５回洗浄した後、顔料が付着した蛍光体を分離、乾燥
し、300メッシュ篩を通すことにより青色顔料付き青色
発光蛍光体を得た。Next, 1 kg of a blue light-emitting phosphor (ZnS: Ag, Al) is suspended in 1, and the above-described conductive blue pigment is added to the suspension.
Stir well. 1.5 g of gelatin and 2.0 g of polyvinylpyrrolidone were added while stirring was continued, and after sufficient suspension, the pH of the suspension was adjusted to 5.0 with acetic acid. After the conductive blue pigment has sufficiently adhered to the phosphor and settled, the supernatant was discarded, washed with water five times, the phosphor with the pigment attached was separated, dried, and passed through a 300 mesh sieve. Thus, a blue light-emitting phosphor with a blue pigment was obtained.
このようにして得られた顔料付き蛍光体をガラス板上
に塗布して蛍光面を２つ作成した。第１の蛍光面につい
て、顔料付き蛍光体の焼けを検査するため、電子線を27
kV、10μＡに設定した条件で、一定時間強制的に励起し
た。同時にコバルトブルーの顔料を蛍光体に付着した従
来の顔料付き蛍光体を同条件で励起し、励起直後の従来
の蛍光体の輝度を100％として、本発明の蛍光体と従来
の蛍光体の輝度の経時変化を測定した。その結果を横軸
に励起時間、縦軸に相対輝度をとったグラフに表したも
のを第２図に示す。The phosphor with pigment thus obtained was applied on a glass plate to form two phosphor screens. An electron beam is applied to the first phosphor screen in order to inspect the burned pigmented phosphor.
Excitation was forcibly performed for a certain period of time under the conditions of kV and 10 μA. At the same time, the conventional phosphor with a pigment in which a cobalt blue pigment is adhered to the phosphor is excited under the same conditions, and the brightness of the phosphor of the present invention and the brightness of the conventional phosphor are set to 100% immediately after the excitation. Was measured over time. FIG. 2 shows the results in a graph in which the horizontal axis represents the excitation time and the vertical axis represents the relative luminance.
第２図から明らかなように、本発明の顔料付き蛍光体
は、電子線の顔料及び蛍光体への到達をITO被膜で阻害
されるためか、実線５に示すように初輝度は若干低い
が、従来の顔料付き蛍光体の輝度は、実線６に示すよう
に４時間の励起で約15％低下するのに対して、本発明の
顔料付き蛍光体は輝度の低下が見られなかった。また４
時間励起終了後、電子線の当てられた蛍光面を目視で観
察しても、従来の蛍光面はやや茶色に変色していたが、
本発明の蛍光体を用いた蛍光面は電子線の当たっていな
い蛍光面の色と遜色なかった。As is clear from FIG. 2, the initial luminance of the phosphor with a pigment of the present invention is slightly lower as shown by the solid line 5 probably because the ITO film prevents the electron beam from reaching the pigment and the phosphor. As shown by the solid line 6, the luminance of the conventional pigmented phosphor decreased by about 15% when excited for 4 hours, whereas the pigmented phosphor of the present invention showed no decrease in luminance. Also 4
After the end of time excitation, even if the fluorescent screen to which the electron beam was applied was visually observed, the conventional fluorescent screen was discolored slightly brown,
The phosphor screen using the phosphor of the present invention was inferior to the color of the phosphor screen not irradiated with the electron beam.
また、第２の蛍光面について、導電性を測定するた
め、電流密度を２μA/cm2に設定し、励起直後の従来の
蛍光体の輝度を100％として、加速電圧を０〜15kVに変
化させたときの相対輝度を測定した。その結果を横軸に
加速電圧、縦軸に相対輝度をとったグラフに表したもの
を第３図に示す。第３図から明らかなように、従来の蛍
光体は、実線ｂに示すように約3kV付近で発光しなくな
るが、本発明の蛍光体は、破線ａに示すように約1kV付
近でも発光可能である。In addition, in order to measure the conductivity of the second phosphor screen, the current density was set to 2 μA / cm 2 , and the acceleration voltage was changed to 0 to 15 kV with the luminance of the conventional phosphor immediately after excitation set to 100%. And the relative luminance was measured. FIG. 3 shows the results in a graph with the acceleration voltage on the horizontal axis and the relative luminance on the vertical axis. As apparent from FIG. 3, the conventional phosphor does not emit light at about 3 kV as shown by the solid line b, but the phosphor of the present invention can emit light at about 1 kV as shown by the broken line a. is there.
