JPH09165572A - Red luminiferous fluorescent material with red color pigment - Google Patents
Red luminiferous fluorescent material with red color pigmentInfo
- Publication number
- JPH09165572A JPH09165572A JP32576495A JP32576495A JPH09165572A JP H09165572 A JPH09165572 A JP H09165572A JP 32576495 A JP32576495 A JP 32576495A JP 32576495 A JP32576495 A JP 32576495A JP H09165572 A JPH09165572 A JP H09165572A
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- Japan
- Prior art keywords
- pigment
- red
- phosphor
- pigment particles
- 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.)
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Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、電子線、Ｘ線、紫
外線等により発光させる表示装置に適した顔料付赤色発
光蛍光体に関し、特にスラリー塗布法で蛍光膜を形成す
るのに適したものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigmented red light emitting phosphor suitable for a display device which emits light by electron beam, X-ray, ultraviolet ray and the like, and particularly suitable for forming a phosphor film by a slurry coating method. Is.
【０００２】[0002]
【従来の技術】従来より、カラーブラウン管や蛍光表示
管、プラズマディスプレイ、ＥＬディスプレイ等の表示
装置の蛍光膜として使用する蛍光体は、その表面に顔料
粒子等の粒子を被覆して、蛍光体を表面改質処理するこ
とが広く行われている。2. Description of the Related Art Conventionally, a phosphor used as a phosphor film of a display device such as a color cathode ray tube, a fluorescent display tube, a plasma display, an EL display or the like is coated with particles such as pigment particles on the surface of the phosphor. Surface modification treatment is widely performed.
【０００３】例えば、蛍光体の発光スペクトルをシャー
プにして色純度を向上させたり、蛍光面における外光の
反射を吸収し、画像のコントラストを向上させるため
に、蛍光体粒子表面に着色フィルター材を付着させる顔
料付着蛍光体が知られている。顔料付蛍光体は、顔料粒
子をアクリルエマルション、ゼラチン、カゼイン、アラ
ビアガム、ポリアクリル酸塩等の熱軟化性バインダーを
用いて蛍光体表面に付着・固定させたものである。例え
ば、特開昭５０−５６１４６号公報には、ゼラチン・ア
ラビアガムを介して粒径０．１〜０．５μｍの顔料粒子
を蛍光体表面に付着する方法が記載されている。For example, in order to sharpen the emission spectrum of the phosphor to improve the color purity and to absorb the reflection of external light on the phosphor screen to improve the contrast of the image, a coloring filter material is provided on the surface of the phosphor particles. Pigment-attached phosphors to be attached are known. The pigmented phosphor is obtained by adhering and fixing pigment particles on the phosphor surface using a heat-softening binder such as acrylic emulsion, gelatin, casein, gum arabic, and polyacrylate. For example, Japanese Patent Application Laid-Open No. 50-56146 describes a method of attaching pigment particles having a particle size of 0.1 to 0.5 μm to the surface of a phosphor via gelatin / gum arabic.
【０００４】近年、表示装置の大画面化に伴い、所望の
コントラストを維持し、かつ、発光輝度を更に向上させ
る要請が高まっている。これに対処するため、蛍光膜特
性をより向上させる手段として、蛍光体表面に付着する
フィルター粒子（青色顔料、赤色顔料、緑色顔料、黒色
顔料などの顔料粒子）や表面改質用小粒子粉体（シリ
カ、アルミナ、チタニア、酸化インジウム、水酸化亜鉛
などの無機化合物粉体）の粒径を小さくし、その付着量
を少なくすることによって、蛍光体表面における蛍光体
の発光の吸収を抑制することが検討されている。In recent years, with the increase in screen size of display devices, there is an increasing demand for maintaining desired contrast and further improving the emission brightness. To deal with this, filter particles (pigment particles such as blue pigments, red pigments, green pigments, and black pigments) attached to the surface of the phosphor and small particle powders for surface modification are used as means for further improving the characteristics of the phosphor film. By suppressing the particle size of (inorganic compound powder such as silica, alumina, titania, indium oxide, zinc hydroxide) and reducing the amount of adhesion, it is possible to suppress the absorption of the light emission of the phosphor on the phosphor surface. Is being considered.
