JPH0826311B2 - Fluorescent body - Google Patents
Fluorescent bodyInfo
- Publication number
- JPH0826311B2 JPH0826311B2 JP62155075A JP15507587A JPH0826311B2 JP H0826311 B2 JPH0826311 B2 JP H0826311B2 JP 62155075 A JP62155075 A JP 62155075A JP 15507587 A JP15507587 A JP 15507587A JP H0826311 B2 JPH0826311 B2 JP H0826311B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- emission
- curve
- present
- color
- 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 - Fee Related
Links
Landscapes
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はクロロ硼酸塩系螢光体に関する。さらに詳し
くは、螢光ランプ、投射管、プラズマディスプレイ、カ
ラーテレビジョン等の青色発光螢光体として良好に使用
できる２価のユーロピウム付活カルシウム、バリウム・
クロロ硼酸塩系螢光体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chloroborate-based phosphor. More specifically, divalent europium-activated calcium, barium, which can be favorably used as a blue-emitting phosphor for fluorescent lamps, projection tubes, plasma displays, color televisions, etc.
A chloroborate-based phosphor.
螢光体は、その発光色（主にピーク波長）及び発光輝
度によって、種々の用途に使い分けられている。Fluorescent materials are used for various purposes depending on the emission color (mainly the peak wavelength) and the emission brightness.
青色発光螢光体のうち、高い発光輝度を有するBAM螢
光体〔BaMg2Al16O27：Eu2+〕及びアパタイト螢光体
〔（Ca、Sr）5(PO4)3Cl：Eu2+〕は、高演色性螢光ラン
プやカラーテレビジョンのブラウン管用の螢光体として
用いられている。上記２つの螢光体以外は発光輝度が不
十分であり、高演色性螢光ランプ等にほとんど実用され
ていない。Among the blue-emitting phosphors, the BAM phosphor [BaMg 2 Al 16 O 27 : Eu 2+ ] and the apatite phosphor [(Ca, Sr) 5 (PO 4 ) 3 Cl: Eu 2 which have high emission brightness. + ] Is used as a fluorescent substance for high color rendering fluorescent lamps and cathode ray tubes of color televisions. Except for the above two fluorescent substances, the luminous brightness is insufficient, and it is hardly practically used for high color rendering fluorescent lamps.
ところが上記２つの螢光体は、いずれも輝度の経時的
劣化が比較的大きい。又、BAM螢光体は製造時に高い焼
成温度（約1400℃以上）を必要とし、製造が必ずしも容
易でなく、製造された螢光体粒子の径が比較的小さいこ
とから螢光膜形成に支障が有る等の欠点を有していた。However, in both of the above two phosphors, the deterioration of luminance with time is relatively large. In addition, BAM phosphors require a high firing temperature (about 1400 ° C or higher) during production, are not always easy to produce, and the diameter of the produced phosphor particles is relatively small, which hinders the formation of the phosphor film. There was a defect such as
このため、高演色性螢光ランプ、カラーテレビジョ
ン、投射管等のブラウン管用及びプラズマディスプレイ
用の青色発光螢光体として適した発光色と高い発光輝度
を有する新規な螢光体の出現が望まれていた。Therefore, it is desired to develop a new phosphor having a high emission color and a high emission brightness suitable as a blue-emitting phosphor for CRTs such as high color rendering fluorescent lamps, color televisions, projection tubes, and plasma displays. It was rare.
ところで従来から、青色発光螢光体として２価のユー
ロピウム付活カルシウム・クロロ硼酸塩螢光体〔（Ca、
Eu2+）2B5O9Cl〕が知られている〔ジャーナル オブ
インオーガニック ニュークリア ケミストリー（Jour
nal of Inorganic Nuclear Chemistry）（1970）32巻、
1089〜1095ページ：以下GTEの論文という〕。この（C
A、Eu2+）2B5O9Cl螢光体は紫外線、Ｘ線、真空紫外線あ
るいは電子線励起下において、第２図曲線２に発光スペ
クトルを示すように約450nmにピークをもつ青色発光を
し、その発光色はCIE表色系色度座標で、ｘ＝0.146、ｙ
＝0.047である。この（Ca、Eu2+）2B5O9Cl螢光体の発光
色は、高演色性ランプ用、あるいはカラーテレビジョン
ブラウン管等の青色発光成分として適したものである。
しかるに上記クロロ硼酸塩螢光体は、現在実用に供され
ている螢光体（例えばBaMg2Al16O27：Eu2+）に比べてCI
E表色系色度座標に於けるｙ値が小さく、輝度も低いた
めにほとんど実用されていない。By the way, conventionally, a divalent europium-activated calcium / chloroborate phosphor [(Ca,
Eu 2+ ) 2 B 5 O 9 Cl] is known [Journal of
In Organic Nuclear Chemistry (Jour
nal of Inorganic Nuclear Chemistry) (1970) 32 volumes,
Pages 1089-1095: GTE papers below]. This (C
A, Eu 2+ ) 2 B 5 O 9 Cl phosphor emits blue light with a peak at about 450 nm as shown by the emission spectrum in Fig. 2 curve 2 under UV, X-ray, vacuum UV or electron beam excitation. The emission color is CIE color system chromaticity coordinate, x = 0.146, y
= 0.047. The emission color of this (Ca, Eu 2+ ) 2 B 5 O 9 Cl phosphor is suitable for a high color rendering lamp or as a blue light emitting component for a color television CRT or the like.