実施例２ まず、Fe2O3換算で10重量％の硫酸第２鉄アンモニウ
ム水溶液200gにIn2O3換算で10重量％の塩化インジウム
（InCl3）水溶液20gを混合した。混合液にアンモニア水
を滴下し、pHを８以上として、水酸化第２鉄（FeOOH）
及び水酸化インジウム（In（OH）３）の共沈物を得た。
共沈物が沈殿するのを待って水で３回洗浄した後、共沈
物を分離し、100℃で３時間乾燥後、500℃で２時間焼成
し、導電性赤色顔料を得た。Example 2 First, 20 g of an indium chloride (InCl 3 ) solution of 10% by weight in terms of In 2 O 3 was mixed with 200 g of an aqueous solution of ferric ammonium sulfate of 10% by weight in terms of Fe 2 O 3 . Ammonia water is added dropwise to the mixture to adjust the pH to 8 or more, and ferric hydroxide (FeOOH)
And a coprecipitate of indium hydroxide (In (OH) 3 ).
After waiting for the coprecipitate to precipitate and washing three times with water, the coprecipitate was separated, dried at 100 ° C. for 3 hours, and calcined at 500 ° C. for 2 hours to obtain a conductive red pigment.
次に、赤色発光蛍光体（Y2O2S:Eu）1kgを実施例と同
様に水１中に懸濁させ、この懸濁液に上記導電性赤色
顔料1gを分取して添加した。その後実施例１と同様にし
てゼラチンとポリビニルピロリドンにより導電性赤色顔
料を赤色発光蛍光体に付着させ、赤色顔料付き赤色発光
蛍光体を得た。Then, the red emitting phosphor (Y 2 O 2 S: Eu ) 1kg similarly suspended in water 1 and Example were added to collected the conductive red pigment 1g min to the suspension. Thereafter, a conductive red pigment was adhered to the red light-emitting phosphor with gelatin and polyvinylpyrrolidone in the same manner as in Example 1 to obtain a red light-emitting phosphor with a red pigment.
本発明の蛍光体と従来の蛍光体とについて、実施例１
と同様にして相対輝度の経時変化を測定した。その結果
を第２図に示す。Example 1 of the phosphor of the present invention and a conventional phosphor
The change with time of the relative luminance was measured in the same manner as described above. The result is shown in FIG.
第２図から明らかなように、従来の蛍光体は、破線８
に示すように、４時間で輝度が10％も低下したが本発明
の蛍光体は、破線７に示すように４時間たっても輝度の
低下は見られず、また蛍光面の変色も見られなかった。As is apparent from FIG. 2, the conventional phosphor has a broken line 8
As shown in Fig. 7, the luminance decreased by 10% in 4 hours, but the phosphor of the present invention did not show a decrease in luminance even after 4 hours as shown by the broken line 7, and no discoloration of the phosphor screen was observed. Was.
実施例３ まず、In2O3換算で１重量％の塩化インジウム（InC
l3）水溶液200gとSnO換算で１重量％の塩化第１スズ（S
nCl2・H2O）水溶液40gとの混合水溶液に、赤色顔料とし
てべんがら（Fe2O3）10gを添加し、分散させた。この分
散液にアンモニア水を滴下して水酸化インジウムと水酸
化スズとを沈殿させながらべんがらの表面に付着させ
た。共沈物の付着した顔料が沈殿するのを待って上澄を
捨て、水で３回洗浄した。その後沈殿物を取り出し450
℃の空気雰囲気で１時間の焼成を行ない、顔料に対し24
重量％のITOを被覆した導電性赤色顔料が得られた。Example 3 First, 1 wt% of indium chloride in In 2 O 3 in terms of (InC
l 3 ) 200 g of aqueous solution and 1% by weight of stannous chloride (S
To a mixed aqueous solution with 40 g of an aqueous solution of nCl 2 · H 2 O) was added 10 g of red iron (Fe 2 O 3 ) as a red pigment and dispersed. Ammonia water was added dropwise to the dispersion to precipitate indium hydroxide and tin hydroxide, and allowed to adhere to the surface of the rice bran. The supernatant was discarded after the pigment with the coprecipitate settled out, and washed three times with water. Then remove the sediment 450
Baking for 1 hour in an air atmosphere at
A conductive red pigment coated with wt% ITO was obtained.