【０００５】特願平７−２０９３６４号明細書には、平
均粒径０．０５μｍの顔料粒子を熱軟化性バインダーを
介して蛍光体表面に付着させる方法が提案されている
が、この顔料付着蛍光体を陰極線管等に用いた場合、粒
径０．１μｍより小さな顔料粒子は電子線によって劣化
を受け、蛍光膜の発光色が時間とともに変化して、フィ
ルター効果が低下する。Japanese Patent Application No. 7-209364 proposes a method in which pigment particles having an average particle diameter of 0.05 μm are attached to the surface of a phosphor through a heat-softening binder. When the body is used for a cathode ray tube or the like, the pigment particles having a particle size smaller than 0.1 μm are deteriorated by an electron beam, the emission color of the fluorescent film changes with time, and the filter effect decreases.
【０００６】[0006]
【発明が解決しようとする課題】そこで、本発明は、上
記の欠点を解消し、蛍光体表面に顔料粒子を付着させる
際に、フィルター効果の経時的劣化の少ない顔料付赤色
発光蛍光体を提供しようというものである。SUMMARY OF THE INVENTION Therefore, the present invention solves the above-mentioned drawbacks and provides a pigmented red light-emitting phosphor with less deterioration of the filter effect over time when the pigment particles are attached to the surface of the phosphor. It is to try.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、蛍光膜の
発光色が電子線劣化により経時変化して、フィルター効
果が損なわれる原因を調べ、顔料特性について鋭意検討
したところ、従来の小粒径顔料粒子が十分に優れた結晶
性を備えていないために、電子線等の照射を長期にわた
り受けると、顔料粒子が劣化しやすいことを見出した。Means for Solving the Problems The inventors of the present invention investigated the cause of the deterioration of the filter effect due to the deterioration of the luminescent color of the fluorescent film over time due to electron beam deterioration, and conducted diligent studies on the pigment characteristics. It has been found that the pigment particles are not easily provided with excellent crystallinity, so that the pigment particles are likely to deteriorate when irradiated with an electron beam or the like for a long period of time.
【０００８】そこで、小粒径顔料粒子の中で特に結晶性
に優れる赤色顔料を選択して、顔料付着蛍光体を作製し
たところ、顔料の経時的な劣化（無定形化）が抑制さ
れ、フィルター効果が長期に渡り安定して持続すること
ができ、その結果、顔料粒子の付着量も少なくすること
ができるので、蛍光体表面における発光吸収を従来より
少なくした顔料付赤色発光蛍光体を提供できるようにな
った。Therefore, when a red pigment, which is particularly excellent in crystallinity, is selected from the small-sized pigment particles to produce a pigment-adhered phosphor, deterioration of the pigment over time (amorphization) is suppressed, and the filter is suppressed. The effect can be stably maintained for a long period of time, and as a result, the amount of the pigment particles attached can be reduced, so that it is possible to provide a red light-emitting phosphor with a pigment that has less emission absorption on the surface of the phosphor than ever before. It became so.
【０００９】本発明の構成を記載すると以下のとおりで
ある。 (1) α−Ｆｅ2 Ｏ3 顔料粒子を付着した顔料付赤色発光
蛍光体において、顔料粒子をＣｕＫα管球を用いて測定
したＸ線回折像の(200) 面における回折ピークの半値幅
が、０．４°以下であるα−Ｆｅ2 Ｏ3 顔料粒子を付着
してなることを特徴とする顔料付赤色発光蛍光体。The structure of the present invention will be described below. (1) In the pigmented red light-emitting phosphor with α-Fe 2 O 3 pigment particles attached, the half-value width of the diffraction peak on the (200) plane of the X-ray diffraction image of the pigment particles measured using a CuKα tube is A pigmented red light-emitting phosphor, comprising α-Fe 2 O 3 pigment particles of 0.4 ° or less attached.