However, the above-mentioned chloroborate phosphor is CI compared to the phosphor currently in practical use (for example, BaMg 2 Al 16 O 27 : Eu 2+ ).
E The y value in the chromaticity coordinates of the E color system is small, and the brightness is also low, so it is hardly used.
また上記（Ca、Eu2+）2B5O9Cl螢光体の母体構成成分
であるカルシウムの全量をバリウムで置換した螢光体で
ある２価のユーロピウム付活バリウム・クロロ硼酸塩螢
光体〔（Ba、Eu2+）2B5O9Cl〕も知られている〔GTEの論
文〕。ところがこの（Ba、Eu2+）2B5O9Cl螢光体は紫外
線、Ｘ線、真空紫外線あるいは電子線励起下において、
第２図曲線３に発光スペクトルを示すように約420nmに
ピークをもつ紫外発光を示し、かつその発光色はCIE表
色系色度座標でｘ＝0.167、ｙ＝0.010であり、発光色及
び発光輝度ともに高演色性ランプ用あるいはカラーテレ
ビジョンブラウン管等の青色発色成分として、前記（C
a、Eu2+）2B5O9Cl以上に実用し得ないものであった。更
にカルシウムの一部をバリウムで置換した２価のユーロ
ピウム付活カルシウム・バリウムクロロ硼酸塩螢光体
〔（Ca、Ba、Eu2+）2B5O9Cl〕がGTEの論文に開示されて
いる。ところが、この論文中に（Ca、Ba、Eu2+）2B5O9C
l螢光体の発光色は、前記（Ca、Eu2+）2B5O9Cl螢光体の
発光色と（Ba、Eu2+）2B5O9Cl螢光体の発光色との間を
カルシウムとバリウムの量比に従って変化する旨の記載
がある。In addition, the divalent europium-activated barium chloroborate fluorescent substance, which is a fluorescent substance in which the total amount of calcium, which is the matrix component of the (Ca, Eu 2+ ) 2 B 5 O 9 Cl fluorescent substance, is replaced by barium. The body [(Ba, Eu 2+ ) 2 B 5 O 9 Cl] is also known [GTE paper]. However, this (Ba, Eu 2+ ) 2 B 5 O 9 Cl phosphor can be excited by UV, X-ray, vacuum UV, or electron beam excitation.
As shown in the emission spectrum of curve 2 in Fig. 2, ultraviolet emission having a peak at about 420 nm is shown, and the emission color is x = 0.167 and y = 0.010 in the CIE color system chromaticity coordinates. For both high brightness and high color rendering lamps, or as a blue color component for color television CRTs,
a, Eu 2+ ) 2 B 5 O 9 Cl was not practically usable. Furthermore bivalent europium-activated calcium-barium-chloro borate phosphor part was replaced by barium calcium [(Ca, Ba, Eu 2+) 2 B 5 O 9 Cl ] is disclosed in the article of GTE There is. However, in this paper (Ca, Ba, Eu 2+ ) 2 B 5 O 9 C
l The emission color of the phosphor is the same as that of the (Ca, Eu 2+ ) 2 B 5 O 9 Cl phosphor and the emission color of the (Ba, Eu 2+ ) 2 B 5 O 9 Cl phosphor. There is a description that it changes according to the amount ratio of calcium and barium between.
更に、（Ca、Ba、Eu2+）2B5O9Clの発光輝度は、（C
a、Eu2+）2B5O9Clを超えることはない旨が記載されてい
る。即ち、（Ca、Ba、Eu2+）2B5O9Clは、前記（Ca、Eu
2+）2B5O9Cl及び（Ba、Eu2+）2B5O9Clと同様に高演色性
ランプ用あるいはカラーテレビジョン、投射管等のブラ
ウン管用及びプラズマディスプレイ用の青色螢光体とし
ては、実用に供し得ないものであった。Furthermore, the emission brightness of (Ca, Ba, Eu 2+ ) 2 B 5 O 9 Cl is (C
a, Eu 2+ ) 2 B 5 O 9 Cl is not exceeded. That is, (Ca, Ba, Eu 2+ ) 2 B 5 O 9 Cl is (Ca, Eu,
2+ ) 2 B 5 O 9 Cl and (Ba, Eu 2+ ) 2 B 5 O 9 Cl, as well as blue fluorescent light for high color rendering lamps, cathode ray tubes such as color televisions and projection tubes, and plasma displays The body was unusable for practical use.
本発明の目的は、実用に十分供し得る発光色と発光輝
度とを有し、かつ実用されている従来の青色発光螢光体
と比較して製造時の焼成温度が低く粒子径も十分大きい
新規な青色発光のクロロ硼酸塩径螢光体を提供すること
にある。The object of the present invention is to have a luminescent color and a luminescent brightness which can be sufficiently provided for practical use, and has a low firing temperature during production and a sufficiently large particle size as compared with a conventional blue light-emitting phosphor which is practically used. Another object of the present invention is to provide a chloroborate phosphor that emits blue light.