次に、実施例２と同様に赤色発光蛍光体（Y2O2:Eu）1
kgを水１中に懸濁させた後、その懸濁液に上記導電性
赤色顔料10gを添加し、十分攪拌した。攪拌を続けなが
らゼラチン3.0gとAl（OH）331.0gとを添加した。導電性
顔料が蛍光体に沈着し、沈降するのを待って上澄みを捨
て、実施例１と同様にして赤色顔料付き赤色発光蛍光体
を得た。Next, as in Example 2, the red-emitting phosphor (Y 2 O 2 : Eu) 1
After suspending kg in water 1, 10 g of the above-mentioned conductive red pigment was added to the suspension and stirred sufficiently. While the stirring was continued, 3.0 g of gelatin and 31.0 g of Al (OH) 3 were added. The conductive pigment was deposited on the phosphor, and after the sedimentation, the supernatant was discarded, and a red light-emitting phosphor with a red pigment was obtained in the same manner as in Example 1.
この蛍光体を用い、実施例１と同様にして蛍光面を作
成し、励起したところ、４時間たっても輝度の低下は見
られず、また、蛍光面の変色も見られなかった。Using this phosphor, a phosphor screen was prepared and excited in the same manner as in Example 1. As a result, no decrease in luminance was observed even after 4 hours, and no discoloration of the phosphor screen was observed.
赤色顔料としてべんがら（Fe2O3）15gに対し、ZnOとA
lの混合物をスパッタリングすることにより、表面に１
重量％のAZO被膜を形成し、導電性赤色顔料を得た。そ
の後、実施例３と同様にして赤色発光蛍光体（Y2O2S:E
u）1kgに１重量％の導電性赤色顔料を付着させ、赤色顔
料付き赤色発光蛍光体を得た。ZnO and A for 15 g of red pigment (Bengara (Fe 2 O 3 ))
l on the surface by sputtering
A weight% of an AZO film was formed to obtain a conductive red pigment. Then, in the same manner as in Example 3, the red light-emitting phosphor (Y 2 O 2 S: E
u) 1% by weight of a conductive red pigment was adhered to 1 kg to obtain a red luminescent phosphor with a red pigment.
この蛍光体を用い、実施例１と同様にして蛍光面を作
成し、励起したところ４時間たっても輝度の低下は見ら
れず、また蛍光面の変色も見られなかった。Using this phosphor, a phosphor screen was prepared in the same manner as in Example 1, and when excited, no decrease in luminance was observed even after 4 hours, and no discoloration of the phosphor screen was observed.
実施例５ In2O3換算で１重量％の塩化インジウム水溶液100gとS
nO換算で１重量％の塩化第１スズ（SnCl2・2H2O）水溶
液20gとの混合水溶液に、0.1％塩化ゲルマニウム（GeCl
2）水溶液1mlを添加し、さらに青色顔料としてコバルト
ブルー10gを添加し、分散させた。この分散液にアンモ
ニア水を滴下して、実施例３と同様にして共沈物を青色
顔料の表面に付着させた。その後実施例３と同様にして
導電性青色顔料が得られた。Example 5 100 g of a 1% by weight aqueous solution of indium chloride in terms of In 2 O 3 and S
0.1% germanium chloride (GeCl 2 ) was added to an aqueous solution mixed with 20 g of an aqueous solution of stannous chloride (SnCl 2 .2H 2 O) of 1% by weight in terms of nO.
2 ) 1 ml of an aqueous solution was added, and 10 g of cobalt blue as a blue pigment was further added and dispersed. Ammonia water was added dropwise to this dispersion, and the coprecipitate was attached to the surface of the blue pigment in the same manner as in Example 3. Thereafter, a conductive blue pigment was obtained in the same manner as in Example 3.
次に青色発光蛍光体（ZnS:Ag,Al）1kgを水１中に懸
濁させた後、この懸濁液にこの導電性青色顔料7gを添加
し、十分攪拌した。その後実施例３と同様にして青色顔
料付き青色発光蛍光体を得た。Next, after suspending 1 kg of a blue light-emitting phosphor (ZnS: Ag, Al) in water 1, 7 g of this conductive blue pigment was added to the suspension and stirred sufficiently. Thereafter, a blue light-emitting phosphor with a blue pigment was obtained in the same manner as in Example 3.