【００１０】(2) 前記顔料粒子の平均粒径が、０．００
５〜０．１μｍの範囲内で単粒子化されていることを特
徴とする上記(1) に記載の顔料付赤色発光蛍光体。 (3) 前記顔料粒子の付着量が、０．０１〜１．０重量％
の範囲内にあることを特徴とする上記(1) 又は(2) に記
載の顔料付赤色発光蛍光体。 (4) 蛍光体粒子表面に熱軟化性バインダー層を設けて前
記顔料粒子を付着したことを特徴とする上記(1) 〜(3)
のいずれか１つに記載の顔料付赤色発光蛍光体。(2) The average particle size of the pigment particles is 0.00
The pigmented red light-emitting phosphor according to the above (1), which is formed into single particles within a range of 5 to 0.1 μm. (3) The amount of the pigment particles attached is 0.01 to 1.0% by weight.
The pigment-containing red light-emitting phosphor according to the above (1) or (2), which is within the range. (4) The above-mentioned (1) to (3), characterized in that the pigment particles are adhered by providing a heat-softening binder layer on the phosphor particle surface.
2. A red light emitting phosphor with a pigment according to any one of 1.
【００１１】[0011]
【発明の実施の形態】本発明は、従来顔料付蛍光体に使
用されたことのない、結晶性に優れた小粒子のα−Ｆｅ
2 Ｏ3 粒子を用いることにより、上記の優れた顔料付赤
色発光蛍光体の提供に成功したものである。また、本発
明で使用するα−Ｆｅ2 Ｏ3 顔料粒子は、上記のように
結晶性が優れているため、陰極線管のような表示装置の
製造工程中の高温工程においても劣化することなく、十
分に対応できる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a small particle α-Fe excellent in crystallinity, which has never been used for a phosphor with a pigment.
By using 2 O 3 particles, the above-described excellent pigmented red light-emitting phosphor was successfully provided. Further, since the α-Fe 2 O 3 pigment particles used in the present invention have excellent crystallinity as described above, they do not deteriorate even in a high temperature step during the manufacturing process of a display device such as a cathode ray tube, It can cope enough.
【００１２】即ち、本発明で用いるα−Ｆｅ2 Ｏ3 粒子
は、顔料粒子粉末のＣｕＫα管球を用いて測定したＸ線
回折像で、(200) 面における回折ピークの半値幅が０．
４°以下で、結晶性に優れたものを使用することによ
り、蛍光膜の発光色が電子線劣化により経時変化を抑制
し、フィルター効果の持続性を確保し、優れた顔料付赤
色発光蛍光体の提供に成功した。前記半値幅が０．４°
を越えると、結晶性が悪くなるため、経時変化を避ける
ことができない。That is, the α-Fe 2 O 3 particles used in the present invention are X-ray diffraction images measured using a CuKα tube of pigment particle powder, and the half width of the diffraction peak on the (200) plane is 0.
By using a material having excellent crystallinity at 4 ° or less, the emission color of the fluorescent film is suppressed from changing over time due to electron beam deterioration, the durability of the filter effect is ensured, and an excellent pigmented red light emitting phosphor is obtained. Was successfully provided. The full width at half maximum is 0.4 °
If it exceeds, crystallinity deteriorates, so that aging cannot be avoided.
