JP5380790B2 - Alkaline earth metal aluminate phosphor and fluorescent lamp using the same - Google Patents
Alkaline earth metal aluminate phosphor and fluorescent lamp using the same Download PDFInfo
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Description
本発明は、アルカリ土類金属アルミン酸塩蛍光体及びそれを用いた蛍光ランプに関し、特に液晶表示装置のバックライトに使用される冷陰極蛍光ランプに関する。 The present invention relates to an alkaline earth metal aluminate phosphor and a fluorescent lamp using the same, and more particularly to a cold cathode fluorescent lamp used for a backlight of a liquid crystal display device.
液晶表示装置は液晶シャッターとバックライトとの組合わせによりパネル上に画像を表示する非発光形表示装置であって、バックライトには主として細管化しやすい冷陰極蛍光ランプが用いられている。そして、このようなバックライトに用いられる冷陰極蛍光ランプには、高光束で色再現範囲が広いことが求められている。また、冷陰極蛍光ランプ用蛍光体としては従来から３波長蛍光体が使用されており、青色発光蛍光体としてユウロピウム付活アルカリ土類金属アルミン酸塩蛍光体や、青緑色〜緑色発光蛍光体としてユウロピウム及びマンガン付活アルカリ土類金属アルミン酸塩蛍光体などが使用されている。しかしながら、これらのアルカリ土類金属アルミン酸塩蛍光体は蛍光ランプ作製時のベーキング工程において輝度低下や色度変化の問題があり、これらの蛍光体を用いた蛍光ランプはランプ光束が経時的に低下するという問題があった。 The liquid crystal display device is a non-light-emitting display device that displays an image on a panel by a combination of a liquid crystal shutter and a backlight, and a cold cathode fluorescent lamp that is easily thinned is mainly used for the backlight. A cold cathode fluorescent lamp used for such a backlight is required to have a high luminous flux and a wide color reproduction range. Further, as phosphors for cold cathode fluorescent lamps, three-wavelength phosphors are conventionally used. As blue light emitting phosphors, europium-activated alkaline earth metal aluminate phosphors and blue green to green light emitting phosphors are used. Europium and manganese activated alkaline earth metal aluminate phosphors are used. However, these alkaline earth metal aluminate phosphors have problems of luminance reduction and chromaticity change in the baking process when making fluorescent lamps, and fluorescent lamps using these phosphors have a decrease in lamp luminous flux over time. There was a problem to do.
ベーキング工程の輝度低下の問題に対し、特開平８−１４３８６３号公報等に、Ｓｍなどの希土類元素を添加したユウロピウム付活アルカリ土類金属アルミン酸塩蛍光体やユウロピウム及びマンガン付活アルカリ土類金属アルミン酸塩蛍光体が開示されているが、いずれも十分ではなく改良が求められていた。
本発明は、このような問題点を解決するためになされたものである。本発明の目的は、発光強度及びベーキング輝度維持率が高いアルカリ土類金属アルミン酸塩蛍光体を提供することであり、さらには、ランプ光束及び光束維持率が高く、色再現範囲の広い蛍光ランプを提供することである。 The present invention has been made to solve such problems. An object of the present invention is to provide an alkaline earth metal aluminate phosphor having a high emission intensity and a high baking luminance maintenance rate, and further, a fluorescent lamp having a high lamp luminous flux and a high luminous flux maintenance factor and a wide color reproduction range. Is to provide.
上記目的を達成するために本発明者らは鋭意検討を重ねた結果、特定の組成を有するアルカリ土類金属アルミン酸塩蛍光体は発光強度及びベーキング輝度維持率が高く、この蛍光体を用いた蛍光ランプはランプ光束及び光束維持率が高く、色再現範囲が広いことを新たに見いだし本発明を完成させるに至った。 In order to achieve the above object, the present inventors have conducted extensive studies, and as a result, the alkaline earth metal aluminate phosphor having a specific composition has high emission intensity and baking luminance maintenance rate, and this phosphor was used. The fluorescent lamp has a high lamp luminous flux and a luminous flux maintenance factor, and has newly found that the color reproduction range is wide, and has completed the present invention.
（１）本発明のアルカリ土類金属アルミン酸塩蛍光体は、母体元素がバリウム、ストロンチウム及びカルシウムから選択される少なくとも１種の元素と、マグネシウム及び亜鉛から選択される少なくとも１種の元素と、アルミニウムと、酸素からなり、付活剤元素がユウロピウム又はユウロピウム及びマンガンからなるアルカリ土類金属アルミン酸塩蛍光体において、蛍光体に対してリチウム、ナトリウム及びカリウムから選択される少なくとも１種の元素を０．１５〜１．６０モル％、フッ素、塩素、臭素及びヨウ素から選択される少なくとも１種の元素を０．０７〜２．１０モル％含有することを特徴とする。 (1) The alkaline earth metal aluminate phosphor of the present invention has at least one element selected from barium, strontium and calcium as a host element, and at least one element selected from magnesium and zinc; In an alkaline earth metal aluminate phosphor made of aluminum and oxygen and having an activator element made of europium or europium and manganese, at least one element selected from lithium, sodium and potassium is used for the phosphor It is characterized by containing 0.07 to 2.10 mol% of at least one element selected from 0.15 to 1.60 mol%, fluorine, chlorine, bromine and iodine.