本発明は、一般式（Ｉ）で表されるカルシウム・バリ
ウム・クロロ硼酸塩系青色蛍光体を提供する。The present invention provides a calcium / barium / chloroborate-based blue phosphor represented by the general formula (I).
（Ca1-i-j、Bai、Eu2+ j）2B5O9Cl （Ｉ） （式中、ｉは0.025≦ｉ≦0.5であり、かつｊは0.005≦
ｊ≦0.25である）。(Ca 1-ij , Ba i , Eu 2+ j ) 2 B 5 O 9 Cl (I) (where i is 0.025 ≦ i ≦ 0.5, and j is 0.005 ≦
j ≦ 0.25).
本発明の螢光体は、例えば式 （Ca1-i-j、Bai、Eu2+ j）2B5O9Cl （Ｉ） （式中、ｉは0.025≦ｉ≦0.32であり、かつｊは0.0005
≦ｊ≦0.25である）で表わされ、かつその発光色のCIE
表色系色度座標のｙ値が0.06以上であるクロロ硼酸塩系
螢光体を挙げることができる。The phosphor of the present invention has, for example, the formula (Ca 1-ij , Ba i , Eu 2+ j ) 2 B 5 O 9 Cl (I) (wherein i is 0.025 ≦ i ≦ 0.32, and j is 0.0005
≤ j ≤ 0.25) and the CIE of the emission color
A chloroborate-based phosphor having a colorimetric chromaticity coordinate y value of 0.06 or more can be mentioned.
本発明のクロロ硼酸塩系螢光体は、螢光体製造時の焼
成雰囲気を、従来クロロ硼酸塩系螢光体製造時に用いら
れたことがない特殊な条件（高還元条件）とすることに
よって製造される。本発明の螢光体は紫外線、Ｘ線、真
空紫外線あるいは電子線励起下で前記カルシウム、バリ
ウム又はその両者を母体構成成分として含むクロロ硼酸
塩系螢光体のいずれとも全く異なる発光色を示し、かつ
発光輝度も著しく高い、特異的な青色発光を示すもので
ある。The chloroborate-based phosphor of the present invention is obtained by setting the firing atmosphere during the production of the phosphor to a special condition (high reduction condition) that has never been used during the production of the chloroborate-based phosphor. Manufactured. The phosphor of the present invention exhibits a completely different emission color from any of the chloroborate-based phosphors containing ultraviolet rays, X-rays, vacuum ultraviolet rays or electron beam excitation as the above-mentioned calcium, barium or both as a matrix constituent component, In addition, it exhibits peculiar blue light emission with extremely high emission brightness.
本発明の螢光体の製造法を、式（Ｉ）で表わされる螢
光体を例として以下に示す。The method for producing the phosphor of the present invention will be described below by taking the phosphor represented by the formula (I) as an example.
式（Ca1-i-j、Bai、Eu2+ j）2B5O9Cl （Ｉ） （式中、ｉは0.025≦ｉ≦0.32であり、かつｊは0.0005
≦ｊ≦0.25である）を満足するように調製されたカルシ
ウム化合物、バリウム化合物、塩化物、硼素化合物及び
ユーロピウム化合物を含む螢光体原料を、高還元性雰囲
気中で焼成することにより、上記式で表わされる本発明
のクロロ硼酸塩系螢光体を製造することができる。Formula (Ca 1-ij , Ba i , Eu 2+ j ) 2 B 5 O 9 Cl (I) (where i is 0.025 ≦ i ≦ 0.32 and j is 0.0005
≦ j ≦ 0.25), and a fluorescent material containing a calcium compound, a barium compound, a chloride, a boron compound, and a europium compound, which is prepared to satisfy the above formula, by firing in a highly reducing atmosphere. The chloroborate-based phosphor of the present invention represented by can be produced.
上記螢光体原料としては例えば以下の化合物を用いる
ことができる。For example, the following compounds can be used as the fluorescent material.