【００１３】本発明で使用する顔料粒子の平均粒径は、
近年の表示装置の大画面化に伴い、所望のコントラスト
を維持し、かつ、発光輝度を更に向上させ、蛍光膜特性
をより向上させるという要請に対処するために０．００
５μｍ以上で０．１μｍ未満の範囲とするのが好まし
い。また、本発明の顔料粒子の付着量は、０．０１〜
１．０重量％、好ましくは０．０５〜０．５重量％の範
囲が適している。The average particle size of the pigment particles used in the present invention is
In order to meet the demands for maintaining a desired contrast, further improving the emission brightness, and further improving the characteristics of the fluorescent film with the increase in screen size of display devices in recent years, 0.00
The range is preferably 5 μm or more and less than 0.1 μm. In addition, the amount of the pigment particles of the present invention attached is from 0.01 to
A range of 1.0% by weight, preferably 0.05 to 0.5% by weight is suitable.
【００１４】本発明において使用される赤色発光蛍光体
は特に制限されないが、Ｙ2 Ｏ3 ；（Ｙ，Ｇｄ）
2 Ｏ3 、Ｇｄ2 Ｏ3 、Ｙ2 Ｏ2 Ｓ；（Ｙ，Ｇｄ）2 Ｏ2
Ｓ、Ｌａ2Ｏ2 Ｓ等を母体とする希土類酸化物系蛍光
体、ＺｎＳ、（Ｚｎ，Ｃｄ）Ｓ、ＣｄＳ等を母体とする
硫化物系蛍光体、（Ｌｎ，Ｃｅ，Ｔｂ）ＰＯ4 （但し、
ＬｎはＬａ，Ｙ，Ｇｄ及びＬｕの中の少なくとも１つ)
、（Ｃａ，Ｓｒ）5 （ＰＯ4 ） 3 Ｃｌ：Ｅｕ、ＢａＭ
ｇ2 Ａ7 Ｏ27：Ｅｕ、Ｃａ2 Ｂ5 Ｏ9 Ｃｌ：Ｅｕ、（Ｃ
ｅ，Ｔｅ）ＭｇＡｌ11Ｏ19、Ｙ2 ＳｉＯ5 ：Ｔｂ，Ｃ
ｅ、ＭｇＯ・Ｂ2 Ｏ3 ：Ｃｅ，Ｔｂ等のランプ用蛍光体
をはじめ、電子線、Ｘ線、紫外線、真空紫外線等により
発光する蛍光体であればいずれも適用できる。Red emitting phosphor used in the present invention
Is not particularly limited, but YTwoOThree; (Y, Gd)
TwoOThree, GdTwoOThree, YTwoOTwoS; (Y, Gd)TwoOTwo
S, LaTwoOTwoRare-earth oxide fluorescent based on S, etc.
Main body is ZnS, (Zn, Cd) S, CdS, etc.
Sulfide phosphor, (Ln, Ce, Tb) POFour(However,
Ln is at least one of La, Y, Gd and Lu)
, (Ca, Sr)Five(POFour) ThreeCl: Eu, BaM
gTwoA7O27: Eu, CaTwoBFiveO9Cl: Eu, (C
e, Te) MgAl11O19, YTwoSiOFive: Tb, C
e, MgO / BTwoOThree: Phosphors for lamps such as Ce and Tb
, Electron beam, X-ray, ultraviolet ray, vacuum ultraviolet ray, etc.
Any phosphor that emits light can be applied.
【００１５】本発明で使用する熱軟化性バインダーとし
ては、アクリルエマルション、ゼラチン、カゼイン、ア
ラビアガム、ポリアクリル酸塩等を挙げることができ
る。なお、顔料粒子と熱軟化性バインダーの蛍光体表面
への吸着性を改良するために、酢酸溶液、シュウ酸、ク
エン酸等の有機酸を添加することができる。Examples of the heat-softenable binder used in the present invention include acrylic emulsion, gelatin, casein, gum arabic and polyacrylate. An organic acid such as acetic acid solution, oxalic acid or citric acid can be added to improve the adsorption of the pigment particles and the heat-softening binder onto the surface of the phosphor.