（２）本発明のアルカリ土類金属アルミン酸塩蛍光体は、（1）に記載のアルカリ土類金属アルミン酸塩蛍光体であって、一般式が次式で表されることを特徴とする。
ａ（Ｍ１ １−ｘＥｕｘ）Ｏ・（Ｍ２ １−ｙＭｎｙ）Ｏ・ｂＡｌ２Ｏ３
（但し、Ｍ１はＢａ、Ｓｒ及びＣａから選択される少なくとも１種の元素、Ｍ２はＭｇ及びＺｎから選択される少なくとも１種の元素、０．８≦ａ≦１．２、４．６≦ｂ≦５．４、０．０３≦ｘ≦０．２、０≦ｙ≦０．３５）
(2) The alkaline earth metal aluminate phosphor of the present invention is the alkaline earth metal aluminate phosphor according to (1), wherein the general formula is represented by the following formula: .
a (M 1 1-x Eu x ) O. (M 2 1-y Mn y ) O.bAl 2 O 3
(However, M 1 is at least one element selected from Ba, Sr and Ca, M 2 is at least one element selected from Mg and Zn, 0.8 ≦ a ≦ 1.2, 4.6 ≦ b ≦ 5.4, 0.03 ≦ x ≦ 0.2, 0 ≦ y ≦ 0.35)
（３）本発明のアルカリ土類金属アルミン酸塩蛍光体は、（1）又は（２）に記載のアルカリ土類金属アルミン酸塩蛍光体であって、リチウム、ナトリウム及びカリウムから選択される少なくとも１種の元素の含有量ｍモル％と、フッ素、塩素、臭素及びヨウ素から選択される少なくとも１種の元素の含有量ｎモル％は、次式の関係を満たすことを特徴とする。
２．０≦３ｍ＋２ｎ≦５．２
(3) The alkaline earth metal aluminate phosphor of the present invention is the alkaline earth metal aluminate phosphor according to (1) or (2), which is at least selected from lithium, sodium and potassium The content m mol% of one element and the content n mol% of at least one element selected from fluorine, chlorine, bromine and iodine satisfy the relationship of the following formula.
2.0 ≦ 3m + 2n ≦ 5.2
（４）本発明のアルカリ土類金属アルミン酸塩蛍光体は、（1）又は（３）に記載のアルカリ土類金属アルミン酸塩蛍光体であって、前記蛍光体の平均粒径が５．５〜７．５μｍの範囲にあり、中央粒径が７．５〜１１．０μｍの範囲にあることを特徴とする。 (4) The alkaline earth metal aluminate phosphor of the present invention is the alkaline earth metal aluminate phosphor according to (1) or (3), wherein the phosphor has an average particle size of 5. It is in the range of 5 to 7.5 μm, and the median particle size is in the range of 7.5 to 11.0 μm.
（５）本発明のアルカリ土類金属アルミン酸塩蛍光体は、（1）又は（４）に記載のアルカリ土類金属アルミン酸塩蛍光体であって、前記蛍光体を５８０℃で１５分間ベーキングしたときの、ベーキング輝度維持率が８５％以上であり、色度ｘの変化量Δｘ、色度ｙの変化量Δｙがそれぞれ下記の数値範囲を満たすことを特徴とする。
ｌΔｘｌ≦０．００１５、ｌΔｙｌ≦０．００９５
(5) The alkaline earth metal aluminate phosphor of the present invention is the alkaline earth metal aluminate phosphor according to (1) or (4), wherein the phosphor is baked at 580 ° C. for 15 minutes. In this case, the baking luminance maintenance ratio is 85% or more, and the change amount Δx of chromaticity x and the change amount Δy of chromaticity y satisfy the following numerical ranges, respectively.
lΔxl ≦ 0.0015, lΔyl ≦ 0.0095
（６）本発明の蛍光ランプは、透光性気密容器と、透光性気密容器内に形成された蛍光体層と、透光性気密容器内に封入された放電媒体と、電極とを具備する蛍光ランプにおいて、前記蛍光体層は（１）乃至（５）に記載のアルカリ土類金属アルミン酸塩蛍光体を含むことを特徴とする。 (6) The fluorescent lamp of the present invention includes a light-transmitting airtight container, a phosphor layer formed in the light-transmitting airtight container, a discharge medium sealed in the light-transmitting airtight container, and an electrode. In the fluorescent lamp, the phosphor layer includes the alkaline earth metal aluminate phosphor described in (1) to (5).
（７）本発明の蛍光ランプは、（６）に記載の蛍光ランプであり、前記蛍光体層が（１）乃至（５）に記載のアルカリ土類金属アルミン酸塩蛍光体のみからなる蛍光ランプであって、１００時間点灯後の光束維持率が９５％以上であることを特徴とする。 (7) The fluorescent lamp according to the present invention is the fluorescent lamp according to (6), wherein the phosphor layer is composed only of the alkaline earth metal aluminate phosphor according to (1) to (5). The luminous flux maintenance factor after lighting for 100 hours is 95% or more.
（８）本発明の蛍光ランプは、（６）又は（７）に記載の蛍光ランプであって、前記蛍光ランプが冷陰極蛍光ランプであることを特徴とする。 (8) The fluorescent lamp of the present invention is the fluorescent lamp described in (6) or (7), wherein the fluorescent lamp is a cold cathode fluorescent lamp.