（１）カルシウム化合物 酸化カルシウムもしくは硝酸塩、炭酸塩等の高温で容
易に酸化カルシウムに変わりうるカルシウム含有化合物 （２）バリウム化合物 酸化バリウムもしくは硝酸塩、炭酸塩等の高温で容易
に酸化バリウムに変わりうるバリウム含有化合物 （３）塩化物 塩化カルシウム、塩化バリウム （４）硼素化合物 酸化硼素、硼酸 （５）ユーロピウム化合物 酸化ユーロピウムもしくは硝酸塩、塩化物等の高温で
容易に酸化ユーロピウムに変わりうるユーロピウム化合
物 上記５つの群の化合物を含む螢光体原料を 式（Ca1-i-j、Bai、Eu2+ j）2B5O9Cl （Ｉ） （式中、ｉは0.025≦ｉ≦0.32であり、かつｊは0.0005
≦ｊ≦0.25である） を満足するように秤量する。秤量した原料は、水等を媒
体として十分に混合してペースト状の混合物を得る。得
られたペースト状の混合物を乾燥（例えば140℃ ８時
間）し、次いで篩分けする。篩分けして得られた螢光体
原料混合物を次いで高還元性雰囲気中で焼成する。高還
元性雰囲気中での焼成は、例えば炭素を共存させること
により実施できる。より具体的には螢光体原料混合物を
るつぼに層状に充填し、各原料混合物の層間及び最上部
に石英クロスを介して無定形炭素あるいは黒鉛等の炭素
を配置し、かつるつぼ内を密閉して行う。るつぼ内の密
閉は、例えばるつぼの開口部に水ガラス等の接着剤を介
して蓋をすることにより得ることができる。焼成温度
は、例えば約800〜1100℃、好ましくは870〜1030℃とす
ることが適当である。焼成時間は、焼成温度、焼成する
原料混合物量等により変化するが、例えば約１〜７時
間、好ましくは２〜５時間とすることが適当である。(1) Calcium compound Calcium-containing compound such as calcium oxide or nitrate, carbonate which can be easily converted to calcium oxide at high temperature (2) Barium compound Barium oxide or barium oxide such as nitrate or carbonate which can be easily converted to barium oxide at high temperature Contained compounds (3) Chloride Calcium chloride, barium chloride (4) Boron compound Boron oxide, boric acid (5) Europium compound Europium compound such as europium oxide or nitrate, chloride, etc. that can easily be converted to europium oxide at high temperature The above five groups A phosphor raw material containing a compound of formula (Ca 1-ij , Ba i , Eu 2+ j ) 2 B 5 O 9 Cl (I) (wherein i is 0.025 ≦ i ≦ 0.32 and j is 0.0005
≦ j ≦ 0.25) is satisfied. The weighed raw materials are sufficiently mixed with water or the like as a medium to obtain a paste-like mixture. The pasty mixture obtained is dried (eg 140 ° C. for 8 hours) and then screened. The phosphor raw material mixture obtained by sieving is then fired in a highly reducing atmosphere. Firing in a highly reducing atmosphere can be carried out, for example, by allowing carbon to coexist. More specifically, the phosphor raw material mixture is packed in layers in a crucible, and amorphous carbon or carbon such as graphite is placed through quartz cloth between the layers of each raw material mixture and at the top, and the inside of the crucible is sealed. Do it. The airtightness inside the crucible can be obtained, for example, by covering the opening of the crucible with an adhesive such as water glass. The firing temperature is, for example, about 800 to 1100 ° C, preferably 870 to 1030 ° C. Although the firing time varies depending on the firing temperature, the amount of the raw material mixture to be fired, etc., it is suitable to be, for example, about 1 to 7 hours, preferably 2 to 5 hours.
上記条件下で焼成を行うことにより、るつぼ内は、炭
素の存在により高還元性雰囲気となる。該高還元性雰囲
気は、るつぼ外の雰囲気を中性もしくは還元性雰囲気と
することにより、より良好に保つことができる。By firing under the above conditions, the inside of the crucible becomes a highly reducing atmosphere due to the presence of carbon. The highly reducing atmosphere can be better maintained by making the atmosphere outside the crucible a neutral or reducing atmosphere.
尚、高還元性雰囲気の形成法として、炭素を共存させ
る方法を例示して説明したが、同様の高還元性雰囲気を
形成できる方法、例えば水蒸気を含んだ水素雰囲気等の
条件下で焼成を実施することもできる。As a method of forming the highly reducing atmosphere, the method of coexisting carbon has been described as an example, but a method capable of forming a similar highly reducing atmosphere, for example, firing under conditions such as a hydrogen atmosphere containing water vapor You can also do it.
焼成後、洗浄、乾燥、篩分け等の螢光体製造法におい
て一般に採用される各操作を行って本発明の螢光体を得
ることができる。After firing, the phosphor of the present invention can be obtained by performing each operation generally employed in the phosphor manufacturing method such as washing, drying and sieving.
螢光体製造においては、一般に得られる螢光体の発光
輝度、粉体特性等を向上させることを目的として螢光体
原料に融剤を添加することが多い。本発明の螢光体の製
造においても、塩化アンモニウム或いは螢光体原料
（３）の塩化物等を融剤として使用できる。螢光体原料
（３）の塩化物等を融剤として使用する場合、螢光体原
料（３）の塩化物は上記混合組成式を満たす量よりも過
剰に使用する。また融剤として過剰量の原料（４）が使
用されることもある。In the manufacture of phosphors, a flux is often added to the phosphor raw material for the purpose of improving the emission brightness, powder characteristics and the like of phosphors generally obtained. Also in the production of the phosphor of the present invention, ammonium chloride or chloride of the phosphor raw material (3) or the like can be used as a flux. When a chloride or the like of the phosphor raw material (3) is used as a flux, the chloride of the phosphor raw material (3) is used in an amount exceeding the amount satisfying the above mixed composition formula. Further, an excessive amount of the raw material (4) may be used as the flux.