【００１６】以下、本発明の蛍光体の製造方法について
詳述する。 （１）顔料粒子分散液を作製する工程 まず、上記の赤色顔料粒子と溶媒を混合する。溶媒は、
水及び／又は有機溶媒を用い、顔料粒子の分散性を良く
するために、さらに、Ｓｉ，Ｐ系化合物、有機酸塩、ア
ニオン系界面活性剤等の無機及び／又は有機系の分散助
剤を添加しても良く、分散性が悪い場合はサンドミルで
処理することもできる。The method for producing the phosphor of the present invention will be described in detail below. (1) Step of producing pigment particle dispersion liquid First, the above-mentioned red pigment particles and a solvent are mixed. The solvent is
In order to improve the dispersibility of the pigment particles by using water and / or an organic solvent, an inorganic and / or organic dispersion aid such as a Si, P-based compound, an organic acid salt or an anionic surfactant is further added. It may be added, and if the dispersibility is poor, it may be treated with a sand mill.
【００１７】（２）顔料粒子を混合して蛍光体表面に付
着する工程 本発明の顔料粒子は、例えば、特願平７−２０９３６４
号公報に記載の方法により、熱軟化性バインダーを介し
て蛍光体表面に付着させることができる。この方法は、
蛍光体粒子と熱軟化性バインダーを溶媒と共に混合した
後、顔料粒子を添加・混合し、次いで前記溶媒を除去
し、前記熱軟化性バインダーを加熱軟化して蛍光体粒子
表面にほぼ単粒子化した状態で前記顔料粒子を付着させ
るものである。(2) Step of mixing pigment particles and adhering them to the surface of the phosphor The pigment particles of the present invention can be obtained, for example, from Japanese Patent Application No. 7-209364.
According to the method described in the publication, it can be attached to the surface of the phosphor through a heat-softening binder. This method
After mixing the phosphor particles and the heat-softening binder with a solvent, the pigment particles were added and mixed, then the solvent was removed, and the heat-softening binder was heat-softened to form almost single particles on the surface of the phosphor particles. In this state, the pigment particles are attached.
【００１８】[0018]
【実施例】以下、カラーブラウン管用蛍光体についての
実施例で本発明を詳しく説明するが、本発明は本実施例
に限定されるものではない。 〔実施例１〕α−Ｆｅ2 Ｏ3 粒子として、弁柄（堺化学
社製、ＦＲＯ−３）を用いた。この顔料粒子粉末を装置
専用セルの板状の窪みに充填し、Ｘ線回折装置（日本電
子社製、ＪＥＯＬ８００）を用い、ＣｕＫα管球より発
せられるＸ線を前記板状試料に照射して、様々な角度か
らその回折強度を測定してＸ線回折像を得た。最も回折
強度の強い回折角２θ＝３３．２°のピークを解析した
ところ、このピークは面間隔０．２７０ｎｍの(200) 面
で回折ピークの強度が１／２に減少する箇所の半値幅が
０．２８°であった。この顔料粒子１００重量部に対
し、２重量部のクエン酸ソーダと、９００重量部の水を
加え、２４時間サンドミルで処理して顔料分散液を調製
した。前記顔料分散液中の顔料粒子の平均粒径は０．０
４μｍであった。EXAMPLES The present invention will be described in detail below with reference to examples of phosphors for color cathode ray tubes, but the present invention is not limited to these examples. [Example 1] As the α-Fe 2 O 3 particles, a valley (FRO-3 manufactured by Sakai Chemical Co., Ltd.) was used. This pigment particle powder was filled in a plate-shaped recess of a cell dedicated to the apparatus, and an X-ray emitted from a CuKα tube was used to irradiate the plate-shaped sample with an X-ray diffractometer (JEOL800, manufactured by JEOL Ltd.), The diffraction intensity was measured from various angles to obtain X-ray diffraction images. Analysis of the peak with the strongest diffraction intensity at the diffraction angle 2θ = 33.2 ° revealed that the peak had a half-value width at the point where the intensity of the diffraction peak decreased to 1/2 on the (200) plane with a spacing of 0.270 nm. It was 0.28 °. To 100 parts by weight of the pigment particles, 2 parts by weight of sodium citrate and 900 parts by weight of water were added and treated with a sand mill for 24 hours to prepare a pigment dispersion liquid. The average particle size of the pigment particles in the pigment dispersion is 0.0
It was 4 μm.