この蛍光体を用い、実施例１と同様にして蛍光面を作
成し、励起したところ、４時間たっても輝度の低下は見
られず、また蛍光面の変色も見られなかった。Using this phosphor, a phosphor screen was prepared and excited in the same manner as in Example 1. As a result, no decrease in luminance was observed even after 4 hours, and no discoloration of the phosphor screen was observed.
実施例６〜11 In2O3粉末1gに、次の表に示す化合物の0.1％水溶液1m
lとをそれぞれ混合し、さらに青色顔料としてコバルト
ブルー10.0gを混合し、融剤としてNH4Cl0.1gを添加し、
還元雰囲気で、800℃で１時間の焼成を行い、導電性青
色顔料を得た。Example 6~11 In 2 O 3 powder 1 g, 0.1% aqueous solution 1m of compounds shown in the following table
l, respectively, further mixed 10.0 g of cobalt blue as a blue pigment, added 0.1 g of NH 4 Cl as a flux,
Baking was performed at 800 ° C. for 1 hour in a reducing atmosphere to obtain a conductive blue pigment.
表 実 施 例 化合物 6 H3BO3 7 TiCl3 8 CeCl3 9 GeCl3 10 Na2SiO4 11 H3PO4 次にこの青色発光蛍光体（ZnS:Ag,Al）1kgを水１中
に懸濁させた後、懸濁液に上記導電性青色顔料5gを添加
し、十分攪拌した。その後、実施例１と同様にして青色
顔料付き青色発光蛍光体を得た。Table Example Example Compound 6 H 3 BO 3 7 TiCl 3 8 CeCl 3 9 GeCl 3 10 Na 2 SiO 4 11 H 3 PO 4 Next, 1 kg of this blue light-emitting phosphor (ZnS: Ag, Al) is suspended in water 1. After the suspension was turbid, 5 g of the above-described conductive blue pigment was added to the suspension, and the mixture was sufficiently stirred. Thereafter, a blue light-emitting phosphor with a blue pigment was obtained in the same manner as in Example 1.
これらの蛍光体を用い各々実施例１と同様にして蛍光
面を作成し、励起したところ、４時間たっても輝度の低
下は見られず、また蛍光面の変色も見られなかった。Each of these phosphors was used to form a phosphor screen in the same manner as in Example 1, and when excited, no decrease in luminance was observed even after 4 hours, and no discoloration of the phosphor screen was observed.
［発明の効果］ 以上述べたように、本発明の顔料付き蛍光体は、導電
性を有する顔料粒子を表面に付着させていることによ
り、チャージアップによる負電荷が、顔料中の導電性物
質を通してメタルバック層に流れていくために、従来よ
り負電荷のたまりにくい蛍光体である。したがって、本
発明の顔料付き蛍光体を用いることにより、コントラス
トが長期間にわたり維持できる蛍光面が得られる。[Effects of the Invention] As described above, in the phosphor with a pigment of the present invention, negative charges due to charge-up are caused to pass through the conductive substance in the pigment by attaching conductive pigment particles to the surface. It is a phosphor that is less likely to collect negative charges than before because it flows into the metal back layer. Therefore, by using the phosphor with a pigment of the present invention, a phosphor screen capable of maintaining the contrast for a long period of time can be obtained.
また、本発明の顔料付き蛍光体は大画面のカラーテレ
ビジョン、例えば実用化されつつあるクリアビジョン、
将来実用化されるであろうハイビジョン等のカラーテレ
ビジョンだけでなく、高電流密度で使用される高精細度
陰極線管用蛍光体としても有効に使用可能である。Further, the pigmented phosphor of the present invention is a large-screen color television, for example, Clear Vision, which is being put into practical use,
It can be effectively used not only as a color television such as a high-definition television which will be put to practical use in the future, but also as a phosphor for a high definition cathode ray tube used at a high current density.