以上のようにして式 （Ca1-i-j、Bai、Eu2+ j）2B5O9Cl （Ｉ） （式中、ｉは0.025≦ｉ≦0.32であり、かつｊは0.0005
≦ｊ≦0.25である）で表され、かつCIE表色系色度座標
のｙ値が0.06以上であることを特徴とする本発明のクロ
ロ硼酸塩系螢光体を製造することができる。As described above, the formula (Ca 1-ij , Ba i , Eu 2+ j ) 2 B 5 O 9 Cl (I) (where i is 0.025 ≦ i ≦ 0.32 and j is 0.0005
≦ j ≦ 0.25), and the y value of the CIE color system chromaticity coordinate is 0.06 or more, so that the chloroborate-based phosphor of the present invention can be produced.
尚、本発明の螢光体には、輝度等の特性を向上させる
ために前述のように２価の元素及び／又は３価の元素を
さらに含有させることができる。そのような元素の例と
して、ストロンチウム、マグネシウムおよび亜鉛を挙げ
ることができる。これらの元素の少なくとも１つを螢光
体に含有させることが好ましく、特にストロンチウムを
含有させることが、ｙ値を更に向上させることができる
点から特に好ましい。The phosphor of the present invention may further contain a divalent element and / or a trivalent element as described above in order to improve characteristics such as brightness. Examples of such elements include strontium, magnesium and zinc. It is preferable to contain at least one of these elements in the phosphor, and it is particularly preferable to contain strontium from the viewpoint that the y value can be further improved.
このようにして得られた本発明の螢光体は、従来の
（Ca、Eu2+）2B5O9Cl螢光体と紫外線、Ｘ線、真空紫外
線あるいは電子線励起下での発光色が異なり発光輝度も
高い青色発光を示す。The thus obtained phosphor of the present invention is the same as the conventional (Ca, Eu 2+ ) 2 B 5 O 9 Cl phosphor and the emission color under the excitation of ultraviolet rays, X-rays, vacuum ultraviolet rays or electron beams. However, blue light is emitted with high emission brightness.
第２図に、本発明の （Ca0.84Ba0.13Eu2+ 0.03）2B5O9Cl螢光体（曲線１）、
従来の（Ca0.97Eu2+ 0.03）2B5O9Cl螢光体（曲線２）お
よび（Ba0.97Eu2+ 0.03）2B5O9Cl螢光体（曲線３）の発
光スペクトルを示す。FIG. 2 shows the (Ca 0.84 Ba 0.13 Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor of the present invention (curve 1),
Shows the emission spectra of a conventional (Ca 0.97 Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor (curve 2) and (Ba 0.97 Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor (curve 3). .
本発明の（Ca0.84Ba0.13Eu2+ 0.03）2B5O9Cl螢光体
は、組成的には（Ca0.97Eu2+ 0.03）2B5O9Cl螢光体と（B
a0.97Eu2+ 0.03）2B5O9Cl螢光体の中間に位置するもので
ある。しかるに本発明の螢光体の発光スペクトルは、前
記GTEの論文の記載に反して曲線２と曲線３との中間に
位置せず、曲線２よりさらに長波長側に位置する。The (Ca 0.84 Ba 0.13 Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor of the present invention is (Ca 0.97 Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor in terms of composition.
a 0.97 Eu 2+ 0.03 ) 2 B 5 O 9 Cl Located in the middle of the phosphor. However, the emission spectrum of the phosphor of the present invention is not located in the middle of the curves 2 and 3 contrary to the description of the GTE article, but is located on the longer wavelength side than the curve 2.
即ち、本発明の螢光体は、従来のクロロ硼酸塩系螢光
体とは全く異なるスペクトルを有する新規なクロロ硼酸
塩系螢光体である。That is, the phosphor of the present invention is a novel chloroborate-based phosphor having a spectrum completely different from that of the conventional chloroborate-based phosphor.
さらに第１図に（Ca0.97-iBaiEu2+ 0.03）2B5O9Cl螢光
体のBa置換量ｉ値と紫外線励起下における発光色のCIE
表色系色度座標のｙ値との関係を示す。図中曲線ａは、
前記製法で造られた新規な発光スペクトルを示す本発明
の螢光体の特性曲線であり、曲線ｂは、従来の発光スペ
クトルを示す螢光体の特性曲線である（なお図中の△印
は前記GTEの論文に開示された螢光体のｙ値をプロット
したものである）第１図からも明らかな如く、曲線ａで
示される螢光体は、従来の螢光体の特性を示す曲線ｂと
全く異った発光色を示す。即ち、曲線ｂのｙ値を示す従
来の螢光体は、ｙ値が0.05に満たないのに対し、曲線ａ
でｙ値を示す螢光体のｙ値は最高0.087に達する。これ
ら２つのタイプの螢光体におけるこの様な発光の相違
は、発光中心となるエネルギーレベルが曲線ａの螢光体
と曲線ｂの螢光体とでは異っている事は明らかである。
しかし現状ではその相違を理論的に解析して螢光体の構
造等を定義する事は困難である。そこで本発明者等は従
来の螢光体（曲線ｂ）と明確に且つ十分に区別出来る、
ｙ値が0.06以上であり、その組成中のバリウム含有量を
カルシウム、バリウム及びユーロピウムの合計の50モル
％以下とする前記クロロ硼酸塩を本発明の螢光体とし
た。In addition, Fig. 1 shows the i-value of Ba substitution in the (Ca 0.97-i Ba i Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor and the CIE of the emission color under UV excitation.