【００１９】次に、平均粒径７．５μｍのカラ一ブラウ
ン管用赤色発光蛍光体（Ｙ2 Ｏ2 Ｓ：Ｅｕ）１０００ｇ
に対し、赤色発光蛍光体に対する添加濃度が０．４重量
％となるよう、前記顔料分散液を水２００ｇで希釈して
加え、十分に混合した。次いで、熱軟化性バインダーと
して赤色発光蛍光体に対する添加濃度が０．１重量％の
アクリル・スチレン系エマルジョン（日本アクリル社
製、Ｂ−３３６、アクリル・スチレン共重合体、共重合
比=3O/7O、粒子径０．０５μｍ）を添加混合し、さら
に、前記顔料粒子・熱軟化性バインダーの蛍光体表面へ
の吸着性を良好にするために、０．１規定のシュウ酸溶
液を赤色発光蛍光体に対する添加濃度が、０．０５重量
％となるように添加した。Next, 1000 g of a red light-emitting phosphor (Y 2 O 2 S: Eu) for a color cathode ray tube having an average particle size of 7.5 μm.
On the other hand, the pigment dispersion was diluted with 200 g of water and added so that the concentration added to the red-emitting phosphor was 0.4% by weight, and they were mixed sufficiently. Then, as a heat-softening binder, an acrylic-styrene emulsion having an additive concentration of 0.1% by weight to the red light-emitting phosphor (manufactured by Nippon Acrylic Co., B-336, acrylic-styrene copolymer, copolymerization ratio = 3O / 7O). , And a particle diameter of 0.05 μm), and further, in order to improve the adsorption of the pigment particles and the heat-softening binder to the surface of the phosphor, a 0.1 N oxalic acid solution was added to the red-emitting phosphor. Was added so that the concentration added to the product was 0.05% by weight.
【００２０】その後、１００℃で加熱乾燥して水分を除
去した後、１２０℃で蛍光体層を攪拌することによって
バインダーを加熱軟化して、顔料を蛍光体に吸着させた
後、冷却して０．４重量％の上記弁柄顔料粒子を付着し
た顔料付赤色発光蛍光体を得た。Then, after heating and drying at 100 ° C. to remove water, the binder is heated and softened by stirring the phosphor layer at 120 ° C. to adsorb the pigment to the phosphor and then cooled to 0. A pigmented red light-emitting phosphor having 0.4% by weight of the above-mentioned red iron oxide pigment particles attached thereto was obtained.
【００２１】〔比較例１〕α−Ｆｅ2 Ｏ3 粒子として、
弁柄（大日精化工業社製、ＴＯＲ）を用いた以外は、実
施例１と同様にして０．４重量％の上記弁柄顔料粒子を
付着した赤色発光蛍光体を得た。また、この顔料粒子を
実施例１同様にしてＸ線回折像を分析したところ、(20
0) 面における回折ピークの半値幅が０．４８°であっ
た。なお、顔料分散液中の顔料粒子の平均粒径は０．０
４μｍであった。Comparative Example 1 As α-Fe 2 O 3 particles,
A red-light-emitting phosphor having 0.4% by weight of the above-mentioned red iron oxide pigment particles adhered was obtained in the same manner as in Example 1 except that a red iron oxide (TOR, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used. An X-ray diffraction image of the pigment particles was analyzed in the same manner as in Example 1 and found to be (20
The full width at half maximum of the diffraction peak on the (0) plane was 0.48 °. The average particle size of the pigment particles in the pigment dispersion is 0.0
It was 4 μm.
【００２２】〔実施例２〕実施例１において、弁柄（堺
化学社製、ＦＲＯ−３）粒子の付着量を０．１重量％に
変更した以外は、実施例１と同じ条件で顔料付赤色発光
蛍光体を得た。[Example 2] Pigmentation was carried out under the same conditions as in Example 1 except that the adhered amount of the sesame (FRO-3, manufactured by Sakai Chemical Industry Co., Ltd.) particles was changed to 0.1% by weight. A red-emitting phosphor was obtained.
【００２３】〔比較例２〕比較例１において、弁柄（大
日精化工業社製、ＴＯＲ）粒子の付着量を０．１重量％
に変更した以外は、実施例１と同じ条件で顔料付赤色発
光蛍光体を得た。[Comparative Example 2] In Comparative Example 1, the amount of the sesame (Dainichi Seika Kogyo TOR) particles deposited was 0.1% by weight.
A red light emitting phosphor with a pigment was obtained under the same conditions as in Example 1 except that the above was changed to.
【００２４】〔比較例３〕α−Ｆｅ2 Ｏ3 粒子として、
比較的大粒径の鉄酸化物（ファイザー社製、Ｒ２１９
９）を用い、該粒子の付着量を０．４重量％に変更した
以外は、実施例１と同様にして顔料付赤色発光蛍光体を
得た。この顔料粒子を実施例１同様にしてＸ線回折像を
分析したところ、(200) 面における回折ピークの半値幅
が０．２５°であった。なお、顔料分散液中の顔料粒子
の平均粒径は０．２０μｍであった。[Comparative Example 3] As α-Fe 2 O 3 particles,
Iron oxide with a relatively large particle size (P219, R219
A red light emitting phosphor with a pigment was obtained in the same manner as in Example 1 except that 9) was used and the amount of the attached particles was changed to 0.4% by weight. When an X-ray diffraction image of the pigment particles was analyzed in the same manner as in Example 1, the half width of the diffraction peak on the (200) plane was 0.25 °. The average particle size of the pigment particles in the pigment dispersion was 0.20 μm.
【００２５】（電子線劣化率試験）実施例１、２及び比
較例１、２、３で得た顔料付赤色発光蛍光体を用い、沈
降塗布法で蛍光膜を作製した。得られた蛍光膜を色彩輝
度計（ＴＯＰＣＯＮ社製、ＢＭ−５）を用い、初期発光
色及び２０ｋＶ、３０μＡの電子線を３０分間照射した
後の発光色を測定した。表１には、顔料粒子の回折ピー
クの半値幅、及び、顔料付赤色発光蛍光体の電子線照射
前後の発光色及びその変化幅を示した。(Electron Beam Degradation Rate Test) Using the pigmented red light emitting phosphors obtained in Examples 1 and 2 and Comparative Examples 1, 2 and 3, a phosphor film was prepared by a sedimentation coating method. An initial luminescent color and a luminescent color after irradiating with an electron beam of 20 kV and 30 μA for 30 minutes were measured for the obtained fluorescent film using a color luminance meter (BM-5, manufactured by TOPCON). Table 1 shows the full width at half maximum of the diffraction peak of the pigment particles, the emission color of the pigmented red light-emitting phosphor before and after electron beam irradiation, and the change width thereof.