第１図は、本発明の蛍光体の一実施例を示す断面図、第
２図は、本発明の蛍光体を用いた蛍光面と従来の蛍光体
を用いた蛍光面との電子線励起による輝度の経時変化を
示すグラフ図、第３図は、本発明の蛍光体を用いた蛍光
面と従来の蛍光体を用いた蛍光面との電子線励起による
輝度と電子線の加速電圧との関係を示すグラフ図であ
る。 １……導電性物質、２……顔料、３……蛍光体。FIG. 1 is a cross-sectional view showing one embodiment of the phosphor of the present invention, and FIG. 2 is a diagram showing a phosphor screen using the phosphor of the present invention and a phosphor screen using a conventional phosphor by electron beam excitation. FIG. 3 is a graph showing a change with time in luminance; FIG. 1 .... conductive material, 2 .... pigment, 3 .... phosphor.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C09K 11/00 - 11/89 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 6 , DB name) C09K 11/00-11/89
Claims (2)
蛍光体を含有する顔料付き蛍光体であって、前記導電性
を有する顔料粒子は、 In2O3、ITO（酸化インジウムスズ）及びAZO（アルミ付
活酸化亜鉛）からなる第１群から選択される少なくとも
１種の酸化物、または SnO、SnO2、Sb2O3、Sb付活SnO2（SSO）、TiO2、WO3、Zn
O、MoO、V2O5、Li2O、K2O、及びNa2Oからなる第２群か
ら選択される少なくとも１種の酸化物と該第１群から選
択される少なくとも１種の酸化物との複合化合物からな
る群から選択される少なくとも１種からなることを特徴
とする顔料付き蛍光体。1. A pigmented phosphor containing a phosphor having conductive pigment particles adhered to the surface thereof, wherein the pigment particles having conductivity include In 2 O 3 , ITO (indium tin oxide) and At least one oxide selected from the first group consisting of AZO (aluminum activated zinc oxide), or SnO, SnO 2 , Sb 2 O 3 , Sb activated SnO 2 (SSO), TiO 2 , WO 3 , Zn
At least one oxide selected from the second group consisting of O, MoO, V 2 O 5 , Li 2 O, K 2 O, and Na 2 O and at least one oxidation selected from the first group A phosphor with a pigment comprising at least one selected from the group consisting of a complex compound with a pigment.
蛍光体を含有する顔料付き蛍光体であって、前記導電性
を有する顔料粒子は、ITOを被覆したコバルトブルー顔
料、ITOを被覆したFe2O3顔料、及び水酸化第２鉄及び水
酸化インジウムの共沈物を焼成することにより得られる
導電性赤色顔料からなる群から選択される少なくとも１
種からなることを特徴とする顔料付き蛍光体。2. A pigmented phosphor containing a phosphor having conductive pigment particles adhered to the surface thereof, wherein said pigment particles having conductivity are coated with an ITO-coated cobalt blue pigment or ITO. At least one selected from the group consisting of Fe 2 O 3 pigments and a conductive red pigment obtained by calcining a coprecipitate of ferric hydroxide and indium hydroxide.
A phosphor with a pigment, comprising a seed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20637790A JP2959817B2 (en) | 1990-08-03 | 1990-08-03 | Phosphor with pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20637790A JP2959817B2 (en) | 1990-08-03 | 1990-08-03 | Phosphor with pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0489888A JPH0489888A (en) | 1992-03-24 |
| JP2959817B2 true JP2959817B2 (en) | 1999-10-06 |
Family
ID=16522328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20637790A Expired - Lifetime JP2959817B2 (en) | 1990-08-03 | 1990-08-03 | Phosphor with pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2959817B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4327620A1 (en) * | 1993-08-17 | 1995-02-23 | Merck Patent Gmbh | Stabilized, conductive pigment |
| US5838118A (en) * | 1996-03-28 | 1998-11-17 | Lucent Technologies Inc. | Display apparatus with coated phosphor, and method of making same |
| TW200540900A (en) * | 2004-05-04 | 2005-12-16 | Chunghwa Picture Tubes Ltd | Display device, screen panel and phosphor material composition thereof |
| CN102812105B (en) * | 2010-05-25 | 2014-11-05 | 海洋王照明科技股份有限公司 | Fluorescent materials used in field emission and preparation methods thereof |
| US20130071689A1 (en) * | 2010-05-31 | 2013-03-21 | Oceans King Lighting Science & Technology Co., Ltd. | Rare earth elements doping on yttrium oxide luminescent thin film containing conductive oxides and preparation methods thereof |
-
1990
- 1990-08-03 JP JP20637790A patent/JP2959817B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0489888A (en) | 1992-03-24 |
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