The relationship with the y value of the chromaticity coordinates of the color system is shown. The curve a in the figure is
It is a characteristic curve of a phosphor of the present invention showing a novel emission spectrum produced by the above-mentioned manufacturing method, and a curve b is a characteristic curve of a phosphor showing a conventional emission spectrum (note that Δ in the figure indicates (The y value of the phosphor disclosed in the GTE article is plotted.) As is clear from FIG. 1, the phosphor shown by the curve a is a curve showing the characteristics of the conventional phosphor. The emission color is completely different from that of b. That is, in the conventional phosphor showing the y value of the curve b, the y value is less than 0.05, while the curve a
The maximum y value of the phosphor showing the y value reaches 0.087. It is clear that such a difference in light emission between these two types of phosphors is different between the phosphor having the curve a and the phosphor having the energy level serving as the emission center.
However, at present, it is difficult to theoretically analyze the difference and define the structure of the fluorescent body. Therefore, the present inventors can clearly and sufficiently distinguish from the conventional fluorescent substance (curve b).
The chloroborate having a y value of 0.06 or more and having a barium content in the composition of 50 mol% or less of the total of calcium, barium and europium was used as the phosphor of the present invention.
なお、本発明の螢光体のｙ値は通常0.095以下であ
り、上記バリウム含有量の下限は通常１モル％程度であ
る。The y value of the phosphor of the present invention is usually 0.095 or less, and the lower limit of the barium content is usually about 1 mol%.
又、第３図に（Ca0.97-iBaiEu2+ 0.03）2B5O9Cl螢光体
のBa置換量ｉ値と紫外線励起下における発光輝度との関
係を示す。図中縦軸の相対発光輝度は（Ca0.97E
u2+ 0.03）2B5O9Cl螢光体の発光輝度を100とした相対値
である。図中曲線ａは、前記製法で造られた新規な発光
スペクトルを示す本発明の螢光体の特性曲線であり、曲
線ｂは、従来の発光スペクトルを示す螢光体の特性曲線
である（なお△印は前記GTEの論文に開示された螢光体
の相対発光輝度をプロットしたものである）。第３図か
らも明らかな如く、本発明の螢光体は、輝度の点で従来
の螢光体と比較して数十％以上も高く、最高で約220％
の高輝度を示す。Further, FIG. 3 shows the relationship between the i-value of the Ba substitution amount of the (Ca 0.97-i Ba i Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor and the emission brightness under the excitation of ultraviolet rays. The relative emission brightness on the vertical axis in the figure is (Ca 0.97 E
u 2+ 0.03 ) 2 B 5 O 9 Cl This is a relative value with the emission brightness of the phosphor as 100. In the figure, a curve a is a characteristic curve of the phosphor of the present invention showing a novel emission spectrum produced by the above manufacturing method, and a curve b is a characteristic curve of a phosphor showing a conventional emission spectrum (note that The triangle mark is a plot of the relative emission brightness of the phosphor disclosed in the GTE article). As is clear from FIG. 3, the phosphor of the present invention is higher than the conventional phosphor by several tens of percent in terms of brightness, and the maximum of about 220%.
Of high brightness.
第１図及び第３図から明らかなように、本発明の螢光
体は0.025≦ｉ≦0.32の範囲において従来の（Ca0.97Eu
2+ 0.03）2B5O9Cl螢光体よりも高輝度かつ発光色のｙ値
が著しく高い発光を示す。なお現在多量に実用されてい
るBAM螢光体の紫外線励起下での代表的なｙ値と相対発
光輝度はそれぞれ、0.074および152％である。As is apparent from FIGS. 1 and 3, the phosphor of the present invention has a conventional (Ca 0.97 Eu) in the range of 0.025 ≦ i ≦ 0.32.
2+ 0.03 ) 2 B 5 O 9 Cl It emits light with higher brightness and a significantly higher y-value of emission color than the phosphor. The typical y-value and relative emission brightness under UV excitation of BAM phosphors, which are used in large quantities at present, are 0.074 and 152%, respectively.
即ち、本発明の螢光体は、発光特性（発光色及び発光
輝度）の点で従来のBAM螢光体と同等若しくは優れたも
のである。更に、本発明の螢光体は、BAM螢光体と比較
して低温で焼成して製造できるものでもあり、実用上極
めて価値の高いものである。That is, the phosphor of the present invention is equivalent to or superior to the conventional BAM phosphor in terms of emission characteristics (emission color and emission brightness). Furthermore, the phosphor of the present invention can be manufactured by firing at a lower temperature than the BAM phosphor, and is extremely valuable in practical use.
なお第１図から第３図まで総て紫外線励起により得ら
れた結果であるが、電子線励起、真空紫外線励起の場合
でも同じ傾向を示すことが確認された。It should be noted that all of FIGS. 1 to 3 are the results obtained by ultraviolet excitation, but it was confirmed that the same tendency was exhibited in the case of electron beam excitation and vacuum ultraviolet excitation.
以下本発明を実施例により説明する。 The present invention will be described below with reference to examples.