【００２６】表１から明らかなように、回折ピークの半
値幅が小さい、即ち結晶性の高い赤色顔料粒子を使用し
た実施例１、２は、電子線照射による発光色の変化を受
けにくいことが確認された。一方、回折ピークの半値幅
の大きな比較例１、２は、電子線照射による発光色の変
化を受けていることが分かる。また、顔料分散液中の顔
料粒子の平均粒径が０．２μｍと、従来の比較的大粒径
の赤色顔料粒子は、回折ピークの半値幅が０．２５°と
小さく、結晶性が優れているため、電子線照射前後の発
光色及びその変化幅は小さく、電子線照射による発光色
の変化は受けにくいが、粒径の大きな顔料を付着してい
るため、発光輝度が９０％と極めて低い値を示した。As is clear from Table 1, Examples 1 and 2 using the red pigment particles having a narrow half-value width of the diffraction peak, that is, having high crystallinity, are not easily affected by the change in the emission color due to electron beam irradiation. confirmed. On the other hand, it can be seen that Comparative Examples 1 and 2 in which the half-value width of the diffraction peak is large are affected by the change in the emission color due to the electron beam irradiation. Further, the average particle size of the pigment particles in the pigment dispersion is 0.2 μm, and the conventional red pigment particles having a relatively large particle size have a small half-value width of the diffraction peak of 0.25 ° and are excellent in crystallinity. Therefore, the emission color before and after the electron beam irradiation and its change width are small, and the change in the emission color due to the electron beam irradiation is not easily received, but since the pigment with a large particle size is attached, the emission brightness is extremely low at 90%. Showed the value.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】本発明は、上記の構成を採用することに
より、赤色顔料付赤色発光蛍光体を陰極線管などに用い
たときに、蛍光膜の発光色が経時変化せず、フィルター
効果を持続させることができ、かつ、優れた発光輝度を
有する赤色顔料付赤色発光蛍光体を提供することができ
るようになった。According to the present invention, by adopting the above-mentioned constitution, when the red-light-emitting phosphor with a red pigment is used in a cathode ray tube or the like, the emission color of the fluorescent film does not change with time and the filter effect is maintained. In addition, it has become possible to provide a red pigment-attached red light-emitting phosphor that can be made to have an excellent emission brightness.
Claims (3)
付赤色発光蛍光体において、顔料粒子をＣｕＫα管球を
用いて測定したＸ線回折像の(200) 面における回折ピー
クの半値幅が、０．４°以下であるα−Ｆｅ2 Ｏ3 顔料
粒子を付着してなることを特徴とする顔料付赤色発光蛍
光体。1. A full width at half maximum of a diffraction peak on the (200) plane of an X-ray diffraction image of a pigment-emitting red light-emitting phosphor having α-Fe 2 O 3 pigment particles attached thereto, the pigment particles being measured using a CuKα tube. Is a pigmented red light-emitting phosphor, to which α-Fe 2 O 3 pigment particles of 0.4 ° or less are attached.
〜０．１μｍの範囲内で単粒子化されていることを特徴
とする請求項１に記載の顔料付赤色発光蛍光体。2. The average particle size of the pigment particles is 0.005.
The pigmented red light-emitting phosphor according to claim 1, wherein the pigment-containing red light-emitting phosphor is formed into a single particle within a range of from 0.1 to 0.1 μm.
を設けて前記顔料粒子を付着したことを特徴とする請求
項１又は２記載の顔料付赤色発光蛍光体。3. A pigment-emitting red light-emitting phosphor according to claim 1, wherein a heat-softening binder layer is provided on the surface of the phosphor particles to attach the pigment particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32576495A JPH09165572A (en) | 1995-12-14 | 1995-12-14 | Red luminiferous fluorescent material with red color pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32576495A JPH09165572A (en) | 1995-12-14 | 1995-12-14 | Red luminiferous fluorescent material with red color pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09165572A true JPH09165572A (en) | 1997-06-24 |
Family
ID=18180368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32576495A Pending JPH09165572A (en) | 1995-12-14 | 1995-12-14 | Red luminiferous fluorescent material with red color pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09165572A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10125240A (en) * | 1996-08-29 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Plasma display panel, and manufacture of phosphor for plasma display panel |
| KR19990011000A (en) * | 1997-07-21 | 1999-02-18 | 구자홍 | How to Form Color CRT Screen |
-
1995
- 1995-12-14 JP JP32576495A patent/JPH09165572A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10125240A (en) * | 1996-08-29 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Plasma display panel, and manufacture of phosphor for plasma display panel |
| KR19990011000A (en) * | 1997-07-21 | 1999-02-18 | 구자홍 | How to Form Color CRT Screen |
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