JP3595380B2 - White phosphorescent phosphor - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は白色蓄光性蛍光体、更に詳しくは可視光下では白色の体色を有し、耐光性に優れると共に、極めて長時間にわたって高輝度の残光特性を有する白色蓄光性蛍光体に関するものである。
【０００２】
【従来の技術】
一般に蛍光体の残光時間は極めて短く、外部刺激を停止すると速やかにその発光は減衰するが、まれに紫外線等で刺激した後その刺激を停止した後もかなりの長時間（数１０分〜数時間）に渡り残光が肉眼で認められるものがあり、これらを通常の蛍光体とは区別して蓄光性蛍光体あるいは燐光体と呼んでいる。
【０００３】
この蓄光性蛍光体としては、ＣａＳ：Ｂｉ（紫青色発光），ＣａＳｒＳ：Ｂｉ（青色発光），ＺｎＳ：Ｃｕ（緑色発光），ＺｎＣｄＳ：Ｃｕ（黄色〜橙色発光）等の硫化物蛍光体が知られているが、これらのいずれの硫化物蛍光体も、化学的に不安定であったり、耐光性に劣るなど実用面での問題点が多い。
現在市場でもっぱら用いられる硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）も、特に湿気が存在すると紫外線により光分解して黒変したり輝度低下するため、屋外で直接日光に曝されるような用途での使用は困難であり、夜光時計や避難誘導標識、屋内の夜間表示等その用途は限定されていた。
【０００４】
またこの硫化亜鉛系蛍光体を夜光時計に用いる場合であっても、肉眼でその時刻を認識可能な残光時間は約３０分から２時間程度であり、実用的には、蛍光体に放射性物質を添加しそのエネルギーで刺激して常時発光する自発光性の夜光塗料を用いざるを得ないのが現状であった。
そこで本発明者は、前述のごとき現状に鑑み、市販の硫化物系蛍光体に比べて遥かに長時間の残光特性を有し、更には化学的にも安定であり、かつ長期にわたり耐光性に優れる蓄光性蛍光体として、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体を提供している。
【０００５】
ただ、前述した硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）も、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体も、体色が緑色であり、したがって緑色に見えても不都合でない場所にしか用いることができないものであった。
一方、体色を白色にしておくと、そのままでも使用しやすいだけでなく、他の顔料等の添加により所望の色とすることができるので、使用範囲が広がることとなるものの、極めて長時間にわたって高輝度の残光特性を有する蓄光性蛍光体のうちで、体色が白色のものが存在しなかった。
【０００６】
【発明が解決しようとする課題】
そこで本発明者は、前述のごとき現状に鑑み、市販の硫化物系蛍光体に比べて遥かに長時間の残光特性を有し、更には化学的にも安定であり、かつ長期にわたり耐光性に優れると共に、通常の可視光下で体色が白色に見える白色蓄光性蛍光体の提供を目的としたものである。
【０００７】
【課題を解決するための手段】
前述したような白色蓄光性蛍光体として、請求項１記載の発明は、ＳｒＡｌ2Ｏ4：Ｅｕ，Ｄｙからなる蓄光性蛍光体に、Ｅｒ2Ｏ3をＳｒＡｌ 2 Ｏ 4 ：Ｅｕ，Ｄｙに対して１〜１５重量％添加したことを特徴とする。
請求項２記載の発明は、ＳｒＡｌ2Ｏ4：Ｅｕ，Ｄｙからなり、ＥｕをＳｒに対して、１≦Ｅｕ≦１０ｍｏｌ％の範囲で添加し、更にＥｕとＤｙとを、３≦Ｄｙ／Ｅｕ≦７０の比で添加し、更にＳｒを３０ｍｏｌ％以上とした蓄光性蛍光体に、Ｅｒ2Ｏ3をＳｒＡｌ 2 Ｏ 4 ：Ｅｕ，Ｄｙに対して１〜１５重量％添加したことを特徴とする。
【０００８】
またこれらの白色蓄光性蛍光体の合成に際しては、フラックスとしてたとえば硼酸を １〜１０重量％の範囲で添加することができる。ここで添加量が、 １重量％以下であるとフラックス効果がなくなるし、１０重量％を越えると固化し、その後の粉砕、分級作業が困難となる。
【０００９】
【実施例】
本発明の発明者らは、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体が、耐光性に優れると共に、極めて長時間にわたって高輝度の残光特性を有することを確認している。
このようなＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体の反射率は、図１に示したように、約５２０ｎｍの波長にピークを有している。
【００１０】
ここにおいて、可視光領域の各波長の反射率がほぼ等しい場合には、可視光下で白色と認識されるものの、このようにピークを有している場合には、ピークの波長に対応した色が認識されることとなる。
したがって、約５２０ｎｍの波長にピークを有しているＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体は、可視光下で、緑色として認識されることとなる。
【００１１】
そこで、次に、発明者らは、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体のピークである約５２０ｎｍで低い反射率を有し、かつＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体の反射率が低下し始める５００ｎｍ程度から高い反射率を有する物質のうちで、極めて長時間にわたって高輝度の残光特性を有する点を疎外しない物質を、種々の実験によって捜した。
【００１２】
その結果、Ｅｒ２ Ｏ３ が好適であることがわかった。
反射率で説明すると、図１に示したように、Ｅｒ２ Ｏ３ は、約４４０ｎｍ、４８０ｎｍ、６２０ｎｍに高い反射率を有し、約５４０ｎｍに一番低い反射率を示しているものである。そして約６２０ｎｍのピークに起因して、可視光下ではごく薄いピンク色に見えるものである。
【００１３】
なお図１に示したように、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体に、Ｅｒ２ Ｏ３ を７重量％添加したものを例にすると、約４５０ｎｍから６５０ｎｍの可視光域の間がほぼ平滑化され、可視光下では白色として認識されることとなる。
更に、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体に、Ｅｒ２ Ｏ３ を添加するに際して、添加量を種々変更して、輝度及び白色度を測定した結果を、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）の輝度及び白色度と共に表１に示してある。
【００１４】
ここにおける輝度は、４００ｌｘの照射を２０分間継続した直後の輝度を１として、この輝度との相対輝度として示したものである。また白色度は、完全な白を１００として捕らえた時の程度を示したものである。なおＥｒ２ Ｏ３ 量（％）は、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体に対するＥｒ２ Ｏ３ の添加量を、重量％で示したものである。
【００１５】
更にここで使用するＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体は、
ＳｒＣＯ３ ：０．８３ｍｏｌ％
Ａｌ２ Ｏ３ ：１．００ｍｏｌ％
Ｅｕ２ Ｏ ３：０．０１０ｍｏｌ％
Ｄｙ２ Ｏ ３：０．０７５ｍｏｌ％
の比率のものであり、最終的には、
（Ｓｒ０．８３Ｅｕ０．０２Ｄｙ０．１５）Ａｌ２ Ｏ４
の蓄光性蛍光体を用いている。
【００１６】
【表１】
この表から、Ｅｒ２ Ｏ３ の添加量が増加するにしたがって、輝度が低下していくことがわかる。ただし、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）の輝度を比較対象にすると、Ｅｒ２ Ｏ３ の添加量が１５重量％の場合であっても、１０分後に４．９１倍の輝度を示しているものである。またＥｒ２ Ｏ３ の添加量を２０重量％とした場合であっても、１０分後に３．３６倍の輝度を有していることが確認されている。したがって、Ｅｒ２ Ｏ３ を添加した場合であっても、従来から用いられていた硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）に比べて、極めて長時間にわたって高輝度の残光特性を有することが確認された。
【００１８】
また白色度に関しては、Ｅｒ２ Ｏ３ の添加量を増やすにしたがって徐々に増加するものの、７重量％程度の場合をピークにして、それ以上添加しても逆に白色度は低下するものである。そして、Ｅｒ２ Ｏ３ の添加量を２０重量％とすると、Ｅｒ２ Ｏ３ の添加量が０重量％であるＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体の白色度とほぼ等しくなってしまう。
【００１９】
そこで、これら輝度と白色度とを勘案すると、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体に対するＥｒ２ Ｏ３ の添加量は、１〜１５重量％の範囲が好適であることが確認された。
更に以上の説明では、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体として、（Ｓｒ０．８３Ｅｕ０．０２Ｄｙ０．１５）Ａｌ２ Ｏ４ を用いた場合で説明したが、Ｓｒ、Ｅｕ、Ｄｙの比率が他の比率であっても、同様の傾向を示し、Ｅｒ２ Ｏ３ の添加量は、１〜１５重量％の範囲が好適であることが確認された。
【００２０】
また更に、３０分後輝度、１００分後輝度においても、同様の傾向にあることが確認されている。
次に、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体において、まず最初に、ＥｕをＳｒに対する添加量ごとに、ＥｕとＤｙとの比を変更した場合について実験した。
【００２１】
表２は、Ｅｕを０．０１ｍｏｌ添加し、更にＤｙを０．０５ｍｏｌ〜０．７ｍｏｌ（５≦Ｄｙ／Ｅｕ≦７０）の範囲で変化させた試料の添加量を示したものである。そしてこの各試料に対応した１０分後輝度、３０分後輝度、１００分後輝度及び白色度を、表３に示す。
【００２２】
【表２】
【表３】
ここでは、Ｅｕを０．０１ｍｏｌ添加し、更にＤｙを０．０５ｍｏｌ〜０．７ｍｏｌ（５≦Ｄｙ／Ｅｕ≦７０）の範囲で変化させた試料のすべてにわたって、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも輝度及び白色度が向上していることが確認された。
表４は、Ｅｕを０．０２ｍｏｌ添加し、更にＤｙを０．１０ｍｏｌ〜０．８ｍｏｌ（５≦Ｄｙ／Ｅｕ≦４０）の範囲で変化させた試料の添加量を示したものである。そしてこの各試料に対応した１０分後輝度、３０分後輝度、１００分後輝度及び白色度を、表５に示す。
【００２５】
【表４】
【表５】
ここでは、Ｅｕを０．０２ｍｏｌ添加し、更にＤｙを０．１０ｍｏｌ〜０．８ｍｏｌ（５≦Ｄｙ／Ｅｕ≦４０）の範囲で変化させた試料のすべてにわたって、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも輝度及び白色度が等しいか若しくは向上していることが確認された。
表６は、Ｅｕを０．０３ｍｏｌ添加し、更にＤｙを０．１０ｍｏｌ〜０．９ｍｏｌ（３．３≦Ｄｙ／Ｅｕ≦３０）の範囲で変化させた試料の添加量を示したものである 。そしてこの各試料に対応した１０分後輝度、３０分後輝度、１００分後輝度及び白色度を、表７に示す。
【００２８】
【表６】
【表７】
ここでは、Ｅｕを０．０３ｍｏｌ添加し、更にＤｙを０．１０ｍｏｌ〜０．９ｍｏｌ（３．３≦Ｄｙ／Ｅｕ≦３０）の範囲で変化させた試料のうちで、０．１０ｍｏｌ〜０．８ｍｏｌ（３．３≦Ｄｙ／Ｅｕ≦２６．７）の範囲では、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも輝度及び白色度が向上していることが確認された。一方、Ｅｕを０．０３ｍｏｌ添加し、更にＤｙを０．９ｍｏｌ（Ｄｙ／Ｅｕ＝３０）添加した場合については、輝度において硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも劣っている。このことは、ＳｒＣＯ３ の添加量が少なくなり過ぎたことが原因であると思われる。そこで、実験を行った確認したところ、Ｓｒが０．１ｍｏｌ（１０ｍｏｌ％）以下になると、輝度において硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも劣ってくることが確認された。
【００３１】
表８は、Ｅｕを０．０５ｍｏｌ添加し、更にＤｙを０．１５ｍｏｌ〜０．８ｍｏｌ（３≦Ｄｙ／Ｅｕ≦１６）の範囲で変化させた試料の添加量を示したものである。そしてこの各試料に対応した１０分後輝度、３０分後輝度、１００分後輝度及び白色度を、表９に示す。
【００３２】
【表８】
【表９】
ここでは、Ｅｕを０．０５ｍｏｌ添加し、更にＤｙを０．１５ｍｏｌ〜０．８ｍｏｌ（３≦Ｄｙ／Ｅｕ≦１６）の範囲で変化させた試料のすべてにわたって、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも輝度及び白色度が等しいか若しくは向上していることが確認された。
表１０は、Ｅｕを０．１ｍｏｌ添加し、更にＤｙを０．３ｍｏｌ〜０．７ｍｏｌ（３≦Ｄｙ／Ｅｕ≦７）の範囲で変化させた試料の添加量を示したものである。そしてこの各試料に対応した１０分後輝度、３０分後輝度、１００分後輝度及び白色度を、表１１に示す。
【００３５】
【表１０】
【表１１】
ここでは、Ｅｕを０．１ｍｏｌ添加し、更にＤｙを０．３ｍｏｌ〜０．７ｍｏｌ（３≦Ｄｙ／Ｅｕ≦７）の範囲で変化させた試料のすべてにわたって、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも輝度及び白色度が等しいか若しくは向上していることが確認された。
次に、各試料にＥｒ２ Ｏ３ を７重量％添加した場合について測定した。その結果を表１２として添付する。
【００３８】
【表１２】
ここでは、各試料共に、輝度が若干低下し、白色度が向上していることが確認できた。このことから、ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなり、ＥｕをＳｒに対して、１≦Ｅｕ≦１０ｍｏｌ％の範囲で添加し、更にＥｕとＤｙとを、３≦Ｄｙ／Ｅｕ≦７０の比で添加した蓄光性蛍光体に、Ｅｒ２ Ｏ３ を７重量％添加することによって、硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも輝度及び白色度が向上していることが確認された。
【００４０】
更に同様に、Ｅｒ２ Ｏ３ を１〜１５重量％添加した場合について測定した結果、表１２と同様に、輝度が若干低下し、白色度が向上していることが確認できた。
また次に、試料１−１から試料５−３について、Ｅｒ２ Ｏ３ を１〜１５重量％添加した場合について測定した結果、Ｅｒ２ Ｏ３ 添加に伴なう白色度の向上は見られたものの、Ｓｒが０．３ｍｏｌ（３０ｍｏｌ％）以下になると、輝度において硫化亜鉛系蓄光性蛍光体（ＺｎＳ：Ｃｕ）よりも劣ってくることが確認された。
【００４１】
【発明の効果】
以上説明したように、本発明は、市販の硫化物系蛍光体に比べて遥かに長時間の残光特性を有し、更には化学的にも安定であり、かつ長期にわたり耐光性に優れると共に、通常の可視光下で体色が白色に見えるものである。
【図面の簡単な説明】
【図１】ＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体の反射率、Ｅｒ２ Ｏ３ の反射率、及びＳｒＡｌ２ Ｏ４ ：Ｅｕ，Ｄｙからなる蓄光性蛍光体にＥｒ２ Ｏ３ を７重量％添加した白色蓄光性蛍光体の反射率を示したグラフである。[0001]
[Industrial applications]
The present invention relates to a white phosphorescent phosphor, and more particularly, to a white phosphorescent phosphor having a white body color under visible light, having excellent light resistance, and having a high luminance afterglow characteristic for an extremely long time. is there.
[0002]
[Prior art]
In general, the afterglow time of the phosphor is extremely short, and its emission is rapidly attenuated when the external stimulus is stopped, but rarely after being stimulated with ultraviolet light or the like, the stimulus is stopped for a considerably long time (several tens of minutes to several For some cases, afterglow is visible to the naked eye over time, and these are called phosphorescent phosphors or phosphorescent phosphors to distinguish them from ordinary phosphors.
[0003]
As the phosphorescent phosphor, sulfide phosphors such as CaS: Bi (purple blue light emission), CaSrS: Bi (blue light emission), ZnS: Cu (green light emission), and ZnCdS: Cu (yellow to orange light emission) are known. However, all of these sulfide phosphors have many problems in practical use, such as being chemically unstable and having poor light resistance.
Zinc sulphide phosphorescent phosphors (ZnS: Cu), which are currently mainly used in the market, are also exposed to direct sunlight outdoors, especially in the presence of moisture, because they are photodegraded by ultraviolet rays to blacken or reduce brightness. It is difficult to use in applications, and its applications such as luminous clocks, evacuation guidance signs, and indoor nighttime display have been limited.
[0004]
Even when this zinc sulfide-based phosphor is used in a luminous timepiece, the afterglow time in which the time can be recognized by the naked eye is about 30 minutes to about 2 hours, and practically, a radioactive substance is added to the phosphor. At present, it is necessary to use a self-luminous luminous paint which is added and stimulated by the energy to emit light constantly.
In view of the above-mentioned situation, the present inventor has a much longer afterglow characteristic than a commercially available sulfide-based phosphor, is chemically stable, and has a long-term light resistance. As a luminous phosphor excellent in luminosity, a luminous phosphor composed of SrAl 2 O 4 : Eu, Dy is provided.
[0005]
However, both the zinc sulfide phosphorescent phosphor (ZnS: Cu) and the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy have a green body color, and therefore are not inconvenient even if they look green. It could only be used for
On the other hand, if the body color is white, not only is it easy to use as it is, but also the desired color can be obtained by adding other pigments, etc. Among the phosphorescent phosphors having a high luminance afterglow characteristic, there was no phosphor having a white body color.
[0006]
[Problems to be solved by the invention]
In view of the above-mentioned situation, the present inventor has a much longer afterglow characteristic than a commercially available sulfide-based phosphor, is chemically stable, and has a long-term light resistance. The object of the present invention is to provide a white phosphorescent phosphor which is excellent in color and has a body color that looks white under ordinary visible light.
[0007]
[Means for Solving the Problems]
As a white phosphorescent phosphors as described above, an invention according to claim 1, SrAl 2 O 4: Eu, the phosphorescent phosphors consisting of Dy, Er 2 O 3 of SrAl 2 O 4: Eu, to Dy 1 to 15% by weight.
The invention according to claim 2 comprises SrAl 2 O 4 : Eu, Dy, wherein Eu is added to Sr in a range of 1 ≦ Eu ≦ 10 mol%, and Eu and Dy are further added to 3 ≦ Dy / Eu. was added at a ratio of ≦ 70, further phosphorescent phosphors was 30 mol% or more of Sr, Er 2 O 3 of SrAl 2 O 4: Eu, characterized in that the addition of 1 to 15 wt% with respect to Dy .
[0008]
In synthesizing these white phosphorescent phosphors, for example, boric acid can be added as a flux in the range of 1 to 10% by weight. Here, if the addition amount is 1% by weight or less, the flux effect is lost, and if it exceeds 10% by weight, it solidifies, and subsequent pulverization and classification work becomes difficult.
[0009]
【Example】
The inventors of the present invention have confirmed that a phosphorescent phosphor made of SrAl 2 O 4 : Eu, Dy has excellent light resistance and has a high luminance afterglow characteristic for an extremely long time.
The reflectance of such a phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy has a peak at a wavelength of about 520 nm as shown in FIG.
[0010]
Here, when the reflectance of each wavelength in the visible light region is substantially equal, it is recognized as white under visible light, but if it has such a peak, the color corresponding to the peak wavelength Will be recognized.
Therefore, the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy having a peak at a wavelength of about 520 nm is recognized as green under visible light.
[0011]
Accordingly, next, the inventors, SrAl 2 O 4: Eu, has a low reflectance at about 520nm is the peak of the phosphorescent phosphor comprising a Dy, and SrAl 2 O 4: Eu, phosphorescent consisting Dy Among the substances having a high reflectance from about 500 nm where the reflectance of the luminescent phosphor starts to decrease, a substance that does not alienate a point having a high luminance afterglow characteristic for an extremely long time was searched for by various experiments.
[0012]
As a result, it was found that Er 2 O 3 was suitable.
In terms of reflectance, as shown in FIG. 1, Er 2 O 3 has high reflectance at about 440 nm, 480 nm, and 620 nm, and shows the lowest reflectance at about 540 nm. And, due to the peak at about 620 nm, it looks very pink under visible light.
[0013]
As shown in FIG. 1, when a phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy is added with 7 wt% of Er 2 O 3 as an example, a visible light range of about 450 nm to 650 nm is obtained. The space is almost smoothed, and is recognized as white under visible light.
Further, when adding Er 2 O 3 to the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy, the amount of addition was changed variously, and the result of measuring the luminance and whiteness was compared with the zinc sulfide phosphorescent. The luminance and whiteness of the phosphor (ZnS: Cu) are shown in Table 1.
[0014]
The luminance here is shown as a relative luminance with respect to the luminance immediately after the irradiation of 400 lx for 20 minutes is set to 1. Further, the whiteness indicates a degree when perfect white is regarded as 100. The Er 2 O 3 amount (%) indicates the amount of Er 2 O 3 added to the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy in terms of% by weight.
[0015]
Further, the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy used here is:
SrCO 3 : 0.83 mol%
Al 2 O 3 : 1.00 mol%
Eu 2 O 3 : 0.010 mol%
Dy 2 O 3 : 0.075 mol%
And ultimately,
(Sr 0.83 Eu 0.02 Dy 0.15 ) Al 2 O 4
Phosphorescent phosphor is used.
[0016]
[Table 1]
From this table, it can be seen that the luminance decreases as the added amount of Er 2 O 3 increases. However, when the luminance of the zinc sulfide-based phosphorescent phosphor (ZnS: Cu) is set as a comparison target, even when the addition amount of Er 2 O 3 is 15% by weight, the luminance of 4.91 times is increased after 10 minutes. It is shown. Further, even when the addition amount of Er 2 O 3 is set to 20% by weight, it is confirmed that the luminance is 3.36 times after 10 minutes. Therefore, even when Er 2 O 3 is added, the phosphor has a high luminance afterglow characteristic for an extremely long time as compared with a conventionally used zinc sulfide phosphorescent phosphor (ZnS: Cu). Was confirmed.
[0018]
The whiteness gradually increases as the amount of Er 2 O 3 added increases, but peaks at about 7% by weight, and conversely, the whiteness decreases when more than 7 wt% is added. . When the addition amount of Er 2 O 3 is set to 20% by weight, the whiteness of the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy, in which the addition amount of Er 2 O 3 is 0% by weight, is almost equal. Would.
[0019]
Considering these luminance and whiteness, it has been confirmed that the addition amount of Er 2 O 3 to the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy is preferably in the range of 1 to 15% by weight. Was done.
Furthermore, in the above description, the case where (Sr 0.83 Eu 0.02 Dy 0.15 ) Al 2 O 4 is used as the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy has been described. Even when the ratio of Eu, Dy and Dy is another ratio, the same tendency is exhibited, and it has been confirmed that the addition amount of Er 2 O 3 is preferably in the range of 1 to 15% by weight.
[0020]
Further, it is confirmed that the same tendency is observed in the luminance after 30 minutes and the luminance after 100 minutes.
Next, in the phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy, first, an experiment was conducted in which the ratio of Eu to Dy was changed for each addition amount of Eu to Sr.
[0021]
Table 2 shows the addition amount of the sample in which 0.01 mol of Eu was added and Dy was further changed in the range of 0.05 mol to 0.7 mol (5 ≦ Dy / Eu ≦ 70). Table 3 shows the luminance after 10 minutes, the luminance after 30 minutes, the luminance after 100 minutes, and the whiteness corresponding to each sample.
[0022]
[Table 2]
[Table 3]
Here, zinc sulfide phosphorescent phosphor (ZnS) was added to all samples in which 0.01 mol of Eu was added and Dy was further changed in the range of 0.05 mol to 0.7 mol (5 ≦ Dy / Eu ≦ 70). : Cu), it was confirmed that the luminance and whiteness were improved.
Table 4 shows the addition amount of the sample in which 0.02 mol of Eu was added and Dy was changed in the range of 0.10 mol to 0.8 mol ( 5 ≦ Dy / Eu ≦ 40). Table 5 shows the luminance after 10 minutes, the luminance after 30 minutes, the luminance after 100 minutes, and the whiteness corresponding to each sample.
[0025]
[Table 4]
[Table 5]
Here, 0.02 mol of Eu was added, and Dy was changed in the range of 0.10 mol to 0.8 mol ( 5 ≦ Dy / Eu ≦ 40). It was confirmed that the brightness and whiteness were equal or improved as compared with ZnS: Cu).
Table 6 shows the addition amount of the sample in which 0.03 mol of Eu was added and Dy was changed in the range of 0.10 mol to 0.9 mol (3.3 ≦ Dy / Eu ≦ 30). Table 7 shows the luminance after 10 minutes, the luminance after 30 minutes, the luminance after 100 minutes, and the whiteness corresponding to each sample.
[0028]
[Table 6]
[Table 7]
Here, of the samples in which 0.03 mol of Eu was added and Dy was changed in the range of 0.10 mol to 0.9 mol (3.3 ≦ Dy / Eu ≦ 30), 0.10 mol to 0.8 mol In the range of (3.3 ≦ Dy / Eu ≦ 26.7), it was confirmed that the brightness and the whiteness were improved as compared with the zinc sulfide phosphorescent phosphor (ZnS: Cu). On the other hand, when 0.03 mol of Eu and 0.9 mol of Dy (Dy / Eu = 30) are further added, the luminance is inferior to that of the zinc sulfide phosphorescent phosphor (ZnS: Cu). This may be due to the fact that the amount of SrCO 3 added was too small. Then, it was confirmed by conducting an experiment that it was confirmed that when Sr was 0.1 mol (10 mol%) or less, the luminance was inferior to that of the zinc sulfide phosphorescent phosphor (ZnS: Cu).
[0031]
Table 8 shows the addition amount of the sample in which 0.05 mol of Eu was added and Dy was changed in the range of 0.15 mol to 0.8 mol (3 ≦ Dy / Eu ≦ 16). Table 9 shows the luminance after 10 minutes, the luminance after 30 minutes, the luminance after 100 minutes, and the whiteness corresponding to each sample.
[0032]
[Table 8]
[Table 9]
Here, 0.05 mol of Eu was added, and Dy was further changed in the range of 0.15 mol to 0.8 mol (3 ≦ Dy / Eu ≦ 16). : Cu), it was confirmed that the brightness and whiteness were equal or improved.
Table 10 shows the addition amount of the sample in which 0.1 mol of Eu was added and Dy was further changed in the range of 0.3 mol to 0.7 mol (3 ≦ Dy / Eu ≦ 7). Table 11 shows the luminance after 10 minutes, the luminance after 30 minutes, the luminance after 100 minutes, and the whiteness corresponding to each sample.
[0035]
[Table 10]
[Table 11]
Here, the zinc sulfide phosphorescent phosphor (ZnS) was added over all samples in which 0.1 mol of Eu was added and Dy was further changed in the range of 0.3 mol to 0.7 mol (3 ≦ Dy / Eu ≦ 7). : Cu), it was confirmed that the brightness and whiteness were equal or improved.
Next, measurement was performed for a case where Er 2 O 3 was added to each sample at 7% by weight. The results are attached as Table 12.
[0038]
[Table 12]
Here, it was confirmed that the brightness of each sample was slightly lowered and the whiteness was improved. From this, SrAl 2 O 4 : Eu, Dy, Eu is added to Sr in the range of 1 ≦ Eu ≦ 10 mol%, and Eu and Dy are further added in a ratio of 3 ≦ Dy / Eu ≦ 70. It was confirmed that by adding Er 2 O 3 to the phosphorescent phosphor added in step ( 2) at 7% by weight, the luminance and whiteness were improved as compared with the zinc sulfide phosphorescent phosphor (ZnS: Cu). .
[0040]
Further, similarly, as a result of a measurement in a case where 1 to 15% by weight of Er 2 O 3 was added, similar to Table 12, it was confirmed that the luminance was slightly lowered and the whiteness was improved.
Next, as for the samples 1-1 to 5-3, when the content of Er 2 O 3 was 1 to 15% by weight, the whiteness was improved with the addition of Er 2 O 3 . However, it was confirmed that when Sr was 0.3 mol (30 mol%) or less, the luminance was inferior to that of the zinc sulfide phosphorescent phosphor (ZnS: Cu).
[0041]
【The invention's effect】
As described above, the present invention has a much longer afterglow characteristic than a commercially available sulfide-based phosphor, is furthermore chemically stable, and has excellent light resistance over a long period of time. The body color looks white under normal visible light.
[Brief description of the drawings]
FIG. 1 shows a reflectivity of a phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy, a reflectivity of Er 2 O 3 , and a phosphorescent phosphor composed of SrAl 2 O 4 : Eu, Dy which is made of Er 2 O 3. Is a graph showing the reflectance of a white phosphorescent phosphor to which 7 wt% was added.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18788495A JP3595380B2 (en) | 1995-06-30 | 1995-06-30 | White phosphorescent phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18788495A JP3595380B2 (en) | 1995-06-30 | 1995-06-30 | White phosphorescent phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0913028A JPH0913028A (en) | 1997-01-14 |
| JP3595380B2 true JP3595380B2 (en) | 2004-12-02 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18788495A Expired - Lifetime JP3595380B2 (en) | 1995-06-30 | 1995-06-30 | White phosphorescent phosphor |
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| JP (1) | JP3595380B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100484097B1 (en) * | 1998-09-25 | 2005-09-02 | 삼성에스디아이 주식회사 | Blue light emitting phosphor for plasma display panel |
| KR20020094171A (en) * | 2001-06-12 | 2002-12-18 | 동국산업 주식회사 | UV-detecting element |
| KR100457864B1 (en) * | 2002-02-23 | 2004-11-18 | 삼성전기주식회사 | Phosphor for white LED lamp |
| JP5149384B2 (en) | 2008-07-14 | 2013-02-20 | 信越化学工業株式会社 | Method for producing long afterglow phosphor |
| WO2010098426A1 (en) * | 2009-02-27 | 2010-09-02 | 信越化学工業株式会社 | Long-afterglow fluorescent ceramic and process for producing same |
| CN103013507A (en) * | 2012-12-26 | 2013-04-03 | 广州有色金属研究院 | Ultrafine rare-earth aluminate long-persistence luminescent material and preparation method thereof |
| CN104804733A (en) * | 2015-05-20 | 2015-07-29 | 江南大学 | Rare-earth strontium aluminate luminous nanorod and preparation method thereof |
-
1995
- 1995-06-30 JP JP18788495A patent/JP3595380B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0913028A (en) | 1997-01-14 |
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