実施例１ 表１に示す螢光体原料を水を媒体としてペーストにし
て充分混合した。得られた混合物を140℃、８時間乾燥
し、150メッシュで篩った。篩分けた原料の2/3をるつぼ
に充填し、その上に石英クロスで覆ったカーボンの包を
載置し、更にその上に残りの原料1/3を充填し、更にそ
の上に石英クロスで覆ったカーボン包を載置し、蓋をし
た。るつぼと蓋の間は水ガラスで封着した。このるつぼ
を1030℃の温度でCO雰囲気中２時間焼成した。Example 1 The phosphor raw material shown in Table 1 was made into a paste using water as a medium and mixed sufficiently. The resulting mixture was dried at 140 ° C for 8 hours and sieved through 150 mesh. Fill a crucible with 2/3 of the sieved raw material, place a carbon wrapper covered with quartz cloth on top of it, and further fill the remaining raw material with 1/3 on top, then place a quartz cloth on top Was placed and covered with a lid. The space between the crucible and the lid was sealed with water glass. The crucible was baked at a temperature of 1030 ° C. in a CO atmosphere for 2 hours.
焼成後、焼成物を粉砕し、温水で数回洗浄し、乾燥
後、篩にかけた。こうして得られた螢光体は、組成式が
（Ca0.84Ba0.13Eu2+ 0.03）2B5O9Clであることが分析の
結果分かった。After firing, the fired product was crushed, washed several times with warm water, dried and sieved. As a result of analysis, it was found that the composition formula of the thus obtained phosphor was (Ca 0.84 Ba 0.13 Eu 2+ 0.03 ) 2 B 5 O 9 Cl.
この螢光体は、紫外線、真空紫外線、Ｘ線および電子
線励起下で青色発光を示した。紫外線励起下における発
光スペクトルを第２図（曲線１）に示す（ピーク波長45
2.5nm）。又、この螢光体の発光色はCIE表色系色度座標
のｙ値が0.085であった。又相対発光輝度はｙ値が0.047
の（Ca0.97Eu2+ 0.03）2B5O9Cl螢光体に比べて100％も高
かった（表２）。This phosphor emitted blue light under excitation of ultraviolet rays, vacuum ultraviolet rays, X-rays and electron beams. The emission spectrum under UV excitation is shown in Fig. 2 (curve 1) (peak wavelength 45
2.5 nm). Further, the emission color of this phosphor had a y value of 0.085 in the chromaticity coordinates of the CIE color system. The relative light emission brightness has a y value of 0.047.
It was 100% higher than that of the (Ca 0.97 Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor (Table 2).
尚、発光輝度は以下のようにして求めた。前面が透明
石英ガラスで出来たセルに螢光体を詰め、該前面を紫外
線ランプ（254nm）で照射し、励起紫外線の反射光をカ
ットするフィルターを有する輝度計で測定した。The emission brightness was determined as follows. A cell made of transparent quartz glass on the front surface was filled with a fluorescent substance, and the front surface was irradiated with an ultraviolet lamp (254 nm), and measurement was carried out with a luminance meter having a filter for cutting off reflected light of excited ultraviolet light.
実施例２〜４ 表１に示す螢光体原料を用いて実施例１と同様にして
本発明の螢光体を得た。得られた螢光体の組成式をそれ
ぞれ表２に示す。又得られた螢光体は、いずれも紫外
線、真空紫外線、Ｘ線及び電子線励起下で青色発光を示
した。紫外線励起下（254nm）における各螢光体のピー
ク波長CIE表色系色度座標のｙ値及び相対発光輝度を表
２に示す。Examples 2 to 4 The phosphor materials of the present invention were obtained in the same manner as in Example 1 except that the phosphor raw materials shown in Table 1 were used. The composition formulas of the obtained phosphors are shown in Table 2. The obtained phosphors all emitted blue light under excitation of ultraviolet rays, vacuum ultraviolet rays, X-rays and electron beams. Table 2 shows the peak wavelength CIE color system chromaticity coordinate y value and relative emission luminance of each phosphor under UV excitation (254 nm).
第１図は、（Ca0.97-iBaiEu2+ 0.03）2B5O9Cl螢光体のBa
置換量ｉ値と発光色のCIE表色系色度座標のｙ値との関
係を示す（曲線a:本発明の螢光体、曲線b:従来の螢光
体）。 第２図は、螢光体の紫外線励起下における発光スペクト
ルを示す（曲線1:（Ca0.84Ba0.13Eu2+ 0.03）2B5O9Cl、
曲線2:（Ca0.97Eu2+ 0.03）2B5O9Cl、曲線3:（Ba0.97Eu
2+ 0.03）2B5O9Cl。 第３図は、（Ca0.97-iBaiEu2+ 0.03）2B5O9Cl螢光体のBa
置換量ｉ値と発光輝度との関係を示す（曲線a:本発明の
螢光体、曲線b:従来の螢光体）。Figure 1 shows Ba of (Ca 0.97-i Ba i Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor.