本発明の蛍光体は、紫外線励起による発光強度が高く、さらに蛍光ランプ作製時のベーキング工程において輝度低下や色度変化が少ないアルカリ土類金属アルミン酸塩蛍光体であり、本発明の蛍光体を用いることによって、ランプ光束及び光束維持率が高く、色再現範囲の広い蛍光ランプを提供することができる。 The phosphor of the present invention is an alkaline earth metal aluminate phosphor that has high emission intensity due to ultraviolet light excitation, and that has little reduction in luminance and change in chromaticity in the baking process when producing a fluorescent lamp. By using it, it is possible to provide a fluorescent lamp having a high lamp luminous flux and a luminous flux maintenance factor and a wide color reproduction range.
以下、本発明の実施の形態を図面に基づいて説明する。ただし、以下に示す実施の形態は、本発明の技術思想を具体化するためのアルカリ土類金属アルミン酸塩蛍光体及びそれを用いた蛍光ランプを例示するものであって、本発明はアルカリ土類金属アルミン酸塩蛍光体及びそれを用いた蛍光ランプを以下のものに特定しない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the embodiment described below exemplifies an alkaline earth metal aluminate phosphor for embodying the technical idea of the present invention and a fluorescent lamp using the same. The metal group aluminate phosphor and the fluorescent lamp using the same are not specified as follows.
ここで、本発明の一実施の形態に係るアルカリ土類金属アルミン酸塩蛍光体の製造方法について詳細に説明する。蛍光体原料として、バリウム、ストロンチウム及びカルシウムから選択される少なくとも１種の元素の化合物と、マグネシウム及び亜鉛から選択される少なくとも１種の元素の化合物と、アルミニウム化合物と、ユウロピウム化合物又はユウロピウム化合物及びマンガン化合物と、リチウム、ナトリウム及びカリウムから選択される少なくとも１種の元素の化合物と、フッ素、塩素、臭素及びヨウ素から選択される少なくとも１種の元素の化合物を混合し、原料混合物を得る。この原料混合物をルツボに充填後、炉内に入れ、還元性雰囲気中１２００〜１６００℃で焼成する。冷却後、焼成品を湿式で分散処理した後、分離乾燥して本発明のアルカリ土類金属アルミン酸塩蛍光体を得る。 Here, a method for producing an alkaline earth metal aluminate phosphor according to an embodiment of the present invention will be described in detail. As a phosphor raw material, a compound of at least one element selected from barium, strontium and calcium, a compound of at least one element selected from magnesium and zinc, an aluminum compound, a europium compound or a europium compound and manganese A compound, a compound of at least one element selected from lithium, sodium and potassium and a compound of at least one element selected from fluorine, chlorine, bromine and iodine are mixed to obtain a raw material mixture. After filling this raw material mixture into a crucible, it is placed in a furnace and fired at 1200 to 1600 ° C. in a reducing atmosphere. After cooling, the fired product is wet-dispersed and then separated and dried to obtain the alkaline earth metal aluminate phosphor of the present invention.
バリウム、ストロンチウム及びカルシウムから選択される少なくとも１種の元素の化合物と、マグネシウム及び亜鉛から選択される少なくとも１種の元素の化合物と、アルミニウム化合物と、ユウロピウム化合物又はユウロピウム化合物及びマンガン化合物については、酸化物又は熱分解により酸化物となる化合物が好ましく用いられる。例えば、炭酸塩、水酸化物、硝酸塩、シュウ酸塩などの高温で分解し酸化物となる化合物が好ましい。また、蛍光体を構成する元素を全部又は一部含む共沈物やこれらを仮焼して得られる酸化物を用いることもできる。リチウム、ナトリウム及びカリウムから選択される少なくとも１種の元素の化合物については、これらのアルカリ金属のハロゲン化物が好ましく用いられる。フッ素、塩素、臭素及びヨウ素から選択される少なくとも１種の元素の化合物については、バリウム、ストロンチウム、カルシウムなどのアルカリ土類金属のハロゲン化物が好ましく用いられる。これらの蛍光体原料をボールミル、Ｖ型混合機などで混合した後、アルミナ、石英、炭化珪素などのルツボに充填し、還元性雰囲気中、１２００〜１６００℃で２〜２０時間焼成することが好ましい。焼成温度が１２００℃より低いと反応が進まず、１６００℃より高いと焼結が過剰に進んで分散処理が困難となる。 For compounds of at least one element selected from barium, strontium and calcium, compounds of at least one element selected from magnesium and zinc, aluminum compounds, europium compounds or europium compounds and manganese compounds, oxidation Or a compound that becomes an oxide by thermal decomposition is preferably used. For example, a compound which decomposes at a high temperature and becomes an oxide such as carbonate, hydroxide, nitrate, oxalate is preferable. Further, a coprecipitate containing all or part of the elements constituting the phosphor or an oxide obtained by calcining these can be used. For the compound of at least one element selected from lithium, sodium and potassium, these alkali metal halides are preferably used. As the compound of at least one element selected from fluorine, chlorine, bromine and iodine, halides of alkaline earth metals such as barium, strontium and calcium are preferably used. After mixing these phosphor raw materials with a ball mill, a V-type mixer or the like, it is preferable to fill in a crucible such as alumina, quartz, or silicon carbide, and to fire in a reducing atmosphere at 1200 to 1600 ° C. for 2 to 20 hours. . If the firing temperature is lower than 1200 ° C., the reaction does not proceed. If the firing temperature is higher than 1600 ° C., the sintering proceeds excessively and the dispersion treatment becomes difficult.
このようにして、蛍光体に対してリチウム、ナトリウム及びカリウムから選択される少なくとも１種の元素を０．１５〜１．６０モル％、フッ素、塩素、臭素及びヨウ素から選択される少なくとも１種の元素を０．０７〜２．１０モル％含有することで、紫外線励起による発光強度が高く、さらに蛍光ランプ作製時のベーキング工程において輝度低下や色度変化が少ない本発明のアルカリ土類金属アルミン酸塩蛍光体を得ることができる。 Thus, at least one element selected from 0.15 to 1.60 mol%, fluorine, chlorine, bromine and iodine is selected from at least one element selected from lithium, sodium and potassium with respect to the phosphor. By containing 0.07 to 2.10 mol% of the element, the alkaline earth metal aluminate of the present invention has high light emission intensity due to ultraviolet excitation, and less luminance reduction and chromaticity change in the baking process when producing a fluorescent lamp. A salt phosphor can be obtained.
次に、本発明のアルカリ土類金属アルミン酸塩蛍光体を用いて冷陰極蛍光ランプを作製する。先ず、蛍光体とピロリン酸カルシウム、カルシウムバリウムボレート等の結着剤をニトロセルロース／酢酸ブチル溶液に添加し、これらを混合し懸濁させて蛍光体塗布懸濁液を調製する。得られた蛍光体塗布懸濁液をガラス管の内面に流し込み、その後これに温風を通じることで乾燥させ、ベーキング、排気、フィラメントの装着、口金の取り付けを行い、冷陰極蛍光ランプを得る。このようにして、ランプ光束及び光束維持率が高く、色再現範囲の広い冷陰極蛍光ランプを得ることができる。 Next, a cold cathode fluorescent lamp is produced using the alkaline earth metal aluminate phosphor of the present invention. First, a phosphor and a binder such as calcium pyrophosphate and calcium barium borate are added to a nitrocellulose / butyl acetate solution, and these are mixed and suspended to prepare a phosphor-coated suspension. The obtained phosphor-coated suspension is poured into the inner surface of the glass tube, and then dried by passing warm air through the glass tube, followed by baking, exhausting, attaching a filament, and attaching a base to obtain a cold cathode fluorescent lamp. In this way, a cold cathode fluorescent lamp having a high lamp luminous flux and a luminous flux maintenance factor and a wide color reproduction range can be obtained.
図１に、本発明の冷陰極蛍光ランプの一例を示す。ガラス等から成る透光性気密容器11の内壁には一種以上の蛍光体と結着剤から成る蛍光体層12が形成される。透光性気密容器11の内部にはネオン等の希ガス及び水銀蒸気から成る放電媒体13が封入され、透光性気密容器11の両端は一対の電極14a、14bによって封止される。両電極間に電圧をかけて放電媒体13に放電を起こさせ、その際励起された水銀から紫外線が放出され、該紫外線により蛍光体層12の蛍光体が励起されて発光する。
FIG. 1 shows an example of the cold cathode fluorescent lamp of the present invention. A
次に、本発明のアルカリ土類金属アルミン酸塩蛍光体の特性について図を用いて説明する。図２に、実施例１においてＮａＦの添加量を変化させて得られる（Ｂａ０．８５Ｅｕ０．１５）Ｏ・（Ｍｇ０．７Ｍｎ０．３）Ｏ・５Ａｌ２Ｏ３蛍光体について、５８０℃で１５分間ベーキングしたときのベーキング輝度維持率と３ｍ＋２ｎとの関係を示した。ここで、ｍとｎは、それぞれ蛍光体中のＮａ含有量（ｍモル％）とＦ含有量（ｎモル％）の値である。ここでＮａ含有量は原子吸光分析法により、Ｆ含有量はイオンクロマトグラフ法により測定した値である。この図から、ベーキング輝度維持率は３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲で高く、２．４≦３ｍ＋２ｎ≦４．８の範囲でより高く、３．０≦３ｍ＋２ｎ≦４．０の範囲でさらに高くなっていることがわかる。 Next, characteristics of the alkaline earth metal aluminate phosphor of the present invention will be described with reference to the drawings. FIG. 2 shows the (Ba 0.85 Eu 0.15 ) O. (Mg 0.7 Mn 0.3 ) O.5Al 2 O 3 phosphor obtained by changing the amount of NaF added in Example 1. The relationship between the baking luminance maintenance rate and 3m + 2n when baked at 580 ° C. for 15 minutes was shown. Here, m and n are values of Na content (m mol%) and F content (n mol%) in the phosphor, respectively. Here, the Na content is a value measured by atomic absorption spectrometry, and the F content is a value measured by ion chromatography. From this figure, the baking luminance maintenance rate is higher in the range of 3m + 2n in the range of 2.0 ≦ 3m + 2n ≦ 5.2, higher in the range of 2.4 ≦ 3m + 2n ≦ 4.8, and 3.0 ≦ 3m + 2n ≦ 4.0. It can be seen that the range is even higher.
図３に、上記蛍光体について、５８０℃で１５分間ベーキングしたときの色度ｘの変化量ｌΔｘｌと３ｍ＋２ｎとの関係を示した。ここで、ｌΔｘｌはΔｘの絶対値である。この図から、色度ｘの変化は３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲で少ないことがわかる。 FIG. 3 shows the relationship between the amount of change 1Δxl in chromaticity x and 3m + 2n when the phosphor is baked at 580 ° C. for 15 minutes. Here, lΔxl is the absolute value of Δx. From this figure, it can be seen that the change in chromaticity x is small when 3m + 2n is in the range of 2.0 ≦ 3m + 2n ≦ 5.2.
図４に、上記蛍光体について、５８０℃で１５分間ベーキングしたときの色度ｙの変化量ｌΔｙｌと３ｍ＋２ｎとの関係を示した。ここで、ｌΔｙｌはΔｙの絶対値である。この図から、色度ｙの変化も３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲で少ないことがわかる。 FIG. 4 shows the relationship between the amount of change 1Δyl in chromaticity y and 3m + 2n when the phosphor is baked at 580 ° C. for 15 minutes. Here, lΔyl is the absolute value of Δy. From this figure, it can be seen that the change in chromaticity y is also small when 3m + 2n is in the range of 2.0 ≦ 3m + 2n ≦ 5.2.
図５に、上記蛍光体について、蛍光体の平均粒径と３ｍ＋２ｎとの関係を示した。ここで、平均粒径は空気透過法によるフィッシャー・サブ・シーブ・サイザー（Ｆ.Ｓ.Ｓ.Ｓ）を用いて測定した値であり、一次粒子の大きさを示す。この図から、３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲において、蛍光体の平均粒径は５．５〜７．５μｍの範囲にあることがわかる。従来、青色発光するユウロピウム付活アルカリ土類金属アルミン酸塩蛍光体や青緑色〜緑色発光するユウロピウム及びマンガン付活アルカリ土類金属アルミン酸塩蛍光体を白色蛍光ランプに用いた場合、他の発光色の蛍光体に比べて比重が小さいため、蛍光体塗布懸濁液中の沈降速度が遅くなって、蛍光ランプの中央部と端部で色差が生じるという問題があった。このような管端色差の問題に対し、アルカリ土類金属アルミン酸塩蛍光体の粒径を他の発光色の蛍光体に比べて大きくし、平均粒径の範囲を５．５〜７．５μｍの範囲とすることで改善できる。 FIG. 5 shows the relationship between the average particle diameter of the phosphor and 3m + 2n for the phosphor. Here, the average particle diameter is a value measured using a Fischer sub-sieve sizer (FSSS) by the air permeation method, and indicates the size of primary particles. From this figure, it can be seen that the average particle diameter of the phosphor is in the range of 5.5 to 7.5 μm when 3m + 2n is in the range of 2.0 ≦ 3m + 2n ≦ 5.2. Conventionally, when europium-activated alkaline earth metal aluminate phosphors emitting blue light or europium and manganese-activated alkaline earth metal aluminate phosphors emitting blue-green to green are used in white fluorescent lamps, other light emission Since the specific gravity is smaller than that of the color phosphor, the sedimentation rate in the phosphor coating suspension is slow, and there is a problem that a color difference occurs between the central portion and the end portion of the fluorescent lamp. To solve the problem of the color difference at the end of the tube, the particle size of the alkaline earth metal aluminate phosphor is made larger than those of other luminescent color phosphors, and the average particle size range is 5.5 to 7.5 μm. It can be improved by setting the range.
図６に、上記蛍光体について、蛍光体の中央粒径と３ｍ＋２ｎとの関係を示した。ここで、中央粒径は電気抵抗法のコールターマルチサイザーII(コールター社製)を用いて測定した値であり、５０％粒子径（体積基準）を示す。この場合、粒子が強く凝集していると一次粒子にまで分散させることは難しく、凝集した二次粒子が測定にかかる。この図から、３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲において、蛍光体の中央粒径は７．５〜１１．０μｍの範囲にあることがわかる。 FIG. 6 shows the relationship between the median particle diameter of the phosphor and 3m + 2n for the phosphor. Here, the median particle diameter is a value measured using an electric resistance method of Coulter Multisizer II (manufactured by Coulter), and indicates a 50% particle diameter (volume basis). In this case, if the particles are strongly aggregated, it is difficult to disperse them to the primary particles, and the aggregated secondary particles are taken for measurement. From this figure, it can be seen that when 3m + 2n is in the range of 2.0 ≦ 3m + 2n ≦ 5.2, the median particle diameter of the phosphor is in the range of 7.5 to 11.0 μm.
上記蛍光体について、実施例１と同様にして単色蛍光ランプを作製し、初期ランプ光束と１００時間点灯後のランプ光束を測定し、初期ランプ光束を１００％にしたときの１００時間点灯後のランプ光束の値を、１００時間点灯後の光束維持率として求めた。図７に、単色蛍光ランプの１００時間点灯後の光束維持率と３ｍ＋２ｎとの関係を示した。この図から、１００時間点灯後の光束維持率は、３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲において高く、ランプ光束の低下が少ないことがわかる。 With respect to the phosphor, a monochromatic fluorescent lamp was produced in the same manner as in Example 1, the initial lamp light flux and the lamp light flux after 100 hours of lighting were measured, and the lamp after 100 hours of lighting when the initial lamp light flux was 100%. The value of the luminous flux was determined as the luminous flux maintenance factor after 100 hours of lighting. FIG. 7 shows the relationship between the luminous flux maintenance factor after lighting the monochromatic fluorescent lamp for 100 hours and 3m + 2n. From this figure, it can be seen that the luminous flux maintenance factor after 100 hours of lighting is high when 3 m + 2n is in the range of 2.0 ≦ 3 m + 2n ≦ 5.2, and the decrease in lamp luminous flux is small.
緑色蛍光体（Ｇ）として上記蛍光体を、青色蛍光体（Ｂ）として（Ｓｒ，Ｃａ，Ｂａ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ蛍光体を、赤色蛍光体（Ｒ）としてＹ２Ｏ３：Ｅｕ蛍光体を用い、それぞれ重量比でＢ：Ｇ：Ｒ＝５０：２０：３０の割合で混合した。この混合蛍光体について、実施例１と同様にして白色蛍光ランプを作製し、初期ランプ光束と１００時間点灯後のランプ光束を測定し、初期ランプ光束を１００％にしたときの１００時間点灯後のランプ光束の値を、１００時間点灯後の光束維持率として求めた。図８に、白色蛍光ランプの１００時間点灯後の光束維持率と３ｍ＋２ｎとの関係を示した。この図からも、１００時間点灯後の光束維持率は、３ｍ＋２ｎが２．０≦３ｍ＋２ｎ≦５．２の範囲において高く、ランプ光束の低下が少ないことがわかる。 The phosphor described above as the green phosphor (G), (Sr, Ca, Ba) 10 (PO 4 ) 6 Cl 2 : Eu phosphor as the blue phosphor (B), and Y 2 O as the red phosphor (R). 3 : Eu phosphors were used and mixed at a weight ratio of B: G: R = 50: 20: 30. For this mixed phosphor, a white fluorescent lamp was prepared in the same manner as in Example 1, the initial lamp light flux and the lamp light flux after 100 hours of lighting were measured, and after 100 hours of lighting when the initial lamp light flux was 100%. The value of the lamp luminous flux was determined as the luminous flux maintenance factor after 100 hours of lighting. FIG. 8 shows the relationship between the luminous flux maintenance factor after lighting the white fluorescent lamp for 100 hours and 3m + 2n. Also from this figure, it can be seen that the luminous flux maintenance factor after 100 hours of lighting is high when 3 m + 2n is in the range of 2.0 ≦ 3 m + 2n ≦ 5.2, and the decrease in lamp luminous flux is small.
以下、本発明の実施例について説明するが、本発明は具体的実施例のみに限定されるものではないことは言うまでもない。 Examples of the present invention will be described below, but it goes without saying that the present invention is not limited to specific examples.
［実施例１］
＜蛍光体＞
原料としてＢａＣＯ３０．８５ｍｏｌ、Ｅｕ２Ｏ３０．０７５ｍｏｌ、ＭｇＣＯ３０．７０ｍｏｌ、ＭｎＣＯ３０．３０ｍｏｌ、Ａｌ２Ｏ３５．０ｍｏｌ、ＮａＦ０．００６２ｍｏｌ、及びＭｇＦ２０．０５７ｍｏｌをボールミルで混合し、この原料混合物をアルミナルツボに充填して還元雰囲気中（２％Ｈ２／Ｎ２）で１４００℃で６時間焼成する。冷却後、水洗して過剰のハロゲン化物を洗浄し、分散処理を行い、篩を通した後、脱水乾燥して、一般式が（Ｂａ０．８５Ｅｕ０．１５）Ｏ・（Ｍｇ０．７０Ｍｎ０．３０）Ｏ・５Ａｌ２Ｏ３で表されるアルカリ土類金属アルミン酸塩蛍光体を得る。この蛍光体は、蛍光体に対しＮａ元素を０．５９モル％、Ｆ元素を０．９０モル％含有し、２５４ｎｍ紫外線励起で緑色に発光する。この場合、３ｍ＋２ｎ＝３×０．５９＋２×０．９０＝３．５７である。
[Example 1]
<Phosphor>
BaCO 3 0.85 mol, Eu 2 O 3 0.075 mol, MgCO 3 0.70 mol, MnCO 3 0.30 mol, Al 2 O 3 5.0 mol, NaF 0.0062 mol, and MgF 2 0.057 mol were mixed in a ball mill as raw materials. Then, the raw material mixture is filled in an alumina crucible and fired at 1400 ° C. for 6 hours in a reducing atmosphere (2% H 2 / N 2 ). After cooling, washing with water to remove excess halide, dispersing, passing through a sieve, dehydrating and drying, the general formula is (Ba 0.85 Eu 0.15 ) O. (Mg 0.70 An alkaline earth metal aluminate phosphor represented by Mn 0.30 ) O.5Al 2 O 3 is obtained. This phosphor contains 0.59 mol% Na element and 0.90 mol% F element with respect to the phosphor, and emits green light when excited with UV light at 254 nm. In this case, 3m + 2n = 3 × 0.59 + 2 × 0.90 = 3.57.
＜単色蛍光ランプ＞
このようにして得られる蛍光体と結着剤をニトロセルロース／酢酸ブチル溶液に添加し、これらを混合して蛍光体塗布スラリーを調製する。これを管径３ｍｍ、長さ４００ｍｍのガラス管に流し込み、その内面に塗布し、温風を通じて乾燥し、５８０℃で１５分間塗布バルブをベーキングして、蛍光膜を形成する。その後、通常の方法に従い、排気、電極のマウント、口金の取り付けを行い、緑色に発光する単色冷陰極蛍光ランプを得る。
<Single color fluorescent lamp>
The phosphor thus obtained and the binder are added to a nitrocellulose / butyl acetate solution and mixed to prepare a phosphor coating slurry. This is poured into a glass tube having a tube diameter of 3 mm and a length of 400 mm, applied to the inner surface, dried through warm air, and baked at 580 ° C. for 15 minutes to form a fluorescent film. Then, according to a normal method, exhaust, electrode mounting, and attachment of a base are performed to obtain a monochrome cold cathode fluorescent lamp that emits green light.
＜白色蛍光ランプ＞
次に、緑色発光の上記アルカリ土類金属アルミン酸塩蛍光体と、（Ｓｒ，Ｃａ，Ｂａ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ青色発光蛍光体と、Ｙ２Ｏ３：Ｅｕ赤色発光蛍光体を重量比で青色：緑色：赤色＝５０：２０：３０の割合で混合する。この混合蛍光体と結着剤をニトロセルロース／酢酸ブチル溶液に添加し、混合して蛍光体塗布スラリーを調製する。これを管径３ｍｍ、長さ４００ｍｍのガラス管に流し込み、その内面に塗布し、温風を通じて乾燥し、５８０℃で１５分間塗布バルブをベーキングして、蛍光膜を形成する。その後、通常の方法に従い、排気、電極のマウント、口金の取り付けを行い、白色冷陰極蛍光ランプを得る。
上記アルカリ土類金属アルミン酸塩蛍光体、単色蛍光ランプ、及び白色蛍光ランプの測定結果を、表２及び表３に示す。
<White fluorescent lamp>
Next, the alkaline earth metal aluminate phosphor emitting green light, (Sr, Ca, Ba) 10 (PO 4 ) 6 Cl 2 : Eu blue light emitting phosphor, and Y 2 O 3 : Eu red light emitting fluorescence. The body is mixed in a weight ratio of blue: green: red = 50: 20: 30. This mixed phosphor and binder are added to a nitrocellulose / butyl acetate solution and mixed to prepare a phosphor-coated slurry. This is poured into a glass tube having a tube diameter of 3 mm and a length of 400 mm, applied to the inner surface, dried through warm air, and baked at 580 ° C. for 15 minutes to form a fluorescent film. Then, according to a normal method, exhaust, electrode mounting, and attachment of a base are performed to obtain a white cold cathode fluorescent lamp.
Tables 2 and 3 show the measurement results of the alkaline earth metal aluminate phosphor, the monochromatic fluorescent lamp, and the white fluorescent lamp.
［実施例２〜４］
蛍光体原料のうちＮａＦとＭｇＦ２を表１に示した量で混合する以外は実施例１と同様にして、アルカリ土類金属アルミン酸塩蛍光体、単色蛍光ランプ、及び白色蛍光ランプを作製し、測定結果を表２及び表３に示す。
[Examples 2 to 4]
An alkaline earth metal aluminate phosphor, a single color fluorescent lamp, and a white fluorescent lamp were prepared in the same manner as in Example 1 except that NaF and MgF 2 were mixed in the amounts shown in Table 1 among the phosphor raw materials. The measurement results are shown in Tables 2 and 3.
［実施例５］
蛍光体原料のうちＮａＦの代わりにＬｉＦを０．００６２ｍｏｌ使用する以外は実施例１と同様にして、アルカリ土類金属アルミン酸塩蛍光体を作製する。この蛍光体の平均粒径は５．３μｍ、中央粒径は７．６μｍである。
[Example 5]
An alkaline earth metal aluminate phosphor is produced in the same manner as in Example 1 except that 0.0062 mol of LiF is used instead of NaF among the phosphor raw materials. This phosphor has an average particle size of 5.3 μm and a median particle size of 7.6 μm.
［実施例６］
蛍光体原料のうちＮａＦの代わりにＫＦを０．００６２ｍｏｌ使用する以外は実施例１と同様にして、アルカリ土類金属アルミン酸塩蛍光体を作製する。この蛍光体の平均粒径は７．３μｍ、中央粒径は１０．３μｍである。
[Example 6]
An alkaline earth metal aluminate phosphor is produced in the same manner as in Example 1 except that 0.0062 mol of KF is used instead of NaF in the phosphor raw material. This phosphor has an average particle size of 7.3 μm and a median particle size of 10.3 μm.
［比較例１］
蛍光体原料のうちＮａＦとＭｇＦ２を表１に示した量で混合する以外は実施例１と同様にして、アルカリ土類金属アルミン酸塩蛍光体、単色蛍光ランプ、及び白色蛍光ランプを作製し、測定結果を表２及び表３に示す。
[Comparative Example 1]
An alkaline earth metal aluminate phosphor, a single color fluorescent lamp, and a white fluorescent lamp were prepared in the same manner as in Example 1 except that NaF and MgF 2 were mixed in the amounts shown in Table 1 among the phosphor raw materials. The measurement results are shown in Tables 2 and 3.
実施例１〜４及び比較例１で得られるアルカリ土類金属アルミン酸塩蛍光体について、蛍光体中のＮａ含有量（ｍモル％）とＦ含有量（ｎモル％）の値を表２に示す。また、蛍光体の平均粒径、中央粒径も表２に示す。この表から、本発明の蛍光体の平均粒径が５．５〜７．５μｍの範囲にあり、中央粒径が７．５〜１１．０μｍの範囲にあることがわかる。さらに、これらの蛍光体について、５８０℃で１５分間ベーキングしたときの、ベーキング輝度維持率、色度ｘの変化量ｌΔｘｌ、色度ｙの変化量ｌΔｙｌも表２に示す。この表から、本発明の蛍光体は下記の数値範囲を満たすことがわかる。
ｌΔｘｌ≦０．００１５、ｌΔｙｌ≦０．００９５
Regarding the alkaline earth metal aluminate phosphors obtained in Examples 1 to 4 and Comparative Example 1, Table 2 shows the values of Na content (mmol%) and F content (nmol%) in the phosphor. Show. Table 2 also shows the average particle diameter and the median particle diameter of the phosphor. From this table, it can be seen that the average particle size of the phosphor of the present invention is in the range of 5.5 to 7.5 μm and the median particle size is in the range of 7.5 to 11.0 μm. Further, Table 2 also shows the baking luminance maintenance ratio, the chromaticity x change amount lΔxl, and the chromaticity y change amount lΔyl when these phosphors are baked at 580 ° C. for 15 minutes. From this table, it can be seen that the phosphor of the present invention satisfies the following numerical range.
lΔxl ≦ 0.0015, lΔyl ≦ 0.0095
実施例１〜４及び比較例１で得られる単色蛍光ランプ及び白色蛍光ランプについて、１００時間点灯後の光束維持率を表３に示す。この表から、本発明の実施例の蛍光ランプはいずれも１００時間点灯後の光束維持率が９５％以上であり、比較例の蛍光ランプに比べて光束維持率が高いことがわかる。 Table 3 shows the luminous flux maintenance factor after lighting for 100 hours for the monochromatic fluorescent lamp and the white fluorescent lamp obtained in Examples 1 to 4 and Comparative Example 1. From this table, it can be seen that the fluorescent lamps of the examples of the present invention all have a luminous flux maintenance factor of 95% or more after lighting for 100 hours, and the luminous flux maintenance factor is higher than that of the fluorescent lamp of the comparative example.
以上に述べたように、本発明によって、紫外線励起による発光強度が高く、さらに蛍光ランプ作製時のベーキング工程において輝度低下や色度変化が少ないアルカリ土類金属アルミン酸塩蛍光体を提供することができ、さらに、ランプ光束及び光束維持率が高く、色再現範囲の広い蛍光ランプを提供することができる。 As described above, according to the present invention, it is possible to provide an alkaline earth metal aluminate phosphor that has high emission intensity due to ultraviolet excitation and that has little reduction in luminance and change in chromaticity in the baking process when producing a fluorescent lamp. Further, it is possible to provide a fluorescent lamp having a high lamp luminous flux and a luminous flux maintenance factor and a wide color reproduction range.
11 透光性気密容器
12 蛍光体層
13 放電媒体
14a、14b 電極
11 Translucent airtight container
12 Phosphor layer
13 Discharge medium
14a, 14b electrode
Claims (6)
ａ（Ｍ１ １−ｘＥｕｘ）Ｏ・（Ｍｇ１−ｙＭｎｙ）Ｏ・ｂＡｌ２Ｏ３
（但し、Ｍ１は、Ｂａであり、ａ、ｂ、ｘ、ｙについて、０．８≦ａ≦１．２、４．６≦ｂ≦５．４、０．０３≦ｘ≦０．２、０＜ｙ≦０．３５である。）
蛍光体に対してナトリウムを０．１５〜１．６０モル％含有し、フッ素を０．０７〜２．１０モル％含有しており、
ナトリウムの含有量ｍモル％と、フッ素の含有量ｎモル％は、２．０≦３ｍ＋２ｎ≦５．２の関係を満たすことを特徴とするアルカリ土類金属アルミン酸塩蛍光体。 An alkaline earth metal aluminate phosphor represented by the following general formula:
a (M 1 1-x Eu x ) O. (Mg 1-y M n y ) O.bAl 2 O 3
(However, M 1 is a Ba, a, b, x, for y, 0.8 ≦ a ≦ 1.2,4.6 ≦ b ≦ 5.4,0.03 ≦ x ≦ 0.2, 0 <y ≦ 0.35.)
Containing 0.15 to 1.60 mol% sodium and 0.07 to 2.10 mol% fluorine with respect to the phosphor,
An alkaline earth metal aluminate phosphor, wherein the sodium content (m mol%) and the fluorine content (n mol%) satisfy a relationship of 2.0 ≦ 3 m + 2n ≦ 5.2.
｜Δｘ｜≦０．００１５、｜Δｙ｜≦０．００９５ A baking luminance maintenance ratio when the phosphor is baked at 580 ° C. for 15 minutes is 85% or more, and a change amount Δx of chromaticity x and a change amount Δy of chromaticity y satisfy the following numerical ranges, respectively. 3. The alkaline earth metal aluminate phosphor according to 1 or 2.
| Δx | ≦ 0.0015, | Δy | ≦ 0.0095
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