JPH08151574A - Fluorescent substance having afterglow property - Google Patents
Fluorescent substance having afterglow propertyInfo
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- JPH08151574A JPH08151574A JP22284395A JP22284395A JPH08151574A JP H08151574 A JPH08151574 A JP H08151574A JP 22284395 A JP22284395 A JP 22284395A JP 22284395 A JP22284395 A JP 22284395A JP H08151574 A JPH08151574 A JP H08151574A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は蓄光蛍光体に利用できる
残光性蛍光体に関し、特に耐熱性、耐水性に優れたユー
ロピウムで付活されたアルミン酸塩残光性蛍光体に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a afterglow phosphor that can be used as a phosphorescent phosphor, and more particularly to a europium-activated aluminate afterglow phosphor having excellent heat resistance and water resistance.
【０００２】[0002]
【従来の技術】蛍光体の中には、太陽光や人工照明の光
を照射すると、暗所で比較的長い時間残光をもつものが
あり、この現象を何回も繰り返すことができることから
蓄光蛍光体と呼ばれる。近年、社会生活が高度化し複雑
さが増すとともに、防災に関する関心が一層高まり、特
に、暗所で光る蓄光蛍光体の防災分野での利用が広がり
つつある。また、最近は蓄光蛍光体をプラスチックに混
入して、プレート、シートなどに加工することにより、
多方面に用途が広がりつつある。2. Description of the Related Art Some phosphors have afterglow for a relatively long time in a dark place when they are irradiated with sunlight or artificial lighting, and this phenomenon can be repeated many times. Called phosphor. In recent years, as social life has become more sophisticated and more complicated, interest in disaster prevention has increased, and in particular, the use of phosphorescent phosphors that glow in the dark is expanding in the field of disaster prevention. In addition, recently, by mixing phosphorescent phosphor into plastic and processing it into plates, sheets, etc.,
Applications are expanding in various fields.
【０００３】従来より、蓄光蛍光体としてＺｎＳ：Ｃｕ
蛍光体が使用されてきたが、必ずしも十分満足されてい
なかった。それはこの蛍光体が次のような本質的な欠点
を有しているためである。一つは、そのりん光輝度（残
光の輝度）が数十時間にわたって確認できるほど高くな
いこと。もう一つは、紫外線により光分解し蛍光体結晶
表面にコロイド状亜鉛金属を析出し外観が黒色に変色
し、りん光輝度が著しく低下する問題がある点である。
このような劣化は高温高湿の条件下で特に起こりやす
く、通常この欠点を改善するのにＺｎＳ：Ｃｕ蛍光体の
表面には耐光処理を施してあるが完全に防止することは
難しい。その為、ＺｎＳ：Ｃｕ蛍光体は屋外など直射日
光にさらされるような場所に用いることを避けなければ
ならない。Conventionally, ZnS: Cu has been used as a phosphorescent phosphor.
Phosphors have been used but have not always been fully satisfactory. This is because this phosphor has the following essential drawbacks. One is that the phosphorescence brightness (brightness of afterglow) is not high enough to be confirmed for several tens of hours. The other is that there is a problem that photolysis is caused by ultraviolet rays and colloidal zinc metal is deposited on the surface of the phosphor crystal to change its appearance to black and phosphorescence brightness is significantly reduced.
Such deterioration is particularly likely to occur under conditions of high temperature and high humidity, and the surface of the ZnS: Cu phosphor is usually light-proofed to improve this drawback, but it is difficult to completely prevent it. Therefore, it is necessary to avoid using the ZnS: Cu phosphor in a place exposed to direct sunlight, such as outdoors.
【０００４】硫化亜鉛蛍光体母体に希土類イオンを含有
させることにより、残光性を示すことが最近報告されて
いる。（"Rare earth effect in nonrioactivenight lu
minous phosphor ZnS:Pb,Cu" Hunan Shifan Daxue,Zira
n Kexue XuebaoVol.14,No.1,page47-51 1991,X May and
M.Hong,(Acta ScientiariumNaturalium Univ.Normalis
Hunanensis)）It has been recently reported that a rare earth ion is contained in a zinc sulfide phosphor matrix to exhibit afterglow. ("Rare earth effect in nonrioactivenight lu
minous phosphor ZnS: Pb, Cu "Hunan Shifan Daxue, Zira
n Kexue Xuebao Vol.14, No.1, page 47-51 1991, X May and
M. Hong, (Acta ScientiariumNaturalium Univ.Normalis
Hunanensis))
【０００５】また、Ｂｉ、Ｃｕ付活硫化カルシウム蛍光
体に希土類元素を含有させることにより、残光性を示す
ことが報告されている。（"Study on effect of rare e
arthin blue-purple night-luminous phosphor CaS:Bi,
Cu" Hunan Shifan Daxue,Ziran Kexue XuebaoVol.15,N
o.2,page145-148,1992, X Mao, S.Lian and Z.Wu (Huna
n Normal Univ.,Hunan,CHN)）It has been reported that a rare earth element is contained in Bi, Cu-activated calcium sulfide phosphor to exhibit afterglow. ("Study on effect of rare e
arthin blue-purple night-luminous phosphor CaS: Bi,
Cu "Hunan Shifan Daxue, Ziran Kexue XuebaoVol.15, N
o.2, page 145-148,1992, X Mao, S.Lian and Z.Wu (Huna
n Normal Univ., Hunan, CHN))
【０００６】しかし、これらの蛍光体は硫化物である以
上既に述べたような欠点を持ち、屋外での使用はできな
いことが容易に想像できる。However, it can be easily imagined that these phosphors, which are sulfides, have the above-mentioned drawbacks and cannot be used outdoors.
【０００７】これに対し、２価のＥｕで付活されたＭＡ
ｌ2Ｏ4で表される化合物で、Ｍはカルシウム、ストロン
チウム、バリウムからなる群から選ばれる少なくとも１
つ以上の金属元素からなる化合物を母結晶にした蓄光性
蛍光体が特開平７−１１２５０号に開示されている。こ
の蛍光体は上述した硫化亜鉛蛍光体の本質的な欠点を解
決したとしている。また、この蛍光体の母体は米国特許
公報２３９２８１４号、米国特許公報３２９４６９９号
で既に知られているものである。On the other hand, MA activated with divalent Eu
is a compound represented by l 2 O 4 and M is at least 1 selected from the group consisting of calcium, strontium and barium.
JP-A-7-11250 discloses a phosphorescent phosphor having a mother crystal of a compound consisting of three or more metal elements. This phosphor is said to solve the above-mentioned essential drawbacks of the zinc sulfide phosphor. The matrix of this phosphor is already known in US Pat. No. 2,392,814 and US Pat. No. 3,294,699.
【０００８】２価のＥｕは間接遷移によりブロードなス
ペクトルの発光を示し、調製条件及び母体結晶の構造に
影響され、例えば母体結晶がアルミネート、ガレート、
ボレート或いはアルミニウムガレートであるかにより、
紫外域から黄色までの広い範囲で発光することは一般的
に知られている。The divalent Eu emits a broad spectrum of light by indirect transition and is influenced by the preparation conditions and the structure of the host crystal. For example, the host crystal is aluminate, gallate,
Depending on whether it is borate or aluminum gallate,
It is generally known that light is emitted in a wide range from the ultraviolet region to the yellow.
【０００９】本発明者等は硼アルミン酸のアルカリ土類
金属塩を蛍光体母体とし、２価のユーロピウムで付活さ
れ、特定の希土類元素で共付活された残光性蛍光体を開
発し、米国特許出願し、特許許可された。（ＵＳＰ５３
７６３０３号）また、本発明者等は同様の蛍光体母体を
使用し、さらに多くの共付活剤の試験を行い、新たに得
た知見を特許出願した。（特願平６−１４７９１２号）The present inventors have developed an afterglow phosphor which is activated with divalent europium and co-activated with a specific rare earth element, using an alkaline earth metal salt of boric aluminate as a phosphor matrix. Filed a US patent and was granted a patent. (USP53
No. 76303) Further, the present inventors used the same phosphor base material, tested more coactivators, and applied for a patent for the newly obtained findings. (Japanese Patent Application No. 6-147912)
【００１０】[0010]
【発明が解決しようとする課題】蓄光蛍光体をプラスチ
ック、セラミックに混入させて使用する場合、これらを
溶融させるため、蓄光蛍光体は３００〜７００℃程度の
温度にさらされる。それで、このような高温下で成形さ
れる工程がある場合でも、発光性能が低下しない蓄光蛍
光体が要求される。また、屋外で使用する場合、特に水
分との接触が起こりやすくなり、そのような環境で使わ
れる場合耐水性も重用である。When the phosphorescent phosphor is mixed with plastic or ceramic for use, the phosphorescent phosphor is exposed to a temperature of about 300 to 700 ° C. in order to melt them. Therefore, even if there is a step of molding at such a high temperature, a phosphorescent phosphor that does not deteriorate the light emitting performance is required. Further, when used outdoors, contact with moisture is particularly likely to occur, and water resistance is also important when used in such an environment.
【００１１】[0011]
【課題を解決するための手段】本発明者は上述の課題を
解決する目的で、残光性蛍光体の結晶成長を促進し、結
晶を安定化させる成分について鋭意検討した結果、硼酸
と燐酸を同時に含有させることで課題を解決できること
を見いだした。For the purpose of solving the above-mentioned problems, the present inventor diligently studied a component which promotes crystal growth of the afterglow phosphor and stabilizes the crystal, and as a result, boric acid and phosphoric acid were selected. It was found that the problem can be solved by including them at the same time.
【００１２】すなわち、本発明の残光性蛍光体は、２価
のユーロピウムで付活されたアルミン酸塩蛍光体におい
て、その化学組成式が下記の範囲にあることを特徴とす
る。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ ０．５≦ｎ≦３．０ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＭｇ、Ｃａ、Ｓｒ、Ｂａ、及び
Ｚｎからなる２価金属の群より選ばれた少なくとも１種
であり、Ｑは共付活剤でありＭｎ、Ｚｒ、Ｎｂ、Ｐｒ、
Ｎｄ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及
びＬｕからなる群より選ばれた少なくとも１種である。That is, the afterglow phosphor of the present invention is a divalent europium-activated aluminate phosphor whose chemical composition formula is within the following range. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 0.5 ≦ n ≦ 3.0 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, M in the composition formula is at least one selected from the group of divalent metals consisting of Mg, Ca, Sr, Ba and Zn, and Q is a co-activator and is Mn, Zr. , Nb, Pr,
It is at least one selected from the group consisting of Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
【００１３】上記した組成をさらに以下の特定範囲に調
整することで、蛍光色及び残光色を選択することができ
る。The fluorescent color and the afterglow color can be selected by further adjusting the above composition to the following specific ranges.
【００１４】発光ピーク波長が５２０ｎｍ付近の緑色発
光の残光性蛍光体を調製する場合、次のような組成範囲
に選択する。すなわち、２価のユーロピウムで付活され
たアルミン酸塩蛍光体において、その化学組成式が下記
の範囲にある結晶構造が単斜晶系を主体とする残光性蛍
光体とする。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ ０．５≦ｎ≦１．５ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＳｒが７０モル％以上である。When a green light-emitting afterglow phosphor having an emission peak wavelength of around 520 nm is prepared, the following composition range is selected. That is, in the aluminate phosphor activated by divalent europium, the afterglow phosphor having a chemical composition formula in the following range and a crystal structure mainly composed of a monoclinic system is used. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 0.5 ≦ n ≦ 1.5 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, S in the composition formula is 70 mol% or more of Sr.
【００１５】発光ピーク波長が４４０ｎｍ付近の青色発
光の残光性蛍光体を調製する場合、次のような組成範囲
に選択する。すなわち、２価のユーロピウムで付活され
たアルミン酸塩蛍光体において、その化学組成式が下記
の範囲にあり、結晶構造が単斜晶系を主体とすることを
特徴とする残光性蛍光体とする。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ ０．５≦ｎ≦１．５ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＣａが７０モル％以上である。When a blue light-emitting afterglow phosphor having an emission peak wavelength of around 440 nm is prepared, the following composition range is selected. That is, in the aluminate phosphor activated with divalent europium, the chemical composition formula thereof is in the following range, and the crystal structure is mainly composed of a monoclinic system. And (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 0.5 ≦ n ≦ 1.5 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≤0.75 However, Ca in the composition formula is 70 mol% or more of Ca.
【００１６】発光ピーク波長が４９０ｎｍ付近の青緑色
発光の残光性蛍光体を調製する場合、次のような組成範
囲に選択する。すなわち、２価のユーロピウムで付活さ
れたアルミン酸塩蛍光体において、その化学組成式が下
記の範囲にあり、結晶構造が斜方晶系を主体とすること
を特徴とする残光性蛍光体とする。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ １．５≦ｎ≦３．０ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＳｒが７０モル％以上である。When preparing a blue-green afterglow phosphor having an emission peak wavelength near 490 nm, the following composition range is selected. That is, in the aluminate phosphor activated with divalent europium, the chemical composition formula thereof is within the following range, and the crystal structure is mainly an orthorhombic system, and a afterglow phosphor. And (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 1.5 ≦ n ≦ 3.0 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, S in the composition formula is 70 mol% or more of Sr.
【００１７】発光ピーク波長が４９０ｎｍ付近の青緑色
発光の残光性蛍光体は、特に、次のような組成範囲に選
択することが発光輝度、残光輝度の点で好ましい。すな
わち、２価のユーロピウムで付活されたアルミン酸塩蛍
光体において、その化学組成式が下記の範囲にあり、結
晶構造が斜方晶系を主体とすることを特徴とする残光性
蛍光体とする。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ １．７≦ｎ≦１．８ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＳｒである。The blue-green afterglow phosphor having an emission peak wavelength of around 490 nm is preferably selected in the following composition range from the viewpoint of emission brightness and afterglow brightness. That is, in the aluminate phosphor activated with divalent europium, the chemical composition formula thereof is within the following range, and the crystal structure is mainly an orthorhombic system, and a afterglow phosphor. And (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 1.7 ≦ n ≦ 1.8 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, M in the composition formula is Sr.
【００１８】本発明の残光性蛍光体に導入する付活剤お
よび共付活剤は、蛍光色および残光輝度に大きく影響す
る。実用上、それぞれ次に示すような範囲に調整する。The activator and co-activator introduced into the afterglow phosphor of the present invention greatly affect the fluorescent color and the afterglow brightness. Practically, the respective ranges are adjusted as shown below.
【００１９】付活剤のＥｕの濃度ｐについては、蛍光体
１モルに対し、母体のＳｒを０．０００１モル以上、
０．５モル以下置換する範囲に調整する。なぜなら０．
０００１モルより少ないと光吸収が悪くなり、その結果
残光輝度が低くなり、逆に、０．５モルよりも多くなる
と、濃度消光を起こし残光輝度が低下するからだ。ｐの
さらに好ましい範囲は０．００１≦ｐ≦０．０６のであ
り、この範囲で残光輝度がさらに高くなる。With respect to the concentration p of Eu of the activator, 0.001 mol or more of Sr of the host is used per 1 mol of the phosphor,
The amount is adjusted to be 0.5 mol or less. Because 0.
If it is less than 0001 mol, the light absorption will be poor, and as a result, the afterglow brightness will be low, and conversely, if it is more than 0.5 mol, concentration quenching will occur and the afterglow brightness will be lowered. The more preferable range of p is 0.001 ≦ p ≦ 0.06, and the afterglow luminance is further increased in this range.
【００２０】共付活剤を導入することによりＥｕの発光
は残光性を示すようになる。共付活剤としてＭｎ、Ｚ
ｒ、Ｎｂ、Ｐｒ、Ｎｄ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅ
ｒ、Ｔｍ、Ｙｂ、及びＬｕからなる群より選ばれた少く
とも一種が有効である。By introducing the co-activator, the luminescence of Eu becomes afterglow. Mn, Z as co-activator
r, Nb, Pr, Nd, Gd, Tb, Dy, Ho, E
At least one selected from the group consisting of r, Tm, Yb, and Lu is effective.
【００２１】Ｄｙは蛍光体母体の２価金属Ｍが特にＳｒ
の場合に残光性向上に効果的であり、Ｄｙ濃度ｑの最適
濃度範囲は０．０００５以上、０．０３以下の範囲であ
る。Dy is a divalent metal M of the phosphor matrix, especially Sr.
In this case, it is effective in improving the afterglow property, and the optimum concentration range of the Dy concentration q is 0.0005 or more and 0.03 or less.
【００２２】Ｎｄは蛍光体母体の２価金属Ｍが特にＣａ
の場合に残光輝度向上に特に効果があり、Ｎｄ濃度ｑの
最適範囲は０．０００５以上、０．０３以下の範囲であ
る。Nd is especially Ca when the divalent metal M of the phosphor matrix is
In this case, it is particularly effective in improving the afterglow brightness, and the optimum range of the Nd concentration q is 0.0005 or more and 0.03 or less.
【００２３】これら共付活剤Ｄｙ、Ｎｄに、他の第２に
共付活剤を付活することにより相乗効果を発揮する。By synergizing these coactivators Dy and Nd with another second coactivator, a synergistic effect is exhibited.
【００２４】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＭｎ濃度ｑの好ましい範囲は０．
０００１以上、０．０６以下で、更に好ましいのは０．
０００５以上、０．０２以下の範囲である。When Dy is selected as the first coactivator, the preferable range of the Mn concentration q of the second coactivator is 0.
0001 or more and 0.06 or less, more preferably 0.
The range is 0005 or more and 0.02 or less.
【００２５】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＴｍ濃度ｑの好ましい範囲は０．
０００３以上、０．０２以下で、更に好ましいのは０．
０００４以上、０．０１以下の範囲である。When Dy is selected as the first coactivator, the preferred range of the Tm concentration q of the second coactivator is 0.
It is 0.03 or more and 0.02 or less, more preferably 0.
The range is 0004 or more and 0.01 or less.
【００２６】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＬｕ濃度ｑの好ましい範囲は０．
０００１以上、０．０６以下で、更に好ましいのは０．
０００４以上、０．０４以下の範囲である。When Dy is selected as the first coactivator, the preferred range of the Lu concentration q of the second coactivator is 0.
0001 or more and 0.06 or less, more preferably 0.
The range is 0004 or more and 0.04 or less.
【００２７】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＮｂ濃度ｑの好ましい範囲は０．
０００１以上、０．０８以下で、更に好ましいのは０．
０００３以上、０．０４以下の範囲である。When Dy is selected as the first coactivator, the preferable range of the Nb concentration q of the second coactivator is 0.
0001 or more and 0.08 or less, more preferably 0.
The range is 0003 or more and 0.04 or less.
【００２８】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＹｂ濃度ｑの好ましい範囲は０．
０００２以上、０．０４以下で、更に好ましいのは０．
０００３以上、０．０１以下の範囲である。When Dy is selected as the first coactivator, the preferable range of the Yb concentration q of the second coactivator is 0.
It is 0002 or more and 0.04 or less, more preferably 0.
The range is 0003 or more and 0.01 or less.
【００２９】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＺｒ濃度ｑの好ましい範囲は０．
００２以上、０．７０以下である。When Dy is selected as the first co-activator, the preferred range of the Zr concentration q of the second co-activator is 0.
It is 002 or more and 0.70 or less.
【００３０】第一の共付活剤としてＤｙを選択する場
合、第二の共付活剤のＥｒ濃度ｑの好ましい範囲は０．
０００１以上、０．０３以下である。更に好ましいのは
０．０００５以上、０．０２以下の範囲である。When Dy is selected as the first co-activator, the preferable range of Er concentration q of the second co-activator is 0.
It is 0001 or more and 0.03 or less. More preferably, the range is 0.0005 or more and 0.02 or less.
【００３１】第一の共付活剤としてＤｙを選択する場
合、第２の共付活剤のＰｒ濃度ｑの好ましい範囲は０．
０００１以上、０．０４以下である。更に好ましいのは
０．０００５以上、０．０３以下の範囲である。When Dy is selected as the first coactivator, the preferred range of Pr concentration q of the second coactivator is 0.
It is 0001 or more and 0.04 or less. More preferably, the range is 0.0005 or more and 0.03 or less.
【００３２】第一の共付活剤としてＮｄを導入する場
合、第２の共付活剤のＴｍ濃度ｑの好ましい範囲は０．
０００１以上、０．０６以下で、更に好ましいのは０．
０００５以上、０．０２以下の範囲である。When Nd is introduced as the first coactivator, the preferred range of the Tm concentration q of the second coactivator is 0.
0001 or more and 0.06 or less, more preferably 0.
The range is 0005 or more and 0.02 or less.
【００３３】第一の共付活剤としてＮｄを導入する場
合、第２の共付活剤のＰｒ濃度ｑの好ましい範囲は０．
０００１以上、０．０６以下で、更に好ましいのは０．
０００５以上、０．０２以下の範囲である。When Nd is introduced as the first coactivator, the preferable range of the Pr concentration q of the second coactivator is 0.
0001 or more and 0.06 or less, more preferably 0.
The range is 0005 or more and 0.02 or less.
【００３４】第一の共付活剤としてＮｄを以下導入する
場合、第２の共付活剤のＨｏ濃度ｑの好ましい範囲は
０．０００１以上、０．０６以下で、更に好ましいのは
０．０００５以上、０．０２以下の範囲である。When Nd is introduced below as the first co-activator, the Ho concentration q of the second co-activator is preferably in the range of 0.0001 to 0.06, and more preferably 0.00. The range is 0005 or more and 0.02 or less.
【００３５】第一の共付活剤としてＮｄを以下導入する
場合、第２の共付活剤のＤｙ濃度ｑの好ましい範囲は
０．０００１以上、０．０６以下で、更に好ましいのは
０．０００５以上、０．０２以下の範囲である。When Nd is introduced below as the first co-activator, the preferable range of the Dy concentration q of the second co-activator is 0.0001 or more and 0.06 or less, and more preferably 0. The range is 0005 or more and 0.02 or less.
【００３６】本発明の残光性蛍光体の母体組成について
は、アルミニウムの一部をホウ素で置換することによ
り、残光特性はさらに大きく改善される。ホウ素はアル
ミニウムの総モル数の０．０００１モルから０．５モル
置換する範囲が適当であり、より好ましくは、０．００
５モルから０．２５モルになる範囲であり、最も好まし
いのは、０．０５モル付近である。ホウ素を導入するに
は、アルミニウムをそれに見合う量だけ差し引いて仕込
むことが好ましい。Regarding the matrix composition of the afterglow phosphor of the present invention, the afterglow characteristics are further improved by substituting part of aluminum with boron. The boron is appropriately substituted in a range of 0.0001 mol to 0.5 mol of the total mol of aluminum, and more preferably 0.00
It is in the range of 5 to 0.25 mol, and the most preferable range is around 0.05 mol. In order to introduce boron, it is preferable to charge aluminum by subtracting an amount corresponding to it.
【００３７】リン酸化合物濃度ｋは０．００１以上、
０．２以下の範囲が好ましく、０．０１以上、０．１以
下の範囲がさらに好ましく、０．０３以上、０．０５以
下の範囲が最も好ましい。The phosphate compound concentration k is 0.001 or more,
The range is preferably 0.2 or less, more preferably 0.01 or more and 0.1 or less, and most preferably 0.03 or more and 0.05 or less.
【００３８】本発明の残光性蛍光体は、原料として例え
ばＳｒＯ、ＭｇＯ、Ａｌ2Ｏ3、Ｅｕ 2Ｏ3のような金属酸
化物、或いはＣａＣＯ3、ＳｒＣＯ3、ＢａＣＯ3のよう
な高温で焼成することで容易に酸化物になるような化合
物を選択する。このような化合物として炭酸塩の他には
硝酸塩、シュウ酸塩、水酸化物などがある。また、ホウ
素化合物としてはホウ酸あるいはアルカリ土類のホウ酸
塩が使用でき、特に、ホウ酸が好ましい。また、本残光
性蛍光体の組成にリン酸を導入させるには、リン酸、無
水リン酸、リン酸アンモニウム、アルカリ土類元素のリ
ン酸塩等が好ましく使用できる。The afterglow phosphor of the present invention is used as a raw material.
For example, SrO, MgO, Al2O3, Eu 2O3Metal acid like
Compound or CaCO3, SrCO3, BaCO3As
A compound that easily becomes an oxide when fired at a very high temperature.
Select an item. Besides such carbonates as such compounds
Examples include nitrates, oxalates, and hydroxides. Also, how
Boric acid or alkaline earth boric acid as the elementary compound
A salt can be used, and boric acid is particularly preferable. Also, this afterglow
To introduce phosphoric acid into the composition of the fluorescent phosphor,
Water phosphoric acid, ammonium phosphate, alkaline earth element
Phosphates and the like can be preferably used.
【００３９】原料の純度は残光輝度に大きく影響し、９
９．９％以上であることが好ましく、９９．９９％以上
であることがさらに好ましい。これらのフラックスを混
合した原料を、還元雰囲気下１２００℃以上１６００℃
以下の温度で焼成し、焼成品を粉砕、篩することで本発
明の残光性蛍光体が得られる。尚、原料の混合比率は、
目的の組成を得る為の理論量を混合することで決定でき
る。The purity of the raw material greatly affects the afterglow brightness.
It is preferably 9.9% or more, and more preferably 99.99% or more. Raw materials mixed with these fluxes are heated to 1200 ° C or higher and 1600 ° C in a reducing atmosphere.
The afterglow phosphor of the present invention is obtained by firing at the following temperature, crushing the fired product, and sieving. The mixing ratio of the raw materials is
It can be determined by mixing theoretical amounts for obtaining the desired composition.
【００４０】これらを混合した原料を、還元雰囲気下１
２００℃以上１６００℃以下の温度範囲で焼成し、焼成
品を粉砕、篩することで本発明の残光性蛍光体が得られ
る。尚、原料の混合比率は、目的の組成を得る為の理論
量を混合することで決定できる。The raw materials obtained by mixing these are mixed with each other under a reducing atmosphere.
The afterglow phosphor of the present invention is obtained by firing in a temperature range of 200 ° C. or higher and 1600 ° C. or lower, and pulverizing and sieving the fired product. The mixing ratio of the raw materials can be determined by mixing theoretical amounts for obtaining the desired composition.
【００４１】[0041]
【作用】本発明の残光性蛍光体は基本的に付活剤の２価
のＥｕによる強い発光を呈するが、２価のＥｕは可視光
から紫外域の広範囲に吸収があり、従って、自然光のよ
うな広範囲な波長域で励起され高効率の発光（蛍光）を
示す。また、共付活剤として、Ｍｎ、Ｚｒ、Ｎｂ、Ｐ
ｒ、Ｎｄ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙ
ｂ、及びＬｕからなる群より選ばれた少なくとも１種を
蛍光体母体にドープさせることで残光現象が現れる。The afterglow phosphor of the present invention basically exhibits strong light emission due to the divalent Eu of the activator, but the divalent Eu has a wide range of absorption from the visible light to the ultraviolet region, and therefore natural light. It exhibits high-efficiency emission (fluorescence) when excited in a wide wavelength range such as. Further, as a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Y
The afterglow phenomenon appears when the phosphor matrix is doped with at least one selected from the group consisting of b and Lu.
【００４２】本発明の残光性蛍光体においてはホウ素を
含有することで、アルミネートの結晶性を良好にし、発
光中心と捕獲中心を安定化させることで残光時間、残光
輝度の改善に有効に働いていると推定できる。また、ホ
ウ素は同時にフラックスとして働き蛍光体の結晶成長を
促進し、りん光輝度が大幅に改善できる。In the afterglow phosphor of the present invention, by containing boron, the crystallinity of the aluminate is improved, and by stabilizing the luminescence center and the trap center, the afterglow time and the afterglow brightness are improved. It can be presumed that it is working effectively. In addition, boron also acts as a flux to promote crystal growth of the phosphor, and phosphorescence brightness can be greatly improved.
【００４３】２価金属、付活剤、共付活剤の酸化物の総
モル数とアルミナ及びホウ酸の総モル数がほぼ１：１す
なわちｎ＝１である場合、Ｘ線回折により解析した結
果、結晶構造はＳｒＡｌ2Ｏ4型の単斜晶系となり、波長
５２０ｎｍにピークのある緑色発光を示す。When the total number of moles of oxides of the divalent metal, the activator and the co-activator and the total number of moles of alumina and boric acid were approximately 1: 1 or n = 1, analysis was performed by X-ray diffraction. As a result, the crystal structure became a SrAl 2 O 4 type monoclinic system, and green emission with a peak at a wavelength of 520 nm was exhibited.
【００４４】これらを１：２すなわちｎ＝２に仕込み焼
成した場合、ホウ素の置換が１モル％程度の低濃度で
は、仕込み組成から生成すべきＳｒＡｌ4Ｏ7の構造を示
すが、ホウ素がこれよりも高濃度では、Ｓｒ4Ａｌ14Ｏ
25とＳｒＡｌ12Ｏ19の混合物となる。すなわち、ホウ素
を含有することにより、結晶構造が変化し、残光性が改
善されている。When these are charged and fired at 1: 2, that is, n = 2, the structure of SrAl 4 O 7 to be produced from the charged composition is shown at a low concentration of about 1 mol% of the substitution of boron. Higher concentration than Sr 4 Al 14 O
It becomes a mixture of 25 and SrAl 12 O 19 . That is, by containing boron, the crystal structure is changed and the afterglow property is improved.
【００４５】特に、ｎ＝１．７５の場合、ピーク波長４
９０ｎｍの青緑色発光が最も強くなり、Ｘ線回折の結
果、原料仕込み量から期待される通りのＳｒ4Ａｌ14Ｏ
25単品を得る。Particularly, when n = 1.75, the peak wavelength is 4
The blue-green light emission of 90 nm becomes the strongest, and as a result of X-ray diffraction, Sr 4 Al 14 O as expected from the charged amount of raw material
Get 25 single items.
【００４６】しかしながら、この残光性蛍光体は耐熱性
が悪く、しかもこの硼酸の添加とともに耐熱性はさらに
悪くなり、しかも焼成品は固くなり、後工程での粉砕及
び篩等の処理が困難となる。これに対し、組成原料とし
て、リン酸化合物を加えて焼成することで、耐熱性、耐
水性が向上する。However, this afterglow phosphor has poor heat resistance, and the addition of boric acid further deteriorates the heat resistance, and the fired product becomes hard, which makes it difficult to perform pulverization and sieving in the subsequent steps. Become. On the other hand, heat resistance and water resistance are improved by adding a phosphoric acid compound as a composition raw material and baking it.
【００４７】加えたホウ酸の大半がアルミナと混晶をつ
くり蛍光体組成に組み込まれるが、一部の過剰となった
ホウ酸は、リン酸化合物及び２価金属と混晶をつくり蛍
光体粒子間の溶融反応を防ぐ働きがあると考えられ、そ
のことが耐熱性向上に寄与している。また、この混晶は
水に不溶性で残光性蛍光体の粒子表面を被覆するため、
残光性蛍光体に耐水性を付与する。Most of the added boric acid forms a mixed crystal with alumina and is incorporated into the phosphor composition, but a part of the boric acid in excess forms a mixed crystal with the phosphoric acid compound and the divalent metal to form phosphor particles. It is considered that it has a function of preventing the melting reaction between them, which contributes to the improvement of heat resistance. Further, since this mixed crystal is insoluble in water and coats the particle surface of the afterglow phosphor,
Water resistance is imparted to the afterglow phosphor.
【００４８】残光性蛍光体の焼成時にリン酸化合物を添
加して焼成すると、大半はリン酸化合物としてその組成
中に含有される。その含有量とりん光輝度、耐熱性、耐
水性への影響をみるため、(Sr0.955Eu0.03Dy0.015)O・0.
91(Al0.95B0.05)2O3・kP2O5残光性蛍光体を試作し、リン
酸化合物の含有量ｋに対するそれぞれの特性を評価し
た。ここで耐熱性、耐水性については次のような方法で
行った。When the phosphoric acid compound is added and baked during the baking of the afterglow phosphor, most of it is contained in the composition as a phosphoric acid compound. To see its content and the effect on phosphorescence brightness, heat resistance, and water resistance, (Sr 0.955 Eu 0.03 Dy 0.015 ) O.0 .
91 (Al 0.95 B 0.05) a prototype 2 O 3 · kP 2 O 5 afterglow phosphor were evaluated their characteristics with respect to the content k of phosphoric acid compound. Here, heat resistance and water resistance were measured by the following methods.
【００４９】耐熱性については、石英ルツボに残光性蛍
光体を１０ｇ入れ、マッフル炉中６００℃で３０分間酸
化焼成を行い、焼成品のりん光輝度を測定し、焼成前の
残光性蛍光体のりん光輝度対する百分率を算出し維持率
として求める。Regarding the heat resistance, 10 g of the afterglow phosphor was put in a quartz crucible and subjected to oxidation firing in a muffle furnace at 600 ° C. for 30 minutes, and the phosphorescence brightness of the fired product was measured. The percentage of the phosphorescence brightness of the body is calculated to obtain the maintenance rate.
【００５０】耐水性については、２５０ｍｌのプラスチ
ック容器に残光性蛍光体を１０ｇ、純水を２００ｇ入
れ、ローラーで３０ｒｐｍの速度で７２時間回転させ
る。次に固液分離し乾燥し、残光性蛍光体のりん光輝度
を測定し、水に接触させる前のりん光輝度対する百分率
を算出し維持率として求める。Regarding the water resistance, 10 g of the afterglow fluorescent substance and 200 g of pure water are put in a 250 ml plastic container, and rotated with a roller at a speed of 30 rpm for 72 hours. Next, solid-liquid separation and drying are performed, and the phosphorescence brightness of the afterglow phosphor is measured, and the percentage of the phosphorescence brightness before contact with water is calculated to obtain the maintenance rate.
【００５１】これらの測定結果をもとに図１〜３に、そ
れぞれりん光輝度、耐熱性、耐水性のリン酸含有量ｋと
の関係を示す。図１から分かるようにリン酸の含有がｋ
≦０．１の広い範囲で励起停止２０分後りん光輝度向上
に効果があり、ｋ＝０．０５付近が最も高くなる。ｋ＞
０．１の範囲ではりん光輝度はリン酸化合物を含有しな
いものよりも低くなる。Based on these measurement results, FIGS. 1 to 3 show the relationship between phosphorescence brightness, heat resistance, and water resistance of phosphoric acid content k, respectively. As can be seen from FIG. 1, the content of phosphoric acid is k
In a wide range of ≤0.1, there is an effect of improving the phosphorescence luminance 20 minutes after the excitation is stopped, and the highest value is obtained around k = 0.05. k>
In the range of 0.1, the phosphorescence brightness is lower than that of the phosphor containing no phosphoric acid compound.
【００５２】図２に示す耐熱試験の結果より、リン酸化
合物の含有は広い濃度範囲で耐熱性に効果があることが
分かり、ｋ≧０．００００５で耐熱性に効果があり、特
にｋ≧０．０１が好ましく、０．０２≦ｋ≦０．０５の
範囲が最も好ましい。From the results of the heat resistance test shown in FIG. 2, it was found that the inclusion of the phosphoric acid compound had an effect on the heat resistance in a wide concentration range, and k ≧ 0.00005 had an effect on the heat resistance, and particularly k ≧ 0. 0.01 is preferable, and the range of 0.02 ≦ k ≦ 0.05 is most preferable.
【００５３】リン酸化合物を含まない残光性蛍光体の耐
水性は何れも０％であって、これは蛍光体結晶が破壊さ
れてしまい、全く光らなくなってしまうことによる。図
３に示すように、耐水性に及ぼすリン酸の効果は広い範
囲に渡り、実際０＜ｋであれば効果があるが、０．００
１≦ｋ≦０．６の範囲で維持率が２０％を越え、０．０
２≦ｋ≦０．１の範囲で維持率が４０％を越え、ｋ＝
０．０５付近が特に維持率が５０％を越えて最も好まし
い。The afterglow phosphors containing no phosphoric acid compound each had a water resistance of 0%, because the phosphor crystals were destroyed and no light was emitted. As shown in FIG. 3, the effect of phosphoric acid on the water resistance has a wide range, and if 0 <k, it is effective.
In the range of 1 ≦ k ≦ 0.6, the maintenance ratio exceeds 20% and 0.0
In the range of 2 ≦ k ≦ 0.1, the maintenance ratio exceeds 40%, and k =
Around 0.05 is most preferable because the maintenance rate exceeds 50%.
【００５４】これらを総合して判断すると、リン酸化合
物濃度ｋは０．００１≦ｋ≦０．２の範囲が好ましく、
０．０１≦ｋ≦０．１の範囲がさらに好ましく、０．０
３≦ｋ≦０．０５の範囲が最も好ましいといえる。しか
し、どのような環境で使用するかにより、ｋの値を選択
すべきである。When these are comprehensively judged, the phosphoric acid compound concentration k is preferably in the range of 0.001 ≦ k ≦ 0.2,
The range of 0.01 ≦ k ≦ 0.1 is more preferable, and 0.0
It can be said that the range of 3 ≦ k ≦ 0.05 is most preferable. However, the value of k should be selected depending on the environment used.
【００５５】２価金属ＭがＳｒである場合の蛍光体結晶
構造をＸ線回折により解析した結果、リン酸化合物を含
有しない残光性蛍光体の結晶はＳｒＡｌ2Ｏ4の単斜晶系
の構造を示すが、硼酸と同時に少しでもリン酸を含有す
ると、α−Ｓｒ3Ｐ2Ｏ8の異種の型の結晶が混在してく
るようになる。さらにリン酸が増えｎ／４≦ｋとなる
と、完全にα−Ｓｒ3Ｐ2Ｏ5だけの結晶になる。また、
２価金属ＭがＣａである場合、リン酸化合物を含有しな
い残光性蛍光体の結晶はＣａＡｌ2Ｏ4の単斜晶系構造を
示すが、少しでもリン酸を含有すると、ＣａＰ2Ｏ6の異
種の型の結晶が混在するようになる。As a result of X-ray diffraction analysis of the phosphor crystal structure in the case where the divalent metal M is Sr, the phosphor of the phosphorescent compound-free afterglow phosphor crystal is a monoclinic system of SrAl 2 O 4. As shown in the structure, when a small amount of phosphoric acid is contained together with boric acid, crystals of different types of α-Sr 3 P 2 O 8 come to be mixed. When the phosphoric acid further increases and n / 4 ≦ k, the crystals become completely α-Sr 3 P 2 O 5 . Also,
When the divalent metal M is Ca, the crystals of the afterglow phosphor containing no phosphoric acid compound show a monoclinic structure of CaAl 2 O 4 , but when phosphoric acid is contained in any amount, CaP 2 O 6 Different types of crystals are mixed.
【００５６】[0056]
［実施例１］蛍光体原料として、ＳｒＣＯ3を１４０．
９８ｇ（０．９５５ｍｏｌ）、Ａｌ2Ｏ3を８８．１４ｇ
（０．８６５ｍｏｌ）、Ｅｕ2Ｏ3を５．２８ｇ（０．０
１５ｍｏｌ）、Ｄｙ2０3を２．８０ｇ（０．００７５ｍ
ｏｌ）、Ｈ3ＢＯ3を５．６３ｇ（０．０９１ｍｏｌ）、
及び（ＮＨ4）2ＨＰＯ4を７．９２ｇ（０．０６０ｍｏ
ｌ）を、混合媒体としてアルミナボール入りのセラミッ
クポットに入れ、ローラーで２時間混合し蛍光体焼成前
混合原料（以下原料生粉という）を得る。次に、原料生
粉をアルミナルツボに入れ、還元雰囲気下１４００℃で
５時間焼成し蛍光体焼成品を得る。次に焼成品を粉砕
し、２００メッシュの篩を通し、本発明の(Sr0.955Eu
0.03Dy0.015)O・0.91(Al0.95B0.05)2O3・0.03P2O5蛍光体
を得る。Example 1 SrCO 3 was added as a phosphor raw material at 140.
98 g (0.955 mol), Al 2 O 3 88.14 g
(0.865 mol), 5.28 g (0.02%) of Eu 2 O 3
15mol), Dy 2 0 3 to 2.80g (0.0075m
ol) and 5.63 g (0.091 mol) of H 3 BO 3 ,
And (NH 4 ) 2 HPO 4 7.92 g (0.060 mo
1) is placed in a ceramic pot containing alumina balls as a mixing medium, and mixed for 2 hours with a roller to obtain a mixed raw material before firing the phosphor (hereinafter referred to as raw raw powder). Next, the raw raw material powder is placed in an alumina crucible and fired at 1400 ° C. for 5 hours in a reducing atmosphere to obtain a phosphor fired product. Next, the calcined product is crushed and passed through a 200-mesh sieve to obtain (Sr 0.955 Eu
0.03 Dy 0.015 ) O.0.91 (Al 0.95 B 0.05 ) 2 O 3 .0.03 P 2 O 5 phosphor is obtained.
【００５７】得られた蛍光体は可視から紫外域の広い範
囲において励起発光し、ブラックライト、殺菌灯によっ
ても励起され発光し、よって、蛍光水銀灯、低圧水銀蒸
気放電灯にも応用できるが、ここでは、蓄光蛍光体の用
途に応じた試験をJIS K 5120に従い行う。The obtained phosphor is excited to emit light in a wide range from visible to ultraviolet and is also excited to emit light by black light and germicidal lamp. Therefore, it can be applied to fluorescent mercury lamp and low-pressure mercury vapor discharge lamp. Then, a test according to the use of the phosphorescent phosphor is performed according to JIS K 5120.
【００５８】蛍光体試料１ｇにアクリル樹脂ワニスを
０．５ｇ加え、試料をすりつぶさないように注意して十
分練り合わせ、アルミニウム板に試料が１００mg/cm2以
上の厚さになるように塗り、乾燥したものを試験片とし
た。この試験片は、蛍光色、りん光輝度、及び耐光性の
測定に用いる。0.5 g of acrylic resin varnish was added to 1 g of the phosphor sample, and the mixture was sufficiently kneaded so as not to grind the sample, and the sample was coated on an aluminum plate to a thickness of 100 mg / cm 2 or more and dried. What was done was made into the test piece. This test piece is used to measure fluorescent color, phosphorescence brightness, and light resistance.
【００５９】蛍光色の測定については、２５３．７ｎｍ
の紫外線を試料に当て、蛍光を分光光度計によりスペク
トル分布を求め、ＣＩＥ表色系の色度を算出した。蛍光
色度はｘ＝０．２４８，ｙ＝０．５６１で、視感度の高
い緑色系を呈し、蓄光蛍光体として優れた基本特性を有
することが明らかである。For the measurement of fluorescent color, 253.7 nm
Was applied to the sample, and the spectral distribution of the fluorescence was obtained with a spectrophotometer, and the chromaticity of the CIE color system was calculated. It is clear that the fluorescent chromaticity is x = 0.248 and y = 0.561, exhibits a green color with high visibility, and has excellent basic characteristics as a phosphorescent phosphor.
【００６０】りん光輝度の測定については、JIS Z 9100
（蓄光安全標識板のりん光輝度の測定方法）を参考に行
った。試験片を暗所に３時間以上外光を遮断した状態で
保管した後、試験片に常用光源Ｄ65の光を２００ルクス
の照度で４分間照射し、照射を止めてから２０分後のり
ん光輝度を(Sr0.955Eu0.03Dy0.015Tm0.003)O・(Al0.95B
0.05)2O3蛍光体のりん光輝度を１００％とした相対値と
して測定した。本発明の残光性蛍光体(Sr0.952Eu0.03Dy
0.015)O・0.91(Al0.95B0.05)2O3・0.03P2O5のりん光輝度
は９８％であった。Regarding the measurement of phosphorescence brightness, JIS Z 9100
The measurement was carried out with reference to (Measurement method of phosphorescence luminance of luminous safety signboard). After the test piece was stored in the dark for 3 hours or more in a state where the external light was blocked, the test piece was irradiated with the light of the common light source D 65 at an illuminance of 200 lux for 4 minutes, and phosphorus was irradiated 20 minutes after the irradiation was stopped. Light intensity (Sr 0.955 Eu 0.03 Dy 0.015 Tm 0.003 ) O ・ (Al 0.95 B
It was measured as a relative value with the phosphorescence brightness of the 0.05 ) 2 O 3 phosphor taken as 100%. Afterglow phosphor of the present invention (Sr 0.952 Eu 0.03 Dy
0.015) Mitsuteru Hayashi intensity of O · 0.91 (Al 0.95 B 0.05 ) 2 O 3 · 0.03P 2 O 5 was 98%.
【００６１】耐光性の試験については、JIS K 5671中の
発光塗料の耐光性の試験方法を参考に次のように行っ
た。先ず、劣化源として３００Ｗの高圧水銀灯の光を試
験片に２０cm離し１００時間照射した後、暗所に１時間
以上外光を遮断した状態で保管し、その後常用光源Ｄ65
の光を２００ルクスの照度で４分間照射し、照射を止め
てから５分後のりん光輝度を測定する。次に高圧水銀灯
による照射してない基準品の５分後のりん光輝度に対す
る相対値として維持率を求め、この結果より耐光性を評
価した。この値が大きい方が耐光性が良いことになる。
従来のＺｎＳ：Ｃｕ蛍光体のりん光輝度が２３％で，高
圧水銀灯の照射により著しく低下しているのに対して、
本発明の残光性蛍光体のりん光輝度は９５％とほとんど
劣化せず極めて耐光性に優れている。The light fastness test was carried out as follows with reference to the light fastness test method of the luminescent paint in JIS K 5671. First, after irradiating 20cm apart 100 hours on the test piece with light of a high pressure mercury lamp of 300W as the deterioration source, in storage after blocking the external light more than 1 hour in the dark, then conventional light source D 65
Is irradiated for 4 minutes with an illuminance of 200 lux, and the phosphorescence brightness is measured 5 minutes after the irradiation is stopped. Next, the maintenance factor was calculated as a relative value with respect to the phosphorescence luminance of the reference product not irradiated with the high-pressure mercury lamp after 5 minutes, and the light resistance was evaluated from this result. The larger this value is, the better the light resistance is.
While the phosphorescence brightness of the conventional ZnS: Cu phosphor is 23%, which is remarkably reduced by irradiation with a high pressure mercury lamp,
The phosphorescence brightness of the afterglow phosphor of the present invention is 95%, which is hardly deteriorated and is extremely excellent in light resistance.
【００６２】耐熱性については、石英ルツボに残光性蛍
光体を１０ｇ入れ、マッフル炉中６００℃で３０分間酸
化焼成を行い、焼成品のりん光輝度を測定し、焼成前の
残光性蛍光体のりん光輝度対する百分率を算出し維持率
として求める。本発明の残光性蛍光体は７６．６％の維
持率を示した。Regarding the heat resistance, 10 g of the afterglow phosphor was put in a quartz crucible and subjected to oxidation firing in a muffle furnace at 600 ° C. for 30 minutes, and the phosphorescence brightness of the fired product was measured. The percentage of the phosphorescence brightness of the body is calculated to obtain the maintenance rate. The afterglow phosphor of the present invention showed a retention rate of 76.6%.
【００６３】耐水性については、２５０ｍｌのプラスチ
ック容器に残光性蛍光体を１０ｇ、純水を２００ｇ入
れ、ローラーで３０ｒｐｍの速度で７２時間回転させ
る。次に固液分離し乾燥し、残光性蛍光体のりん光輝度
を測定し、水に接触させる前のりん光輝度対する百分率
を算出し維持率として求める。本発明の残光性蛍光体は
４９．１％の維持率を示した。Regarding the water resistance, a 250 ml plastic container was charged with 10 g of the afterglow phosphor and 200 g of pure water, and was rotated with a roller at a speed of 30 rpm for 72 hours. Next, solid-liquid separation and drying are performed, and the phosphorescence brightness of the afterglow phosphor is measured, and the percentage of the phosphorescence brightness before contact with water is calculated to obtain the maintenance rate. The afterglow phosphor of the present invention showed a retention rate of 49.1%.
【００６４】［比較例１］（ＮＨ4）2ＨＰＯ4を添加し
ない以外実施例１と同様にして、比較例の残光性蛍光体
(Sr0.955Eu0.03Dy0.015)O・0.91(Al0.95B0.05)2O3を試作
する。励起停止２０分後のりん光輝度は６１％、耐熱性
試験の維持率は２５．１％、耐水性については維持率は
０％で全く発光しなかった。Comparative Example 1 The afterglow phosphor of Comparative Example was prepared in the same manner as in Example 1 except that (NH 4 ) 2 HPO 4 was not added.
(Sr 0.955 Eu 0.03 Dy 0.015 ) O ・ 0.91 (Al 0.95 B 0.05 ) 2 O 3 is experimentally manufactured. 20 minutes after the excitation was stopped, the phosphorescence luminance was 61%, the heat resistance test maintenance rate was 25.1%, and the water resistance maintenance rate was 0%, and no light emission was observed.
【００６５】２価金属ＭがＳｒである場合の他の実施例
２〜１３、リン酸化合物を含まない比較例２〜１０につ
いても同様に試作し、同様に測定し、実施例１、比較例
１を含めて結果を表１及び表２にまとめる。Other Examples 2 to 13 in the case where the divalent metal M is Sr and Comparative Examples 2 to 10 not containing a phosphoric acid compound were similarly prototyped and measured in the same manner. The results including 1 are summarized in Tables 1 and 2.
【００６６】[0066]
【表１】 [Table 1]
【００６７】[0067]
【表２】 [Table 2]
【００６８】［実施例１４］蛍光体原料として、ＣａＣ
Ｏ3を９５．５９ｇ（０．９５５ｍｏｌ）、Ａｌ2Ｏ 3を
９４．０１ｇ（０．９２２ｍｏｌ）、Ｅｕ2Ｏ3を２．６
４ｇ（０．００７５ｍｏｌ）、Ｎｄ2０3を５．０５ｇ
（０．０１５ｍｏｌ）、Ｈ3ＢＯ3を６．００ｇ（０．０
９７ｍｏｌ）、及び（ＮＨ4）2ＨＰＯ4を７．９２ｇ
（０．０６０ｍｏｌ）を、混合媒体としてアルミナボー
ル入りのセラミックポットに入れ、ローラーで２時間混
合し蛍光体焼成前混合原料（以下原料生粉という）を得
る。次に、原料生粉をアルミナルツボに入れ、還元雰囲
気下１４００℃で５時間焼成し蛍光体焼成品を得る。次
に焼成品を粉砕し、２００メッシュの篩を通し、本発明
の(Ca0.955Eu0.015Nd0.03)O・0.97(Al0.95B0.05)2O3・0.0
3P2O5蛍光体を得る。[Example 14] CaC was used as a phosphor raw material.
O395.59 g (0.955 mol), Al2O 3To
94.01 g (0.922 mol), Eu2O3To 2.6
4 g (0.0075 mol), Nd2035.05g
(0.015 mol), H3BO36.00 g (0.0
97 mol), and (NHFour)2HPOFour7.92 g
(0.060 mol) as alumina
Put it in a ceramic pot with a roller and mix it with a roller for 2 hours.
Combined phosphor to obtain raw material before firing (hereinafter referred to as raw raw powder)
It Next, put the raw raw material powder in an alumina crucible and put it in a reducing atmosphere.
It is fired at 1,400 ° C. under air for 5 hours to obtain a fired phosphor product. Next
The fired product was crushed into pieces, passed through a 200-mesh sieve, and
Of (Ca0.955EU0.015Nd0.03) O ・ 0.97 (Al0.95B0.05)2O3・ 0.0
3P2OFiveObtain a phosphor.
【００６９】２価金属ＭがＣａである場合の他の実施例
１５〜１８、リン酸化合物を含まない比較例１５〜１８
についても同様に試作し、同様に測定し、実施例１４、
比較例１４を含めて結果を表３、表４にまとめる。Other Examples 15 to 18 when the divalent metal M is Ca, Comparative Examples 15 to 18 containing no phosphoric acid compound
Was also manufactured in the same manner and measured in the same manner as in Example 14,
The results including Comparative Example 14 are summarized in Tables 3 and 4.
【００７０】これらより、本発明の残光性蛍光体は２価
金属ＭがＳｒの緑色系の場合も、ＭがＣａの青色系の場
合も、りん光輝度、耐熱性、及び耐水性において優れて
いる。特に、耐水性に対するリン酸化合物の効果は絶大
であり、ＭがＳｒの場合、リン酸化合物を加えない比較
例では維持率がすべて０％であるのに対し、本発明品は
大きく改善されている。From the above, the afterglow phosphor of the present invention is excellent in phosphorescence brightness, heat resistance and water resistance regardless of whether the divalent metal M is Sr green or M is Ca blue. ing. In particular, the effect of the phosphoric acid compound on the water resistance is tremendous, and when M is Sr, the maintenance ratios are all 0% in Comparative Examples in which the phosphoric acid compound is not added, whereas the product of the present invention is greatly improved. There is.
【００７１】[0071]
【表３】 [Table 3]
【００７２】[0072]
【表４】 [Table 4]
【００７３】［実施例１９］蛍光体原料として、ＳｒＣ
Ｏ3を１４０．９８ｇ（０．９５５ｍｏｌ）、Ａｌ2Ｏ3
を１６９．４０ｇ（１．６６３ｍｏｌ）、Ｅｕ2Ｏ3を
５．２８ｇ（０．０１５ｍｏｌ）、Ｄｙ2０3を２．８０
ｇ（０．００７５ｍｏｌ）、Ｈ3ＢＯ3を１０．８ｇ
（０．１７５ｍｏｌ）、及び（ＮＨ4）2ＨＰＯ4を７．
９２ｇ（０．０６０ｍｏｌ）を、混合媒体としてアルミ
ナボール入りのセラミックポットに入れ、ローラーで２
時間混合し蛍光体焼成前混合原料（以下原料生粉とい
う）を得る。次に、原料生粉をアルミナルツボに入れ、
還元雰囲気下１４００℃で５時間焼成し蛍光体焼成品を
得る。次に焼成品を粉砕し、２００メッシュの篩を通
し、本発明の(Sr0.955Eu0.03Dy0.015)O・1.75(Al0.95B
0.05)2O3・0.03P2O5蛍光体を得る。[Example 19] SrC was used as a phosphor raw material.
O 3 140.98 g (0.955 mol), Al 2 O 3
The 169.40g (1.663mol), and Eu 2 O 3 5.28g (0.015mol) , Dy 2 0 3 2.80
g (0.0075 mol), 10.8 g of H 3 BO 3
(0.175 mol), and (NH 4 ) 2 HPO 4 .
92 g (0.060 mol) was placed in a ceramic pot containing alumina balls as a mixed medium, and the mixture was mixed with a roller to 2
The materials are mixed for a period of time to obtain a mixed raw material (hereinafter referred to as raw raw powder) before firing. Next, put raw raw flour into an alumina crucible,
The phosphor is fired at 1400 ° C. for 5 hours in a reducing atmosphere to obtain a fired phosphor. Next, the calcined product was pulverized and passed through a 200-mesh sieve to obtain (Sr 0.955 Eu 0.03 Dy 0.015 ) O.1.75 (Al 0.95 B) of the present invention.
0.05 ) 2 O 3 .0.03P 2 O 5 phosphor is obtained.
【００７４】２価金属ＭがＣａである場合の他の実施例
１５〜１８、リン酸化合物を含まない比較例１５〜１８
についても同様に試作し、同様に測定し、実施例１４、
比較例１４を含めて結果を表３、表４にまとめる。Other Examples 15 to 18 when the divalent metal M is Ca, Comparative Examples 15 to 18 containing no phosphoric acid compound
Was also manufactured in the same manner and measured in the same manner as in Example 14,
The results including Comparative Example 14 are summarized in Tables 3 and 4.
【００７５】［実施例２０、２１］原料調合時に他の共
付活剤原料を仕込む以外実施例１９と同様の方法で残光
性蛍光体を調製し、同様に測定し、結果を表５、表６に
まとめる。[Examples 20 and 21] Afterglow phosphors were prepared in the same manner as in Example 19 except that other coactivator raw materials were charged during the preparation of the raw materials, and the results were measured in the same manner. It is summarized in Table 6.
【００７６】[0076]
【表５】 [Table 5]
【００７７】[0077]
【表６】 [Table 6]
【００７８】これらより、本発明の残光性蛍光体は２価
金属ＭがＳｒの緑色系の場合、ＭがＣａの青色系の場
合、２価金属と硼アルミン酸の比が大きい青緑色系の場
合についても、りん光輝度、耐熱性、及び耐水性におい
て優れている。特に、耐水性に対するリン酸化合物の効
果は絶大であり、ＭがＳｒの場合、リン酸化合物を加え
ない比較例では維持率がすべて０％であるのに対し、本
発明品は大きく改善されている。特に、From the above, the afterglow phosphor of the present invention is a blue-green system in which the divalent metal M is Sr in the green system, M is Ca in the blue system, and the ratio of the divalent metal to the borate is large. Also in the case of, the phosphorescence brightness, heat resistance, and water resistance are excellent. In particular, the effect of the phosphoric acid compound on the water resistance is tremendous, and when M is Sr, the maintenance ratios are all 0% in Comparative Examples in which the phosphoric acid compound is not added, whereas the product of the present invention is greatly improved. There is. In particular,
【００７９】[0079]
【発明の効果】本発明は以上説明したように構成されて
いるので、以下に記載されるような効果を奏する。Since the present invention is configured as described above, it has the following effects.
【００８０】蓄光蛍光体をプラスチック、セラミックに
混入させて使用する場合、これらを溶融させるため、蓄
光蛍光体は３００〜７００℃程度の温度下にさらされ
る。また、屋外で使用する場合、特に水分との接触は起
こりやすくなる。これに対し、本発明の残光性蛍光体は
耐熱性、耐水性が向上され、さらに耐光性においても優
れているため、このような条件下においても実用するこ
とができる。When the phosphorescent substance is mixed with plastic or ceramic for use, the phosphorescent substance is exposed to a temperature of about 300 to 700 ° C. in order to melt them. In addition, when used outdoors, contact with moisture is particularly likely to occur. On the other hand, the afterglow phosphor of the present invention has improved heat resistance and water resistance, and is also excellent in light resistance, and therefore can be put to practical use under such conditions.
【００８１】また、本発明残光性蛍光体は焼成工程でで
きる焼成品は柔らかく、後工程での粉砕、フルイ等の処
理を簡単化でき、収率を向上することができる。さら
に、予期せぬ効果としてりん光輝度が向上する。Further, the afterglow phosphor of the present invention is soft in the fired product obtained in the firing step, and the processing such as pulverization and sieving in the subsequent step can be simplified and the yield can be improved. Furthermore, as an unexpected effect, the phosphorescence brightness is improved.
【図１】本発明の残光性蛍光体のリン酸化合物含有量と
励起停止２０分後りん光輝度の関係を示す特性図であ
る。FIG. 1 is a characteristic diagram showing the relationship between the content of a phosphoric acid compound in the afterglow phosphor of the present invention and the phosphorescence luminance 20 minutes after the termination of excitation.
【図２】本発明の残光性蛍光体の耐熱試験におけるリン
酸化合物含有量と維持率の関係を示す特性図である。FIG. 2 is a characteristic diagram showing a relationship between a phosphoric acid compound content and a retention rate in a heat resistance test of the afterglow phosphor of the present invention.
【図３】本発明の残光性蛍光体の耐水試験におけるリン
酸化合物含有量と維持率の関係を示す特性図である。FIG. 3 is a characteristic diagram showing a relationship between a phosphoric acid compound content and a retention rate in a water resistance test of the afterglow phosphor of the present invention.
Claims (5)
ン酸塩蛍光体において、その化学組成式が下記の範囲に
あることを特徴とする残光性蛍光体。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ ０．５≦ｎ≦３．０ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＭｇ、Ｃａ、Ｓｒ、Ｂａ、及び
Ｚｎからなる２価金属の群より選ばれた少なくとも１種
であり、Ｑは共付活剤でありＭｎ、Ｚｒ、Ｎｂ、Ｐｒ、
Ｎｄ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及
びＬｕからなる群より選ばれた少なくとも１種である。1. A afterglow phosphor having a chemical composition formula in the following range in an aluminate phosphor activated with divalent europium. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 0.5 ≦ n ≦ 3.0 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, M in the composition formula is at least one selected from the group of divalent metals consisting of Mg, Ca, Sr, Ba and Zn, and Q is a co-activator and is Mn, Zr. , Nb, Pr,
It is at least one selected from the group consisting of Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
ン酸塩蛍光体において、その化学組成式が下記の範囲に
あり、その結晶構造が単斜晶系を主体とすることを特徴
とする請求項１に記載の残光性蛍光体。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ ０．５≦ｎ≦１．５ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＳｒが７０モル％以上である。2. A divalent europium-activated aluminate phosphor having a chemical composition formula in the following range and a crystal structure mainly composed of a monoclinic system. Item 1. The afterglow phosphor according to Item 1. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 0.5 ≦ n ≦ 1.5 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, S in the composition formula is 70 mol% or more of Sr.
ン酸塩蛍光体において、その化学組成式が下記の範囲に
あり、その結晶構造が単斜晶系を主体とすることを特徴
とする請求項１に記載の残光性蛍光体。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ ０．５≦ｎ≦１．５ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＣａが７０モル％以上である。3. A divalent europium-activated aluminate phosphor having a chemical composition formula in the following range and a crystal structure mainly composed of a monoclinic system. Item 1. The afterglow phosphor according to Item 1. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 0.5 ≦ n ≦ 1.5 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≤0.75 However, Ca in the composition formula is 70 mol% or more of Ca.
ン酸塩蛍光体において、その化学組成式が下記の範囲に
あり、その結晶構造が斜方晶系を主体とすることを特徴
とする請求項１に記載の残光性蛍光体。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ １．５≦ｎ≦３．０ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＳｒが７０モル％以上である。4. The aluminate phosphor activated with divalent europium has a chemical composition formula within the following range, and its crystal structure is mainly orthorhombic. Item 1. The afterglow phosphor according to Item 1. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 1.5 ≦ n ≦ 3.0 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, S in the composition formula is 70 mol% or more of Sr.
ン酸塩蛍光体において、その化学組成式が下記の範囲に
あり、その結晶構造が斜方晶系であることを特徴とする
請求項１に記載の残光性蛍光体。 （Ｍ1-p-qＥｕpＱq）Ｏ・ｎ（Ａｌ1-mＢm）2Ｏ3・ｋＰ2
Ｏ5 ０．０００１≦ｐ≦０．５ ０．０００１≦ｑ≦０．５ １．７≦ｎ≦１．８ ０．０００１≦ｍ≦０．５ ０＜ｋ≦０．２ ０．０００２≦ｐ＋ｑ≦０．７５ ただし、組成式中のＭはＳｒである。5. The aluminate phosphor activated with divalent europium has a chemical composition formula in the following range and a crystal structure of an orthorhombic system. The afterglow phosphor described in 1. (M 1-pq Eu p Q q ) O ・ n (Al 1-m B m ) 2 O 3・ kP 2
O 5 0.0001 ≦ p ≦ 0.5 0.0001 ≦ q ≦ 0.5 1.7 ≦ n ≦ 1.8 0.0001 ≦ m ≦ 0.5 0 <k ≦ 0.2 0.0002 ≦ p + q ≦ 0.75 However, M in the composition formula is Sr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22284395A JP3232549B2 (en) | 1994-09-29 | 1995-08-31 | Afterglow phosphor |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-234606 | 1994-09-29 | ||
| JP23460694 | 1994-09-29 | ||
| JP22284395A JP3232549B2 (en) | 1994-09-29 | 1995-08-31 | Afterglow phosphor |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001203455A Division JP3646675B2 (en) | 1994-09-29 | 2001-07-04 | Afterglow phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08151574A true JPH08151574A (en) | 1996-06-11 |
| JP3232549B2 JP3232549B2 (en) | 2001-11-26 |
Family
ID=26525117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22284395A Expired - Lifetime JP3232549B2 (en) | 1994-09-29 | 1995-08-31 | Afterglow phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3232549B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008061436A1 (en) | 2006-11-20 | 2008-05-29 | Sichuan Sunfor Light Co., Ltd. | Waterproof multi-element co-activated long afterglow light-accumulating phosphors |
| JP2009224032A (en) * | 2008-03-13 | 2009-10-01 | Hitachi Ltd | Display device and plasma display panel |
| JP2009256555A (en) * | 2008-04-21 | 2009-11-05 | National Institute Of Advanced Industrial & Technology | Accumulative phosphor and method for producing the same |
| US7955523B2 (en) | 2005-07-01 | 2011-06-07 | Sichuan Sunfor Light Co., Ltd. | Long afterglow luminescent material with compounded substrates and its preparation method |
| JP2017155217A (en) * | 2016-02-26 | 2017-09-07 | 日亜化学工業株式会社 | Phosphor, light-emitting device and manufacturing method of phosphor |
-
1995
- 1995-08-31 JP JP22284395A patent/JP3232549B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7955523B2 (en) | 2005-07-01 | 2011-06-07 | Sichuan Sunfor Light Co., Ltd. | Long afterglow luminescent material with compounded substrates and its preparation method |
| WO2008061436A1 (en) | 2006-11-20 | 2008-05-29 | Sichuan Sunfor Light Co., Ltd. | Waterproof multi-element co-activated long afterglow light-accumulating phosphors |
| EP2093273A1 (en) * | 2006-11-20 | 2009-08-26 | Sichuan Sunfor Light Co., Ltd. | Waterproof multi-element co-activated long afterglow light-accumulating phosphors |
| EP2093273A4 (en) * | 2006-11-20 | 2009-12-16 | Sichuan Sunfor Light Co Ltd | Waterproof multi-element co-activated long afterglow light-accumulating phosphors |
| JP2009224032A (en) * | 2008-03-13 | 2009-10-01 | Hitachi Ltd | Display device and plasma display panel |
| JP2009256555A (en) * | 2008-04-21 | 2009-11-05 | National Institute Of Advanced Industrial & Technology | Accumulative phosphor and method for producing the same |
| JP2017155217A (en) * | 2016-02-26 | 2017-09-07 | 日亜化学工業株式会社 | Phosphor, light-emitting device and manufacturing method of phosphor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3232549B2 (en) | 2001-11-26 |
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