The relationship between the i value of the substitution amount and the y value of the chromaticity coordinates of the CIE color system of the luminescent color is shown (curve a: phosphor of the present invention, curve b: conventional phosphor). Figure 2 shows the emission spectrum of the phosphor under UV excitation (curve 1: (Ca 0.84 Ba 0.13 Eu 2+ 0.03 ) 2 B 5 O 9 Cl,
Curve 2: (Ca 0.97 Eu 2+ 0.03 ) 2 B 5 O 9 Cl, Curve 3: (Ba 0.97 Eu
2+ 0.03 ) 2 B 5 O 9 Cl. Figure 3 shows (Ca 0.97-i Ba i Eu 2+ 0.03 ) 2 B 5 O 9 Cl phosphor Ba.
The relationship between the substitution amount i value and the emission brightness is shown (curve a: phosphor of the present invention, curve b: conventional phosphor).
Claims (1)
ウム・クロロ硼酸塩系青色蛍光体。 （Ca1-i-j、Bai、Eu2+ j）2B5O9Cl （Ｉ） （式中、ｉは0.025≦ｉ≦0.32であり、かつｊは0.005≦
ｊ≦0.25である）。1. A calcium / barium / chloroborate-based blue phosphor represented by the general formula (I). (Ca 1-ij , Ba i , Eu 2+ j ) 2 B 5 O 9 Cl (I) (In the formula, i is 0.025 ≦ i ≦ 0.32, and j is 0.005 ≦.
j ≦ 0.25).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155075A JPH0826311B2 (en) | 1987-06-22 | 1987-06-22 | Fluorescent body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155075A JPH0826311B2 (en) | 1987-06-22 | 1987-06-22 | Fluorescent body |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPS64189A JPS64189A (en) | 1989-01-05 |
| JPH01189A JPH01189A (en) | 1989-01-05 |
| JPH0826311B2 true JPH0826311B2 (en) | 1996-03-13 |
Family
ID=15598107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62155075A Expired - Fee Related JPH0826311B2 (en) | 1987-06-22 | 1987-06-22 | Fluorescent body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0826311B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE33142E (en) * | 1984-10-19 | 1990-01-09 | Hitachi, Ltd. | Centrifugal compressor |
| JPH04322972A (en) * | 1991-04-24 | 1992-11-12 | Osaka Diamond Ind Co Ltd | Binder material for diamond abrasive grain |
| JPH04322971A (en) * | 1991-04-24 | 1992-11-12 | Osaka Diamond Ind Co Ltd | Diamond grinding wheel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5679176A (en) * | 1979-11-30 | 1981-06-29 | Kasei Optonix Co Ltd | Fluorescent substance |
-
1987
- 1987-06-22 JP JP62155075A patent/JPH0826311B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS64189A (en) | 1989-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100417885B1 (en) | Aluminate Phosphor, Its Manufacturing Method And Vacuum Ultraviolet-Excitation Light Emitting Device | |
| US4647399A (en) | Process for producing Ce-Mn coactivated fluoroapatite phosphors as the yellow emitting component for high efficacy lamp blends | |
| US4751426A (en) | Fluorescent lamp using multi-layer phosphor coating | |
| US4353808A (en) | Phosphors and process for producing the same | |
| JP2001172623A (en) | Fluorescent substance and fluorescent lamp using the same | |
| EP2785815B1 (en) | Phosphor blends for fluorescent lamps | |
| JP3977551B2 (en) | Fluorescent substance for vacuum ultraviolet ray, phosphor paste composition, and vacuum ultraviolet ray excited light emitting device | |
| US5231328A (en) | Phosphor and ultraviolet ray excited fluorescent tube employing it | |
| JPH0826311B2 (en) | Fluorescent body | |
| KR100867289B1 (en) | Alkaline earth aluminate phosphor, phosphor paste composition and vacuum ultraviolet excitation light emitting element | |
| JP3856356B2 (en) | Phosphor paste composition and vacuum ultraviolet light-excited light emitting device | |
| JP5380790B2 (en) | Alkaline earth metal aluminate phosphor and fluorescent lamp using the same | |
| JPH1173138A (en) | Red light emitting phosphor, and plasma display device and noble gas discharging light emitting device using it | |
| US4233538A (en) | Luminescent lead-activated alkaline earth metal rare earth metal borates and mercury vapor discharge lamp containing the same | |
| JP2003027054A (en) | Aluminosilicate phosphor excitable with vacuum ultraviolet ray, method for producing the same, and vacuum-ultraviolet-ray-excitable luminescent element using the same | |
| KR100760870B1 (en) | Aluminate phosphor, process for producing the same, phosphor paste composition and vacuum ultraviolet-excited light-emitting device | |
| JPH01189A (en) | fluorescent material | |
| JPS61118489A (en) | Calcium halophosphate and its production | |
| EP0296531B1 (en) | Phospor process for its production and ultraviolet ray excited fluorescent tube employing it | |
| US4594178A (en) | Process for producing a yellow emitting phosphor | |
| JPH02228390A (en) | Highly color rendering fluorescent lamp | |
| KR960000869B1 (en) | Fluorescent material and its preparation method of the same | |
| JPH09291280A (en) | Fluorescent substance and fluorescent lamp | |
| KR800001170B1 (en) | Fluorescent material | |
| JPH0662946B2 (en) | Slow electron beam excited phosphor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |