JP3956551B2 - Method for producing aluminate phosphor for phosphorescent material - Google Patents
Method for producing aluminate phosphor for phosphorescent material Download PDFInfo
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- JP3956551B2 JP3956551B2 JP28540199A JP28540199A JP3956551B2 JP 3956551 B2 JP3956551 B2 JP 3956551B2 JP 28540199 A JP28540199 A JP 28540199A JP 28540199 A JP28540199 A JP 28540199A JP 3956551 B2 JP3956551 B2 JP 3956551B2
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- aluminate
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Description
【０００１】
【発明の属する技術分野】
本発明は、紫外線、可視光で励起されて長時間の残光性を示す蓄光材等に使用される蓄光材用アルミン酸塩系蛍光体の製造方法に関する。
【従来の技術】
【０００２】
従来、夜間表示や夜光時計用として、放射性物質を蛍光体に添加した自発光性夜行塗料が利用されてきた。最近に至り放射性物質を用いない長時間の残光性を有する蓄光性蛍光体の応用が広く検討されている。蓄光性蛍光体としては、例えば、ユーロピウム付活ストロンチウムアルミネイト（ＳｒＡｌ2Ｏ4：Ｅｕ等)が主として検討されている。
【０００３】
蛍光体の特性は、蛍光体の構成イオンの分散性に影響を受け、発光効率は蛍光体の構成イオンの分散性、中でも付活剤や共付活剤の分散性が良好なほうが高いことは良く知られている。蓄光性蛍光体においても残光輝度は構成イオンの分散性が良好になるほど高くなると言われている。
さらに、蛍光体の発光特性は微量不純物に大きく影響を受けることはよく知られている。そのため、蓄光材用アルミン酸塩系蛍光体の基体となるアルミネイトには高純度に精製したα−アルミナあるいは高純度γ−アルミナ、高純度水酸化アルミニウム等の高純度アルミニウム化合物粉末が主原料として用いられる。
【０００４】
また、アルミニウム化合物としては、主にα−アルミナあるいはγ−アルミナ等のアルミナを用いることが多いが、アルミナを用いる場合、各構成イオンの分散が良好な単一相の蓄光材用アルミン酸塩系蛍光体を得るのに、１６００℃以上の高温焼成を必要とすることが知られている。この場合、必要とする焼成炉等の装置部材が高価のものに限定される。
【０００５】
かかる背景からして、発光効率および残光輝度が向上する蓄光材用アルミン酸塩系蛍光体を得るために、構成イオンの分散がより良好な蓄光材用アルミン酸塩系蛍光体を合成することが求められてきた。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、発光効率が良好で、残光輝度が高い、各構成イオンの分散性が良好な蓄光材用アルミン酸塩系蛍光体を容易に製造可能な方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、係る状況下、上記の課題を解決すべく鋭意研究を重ねた結果、アルミニウム化合物が分散した有機溶媒に有機酸を添加して混合して得られたスラリーに、Ｅｕ、Ｄｙ、Ｎｄ、Ｓｒ、Ｃａ、Ｐｂ、Ｚｎ、Ｂｉからなる群から選ばれる少なくとも１つ以上の陽イオン水溶液を添加すると、有機酸がアルミニウムと錯体を形成することなく該陽イオンと共沈して、該陽イオンの有機酸塩をアルミニウム化合物の周囲に析出し、これを分離して得られる蓄光材用アルミン酸塩系蛍光体の前駆体を焼成すると、均一組成の蓄光材用アルミン酸蛍光体を容易に取得できる方法を見出し、本発明を完成するに至った。
【０００８】
すなわち、本発明は以下の（１）および（２）に関するものである。
（１）アルミニウム化合物と有機酸を有機溶媒を用いて混合して得られたスラリーと、Ｅｕ、Ｄｙ、Ｎｄ、Ｓｒ、Ｃａ、Ｐｂ、ＺｎおよびＢｉからなる群から選ばれる少なくとも１つ以上の陽イオン水溶液とを混合し、該陽イオンが有機酸塩として周囲に析出したアルミニウム化合物を分離して得られる蓄光材用アルミン酸塩系蛍光体の前駆体を、焼成することを特徴とする蓄光材用アルミン酸塩系蛍光体の製造方法。
（２）上記（１）記載の製造方法によって得られた一次粒子径が０．０５μｍ以上５μｍ以下の粒子が８０重量％以上含まれることを特徴とする蓄光材用アルミン酸塩系蛍光体。
【０００９】
【発明の実施の形態】
以下に本発明について詳しく説明する。
本発明においてアルミニウム化合物としては、アルミニウムを含む固体であれば、いかなるものを用いても良く、例えば、水酸化アルミニウム、酸化アルミニウム、硫酸アルミニウムが挙げられる。
【００１０】
本発明においてアルミニウム化合物と有機酸を有機溶媒を用いて混合して得られたスラリーとする際に用いる有機溶媒は、アルミニウム化合物を分散させるものならばいかなる有機溶媒であっても良く、例えば、メタノール、エタノール、イソプロパノール、プロパノール、ブタノール等のアルコール類、クロロホルム、ケロシン等が挙げられる。アルミニウム化合物が分散しやすいアルコール類が好ましい。
【００１１】
本発明において用いる有機酸としては、−ＣＯＯＨ基を有する有機酸が好ましく、例えば、シュウ酸、蟻酸、酢酸、酒石酸等が挙げられる。特に、シュウ酸を用いた場合、 Ｅｕ、Ｄｙ、Ｎｄ、Ｓｒ、Ｃａ、Ｐｂ、Ｚｎ、Ｂｉの陽イオンと反応しやすく、 Ｅｕ、Ｄｙ、Ｎｄ、Ｓｒ、Ｃａ、Ｐｂ、Ｚｎ、Ｂｉ の陽イオンがアルミニウム化合物の周囲にシュウ酸塩として析出しやすいため、より好ましい。また、用いる有機酸の量としては、好ましくはアルミニウム以外の陽イオンが有機酸塩として析出するのに必要な化学量論量の１倍以上、より好ましくは３倍以上である。
【００１２】
本発明において用いる陽イオン水溶液としては、陽イオンの塩化物水溶液、陽イオンの硝酸塩水溶液等を挙げることができる。また、構成陽イオンとしては、例えば、ユーロピウム、ジスプロシウム付活ストロンチウムアルミネイト（ＳｒＡｌ2Ｏ4：Ｅｕ、Ｄｙ)を製造する時は、Ｅｕ、Ｄｙ、Ｓｒのイオンを用いれば良い。
【００１３】
具体的な組成としては、例えば、蓄光材用アルミン酸塩系蛍光体が、一般式ｘＭＯ・ｚＡｌ2Ｏ3で示される複合酸化物基体にユーロピウム（Ｅｕ）が付活剤として、さらにジスプロシウム（Ｄｙ）、ネオジム（Ｎｄ）から選ばれる少なくとも１種の金属元素が共付活剤として添加された化合物の場合、ｘが０．５から１．１、ｚが１の範囲にあることが好ましい。
【００１４】
例えば、蓄光材用アルミン酸塩系蛍光体が、一般式ｘ1ＳｒＯ・ｚ1Ａｌ2Ｏ3で示される複合酸化物基体にＥｕが付活剤として、さらにＤｙが共付活剤として添加された化合物の場合、ｘ1が０．９から１．１でかつ、ｚ1が１、あるいはｘ1が３．９から４．１でかつ、ｚ1が７の範囲にあることが好ましい。
【００１５】
例えば、蓄光材用アルミン酸塩系蛍光体が、一般式ｘ2ＣａＯ・ｚ2Ａｌ2Ｏ3で示される複合酸化物基体にＥｕが付活剤として、さらにＮｄが共付活剤として添加された化合物の場合、ｘ2が０．９から１．１でかつ、ｚ2が１の範囲にあることが好ましい。
【００１６】
また、混合の方法は、いかなる方法によっても良いが、例えば攪拌による混合方法が制御しやすく、低コストであるので好ましい。
【００１７】
本発明において、 Ｅｕ、Ｄｙ、Ｎｄ、Ｓｒ、Ｃａ、Ｐｂ、Ｚｎ、Ｂｉ からなる群から選ばれる少なくとも１つ以上の陽イオンが有機酸塩として周囲に析出したアルミニウム化合物は、通常、固液分離にて分離し、蓄光材用アルミン酸塩系蛍光体の前駆体を得る。このときの固液分離の方法はいかなる方法によっても良いが、例えば、濾過・乾燥する方法、スプレードライにより顆粒化する方法、エバポレーションにより固液分離する方法などが挙げられる。
【００１８】
次に、蓄光材用アルミン酸塩系蛍光体の前駆体を焼成する方法はいかなる方法によっても良いが、例えば、前駆体をアルミナボートに充填し、所定のガス雰囲気中で所定の温度で焼成して蓄光材用アルミン酸塩系蛍光体を得ることができる。
【００１９】
また、焼成後に得られた蓄光材用アルミン酸塩系蛍光体に、分散、水洗、乾燥、篩い分け等の処理を行ってもよい。
【００２０】
本発明にて得られた蓄光材用アルミン酸塩系蛍光体は、一次粒子径が０．０５μｍ以上５μｍ以下の粒子を８０重量％以上含み、通常の方法にて得られたアルミン酸塩系蛍光体の一次粒子径よりも小さい。このように、蛍光体の一次粒子径を小さくかつ粒度分布をシャープにすることにより、ペースト化する際、効率良く、蛍光体を分散することが可能となり、発光輝度の高い樹脂組成物を作製することが可能となる。
【００２１】
本発明による蓄光材用アルミン酸塩系蛍光体は、構成イオンの分散が極めて良好であるために、残光特性に優れており蓄光材として極めて有用である。
【００２２】
【実施例】
次に、本発明を実施例によりさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
【００２３】
実施例１
アルミニウムイソプロポキシドの加水分解反応によって得られた水酸化アルミニウム（灼熱減量が２６．３％）６．７１ｇをイソプロパノール１００ｇに分散させ、攪拌を行いながら、シュウ酸が１０ｇ溶解したイソプロパノール２１０ｇを添加して、スラリーＡを調製した。
次に塩化ストロンチウム６水和物、塩化ユウロピウム６水和物、塩化ジスプロシウムそれぞれ所定量を純水２０ｇに溶解し、ストロンチウムイオン、ユウロピウムイオン、ジスプロシウムイオンの混合水溶液を調製した。
次いで、スラリーＡを攪拌しながら、混合水溶液を添加して、水酸化アルミニウムの周囲にストロンチウム、ユウロピウム、ジスプロシウムをシュウ酸塩として析出させ、エバポレーションにより固液分離を行い、蓄光材用蛍光体の前駆体を調製した。
得られた前駆体を弱還元雰囲気中で１３００℃で３時間焼成し、蓄光材用蛍光体（Ｓｒ0.93，Ｅｕ0.02，Ｄｙ0.05）Ｏ・Ａｌ2Ｏ3を得た。得られた（Ｓｒ0.93，Ｅｕ0.02，Ｄｙ0.05）Ｏ・Ａｌ2Ｏ3は高い残光輝度を示した。
【００２４】
【発明の効果】
本発明によれば、各構成イオンの分散が極めて良好な蓄光材用アルミン酸塩系蛍光体を容易に製造することができ、発光効率が良好で、残光が長い蓄光材用アルミン酸塩系蛍光体を安価にて提供することができる。この蓄光材用アルミン酸塩系蛍光体は工業上極めて有用なものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an aluminate phosphor for a phosphorescent material used for a phosphorescent material or the like that is excited by ultraviolet light or visible light and exhibits long-time persistence.
[Prior art]
[0002]
Conventionally, a self-luminous nocturnal paint in which a radioactive substance is added to a phosphor has been used for night display and a night clock. Recently, the application of phosphorescent phosphors having long-time persistence without using radioactive materials has been widely studied. As the phosphorescent phosphor, for example, europium activated strontium aluminate (SrAl 2 O 4 : Eu etc.) is mainly studied.
[0003]
The characteristics of the phosphor are affected by the dispersibility of the constituent ions of the phosphor, and the luminous efficiency is higher when the dispersibility of the constituent ions of the phosphor, in particular, the dispersibility of the activator and coactivator is better. Well known. Even in a phosphorescent phosphor, it is said that the afterglow luminance increases as the dispersibility of constituent ions becomes better.
Furthermore, it is well known that the light emission characteristics of phosphors are greatly affected by trace impurities. Therefore, high purity aluminum compound powders such as highly purified α-alumina, high purity γ-alumina, and high purity aluminum hydroxide are used as the main raw material for the aluminate that is the base of the aluminate phosphor for phosphorescent materials. Used.
[0004]
In addition, as an aluminum compound, alumina such as α-alumina or γ-alumina is often used, but when alumina is used, a single-phase aluminate-based phosphorescent material in which each constituent ion is well dispersed. It is known that high temperature firing at 1600 ° C. or higher is required to obtain a phosphor. In this case, necessary apparatus members such as a firing furnace are limited to expensive ones.
[0005]
From such a background, in order to obtain an aluminate phosphor for phosphorescent material with improved luminous efficiency and afterglow brightness, an aluminate phosphor for phosphorescent material with better dispersion of constituent ions is synthesized. Has been demanded.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of easily producing an aluminate phosphor for a phosphorescent material having good luminous efficiency, high afterglow brightness, and good dispersibility of each constituent ion.
[0007]
[Means for Solving the Problems]
Under the circumstances, the present inventors have conducted intensive research to solve the above problems, and as a result, Eu, Dy were added to a slurry obtained by adding and mixing an organic acid to an organic solvent in which an aluminum compound was dispersed. When at least one cation aqueous solution selected from the group consisting of Nd, Sr, Ca, Pb, Zn and Bi is added, the organic acid coprecipitates with the cation without forming a complex with aluminum, When the precursor of the aluminate phosphor for phosphorescent material obtained by depositing the organic acid salt of the cation around the aluminum compound and separating it is fired, the aluminate phosphor for phosphorescent material of uniform composition is obtained. A method that can be easily obtained was found and the present invention was completed.
[0008]
That is, the present invention relates to the following (1) and (2).
(1) A slurry obtained by mixing an aluminum compound and an organic acid using an organic solvent, and at least one positive electrode selected from the group consisting of Eu, Dy, Nd, Sr, Ca, Pb, Zn, and Bi. A phosphorescent material characterized by firing an aluminate-based phosphor precursor for a phosphorescent material obtained by mixing an aqueous ionic solution and separating an aluminum compound in which the cation is deposited as an organic acid salt around Method for producing aluminate-based phosphors.
(2) An aluminate-based phosphor for a phosphorescent material comprising 80% by weight or more of particles having a primary particle size of 0.05 μm or more and 5 μm or less obtained by the production method according to (1) above.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
In the present invention, any aluminum compound may be used as long as it contains aluminum, and examples thereof include aluminum hydroxide, aluminum oxide, and aluminum sulfate.
[0010]
In the present invention, the organic solvent used for preparing the slurry obtained by mixing the aluminum compound and the organic acid using the organic solvent may be any organic solvent as long as the aluminum compound is dispersed, for example, methanol. , Ethanol, isopropanol, propanol, butanol and other alcohols, chloroform, kerosene and the like. Alcohols in which the aluminum compound is easily dispersed are preferable.
[0011]
The organic acid used in the present invention is preferably an organic acid having a —COOH group, and examples thereof include oxalic acid, formic acid, acetic acid, tartaric acid and the like. In particular, when oxalic acid is used, it easily reacts with cations of Eu, Dy, Nd, Sr, Ca, Pb, Zn and Bi, and cations of Eu, Dy, Nd, Sr, Ca, Pb, Zn and Bi Is more preferable because it tends to precipitate as an oxalate around the aluminum compound. Further, the amount of the organic acid to be used is preferably 1 or more times, more preferably 3 or more times the stoichiometric amount necessary for cation other than aluminum to precipitate as an organic acid salt.
[0012]
Examples of the cation aqueous solution used in the present invention include a cation chloride aqueous solution and a cation nitrate aqueous solution. Further, as constituent cations, for example, when producing europium or dysprosium activated strontium aluminate (SrAl 2 O 4 : Eu, Dy), ions of Eu, Dy, Sr may be used.
[0013]
Specific examples of the composition include an aluminate-based phosphor for a phosphorescent material, a composite oxide substrate represented by the general formula xMO.zAl 2 O 3 , europium (Eu) as an activator, and dysprosium (Dy In the case of a compound to which at least one metal element selected from neodymium (Nd) is added as a coactivator, x is preferably in the range of 0.5 to 1.1 and z is 1.
[0014]
For example, an aluminate phosphor for a phosphorescent material is added to a composite oxide substrate represented by the general formula x 1 SrO · z 1 Al 2 O 3 with Eu as an activator and Dy as a coactivator. In the case of the above compound, it is preferable that x 1 is 0.9 to 1.1 and z 1 is 1, or x 1 is 3.9 to 4.1 and z 1 is in the range of 7.
[0015]
For example, an aluminate phosphor for a phosphorescent material is added to a composite oxide substrate represented by the general formula x 2 CaO · z 2 Al 2 O 3 with Eu as an activator and Nd as a coactivator. In the case of the above compounds, it is preferable that x 2 is 0.9 to 1.1 and z 2 is in the range of 1.
[0016]
The mixing method may be any method. For example, the mixing method by stirring is easy to control and is low in cost.
[0017]
In the present invention, an aluminum compound in which at least one cation selected from the group consisting of Eu, Dy, Nd, Sr, Ca, Pb, Zn, and Bi is deposited as an organic acid salt is usually solid-liquid separated. To obtain a precursor of an aluminate phosphor for a phosphorescent material. The solid-liquid separation method at this time may be any method, and examples thereof include a filtration / drying method, a granulation method by spray drying, and a solid-liquid separation method by evaporation.
[0018]
Next, any method may be used to fire the aluminate phosphor precursor for the phosphorescent material. For example, the precursor is filled in an alumina boat and fired at a predetermined temperature in a predetermined gas atmosphere. Thus, an aluminate phosphor for a phosphorescent material can be obtained.
[0019]
Moreover, you may perform processes, such as dispersion | distribution, water washing, drying, and sieving, to the aluminate type phosphor for phosphorescent materials obtained after baking.
[0020]
The aluminate-based phosphor for phosphorescent material obtained in the present invention contains 80% by weight or more of particles having a primary particle diameter of 0.05 μm or more and 5 μm or less, and the aluminate-based phosphor obtained by a usual method. Smaller than the primary particle size of the body. Thus, by reducing the primary particle size of the phosphor and sharpening the particle size distribution, it becomes possible to disperse the phosphor efficiently when making a paste, and a resin composition with high emission luminance is produced. It becomes possible.
[0021]
The aluminate-based phosphor for a phosphorescent material according to the present invention is very useful as a phosphorescent material because it has excellent afterglow characteristics due to extremely good dispersion of constituent ions.
[0022]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[0023]
Example 1
6.71 g of aluminum hydroxide obtained by hydrolysis of aluminum isopropoxide (26.3% loss on ignition) was dispersed in 100 g of isopropanol, and 210 g of isopropanol in which 10 g of oxalic acid was dissolved was added while stirring. Thus, slurry A was prepared.
Next, predetermined amounts of strontium chloride hexahydrate, europium chloride hexahydrate and dysprosium chloride were dissolved in 20 g of pure water to prepare a mixed aqueous solution of strontium ions, europium ions and dysprosium ions.
Next, while stirring the slurry A, a mixed aqueous solution is added, and strontium, europium, and dysprosium are precipitated as oxalate around the aluminum hydroxide, and solid-liquid separation is performed by evaporation. A precursor was prepared.
The obtained precursor was calcined at 1300 ° C. for 3 hours in a weak reducing atmosphere to obtain a phosphor for phosphorescent material (Sr 0.93 , Eu 0.02 , Dy 0.05 ) O.Al 2 O 3 . The obtained (Sr 0.93 , Eu 0.02 , Dy 0.05 ) O.Al 2 O 3 showed high afterglow luminance.
[0024]
【The invention's effect】
According to the present invention, it is possible to easily produce an aluminate phosphor for a phosphorescent material in which the dispersion of each constituent ion is extremely good, the luminous efficiency is good, and the aluminate for phosphorescent material has a long afterglow. A phosphor can be provided at low cost. This aluminate-based phosphor for phosphorescent material is extremely useful industrially.
Claims (6)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28540199A JP3956551B2 (en) | 1999-10-06 | 1999-10-06 | Method for producing aluminate phosphor for phosphorescent material |
| TW089120565A TWI272299B (en) | 1999-10-06 | 2000-10-03 | A process for producing aluminate-based phosphor |
| US09/677,769 US6565771B1 (en) | 1999-10-06 | 2000-10-03 | Process for producing aluminate-based phosphor |
| KR1020000058210A KR100700952B1 (en) | 1999-10-06 | 2000-10-04 | Method for producing aluminate-based fluorescent material |
| EP00121707A EP1090975B1 (en) | 1999-10-06 | 2000-10-04 | A process for producing aluminate-based phosphor |
| EP05000399A EP1553156A3 (en) | 1999-10-06 | 2000-10-04 | A process for producing aluminate-based phosphor |
| DE60021328T DE60021328T2 (en) | 1999-10-06 | 2000-10-04 | Production process for the production of aluminate phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28540199A JP3956551B2 (en) | 1999-10-06 | 1999-10-06 | Method for producing aluminate phosphor for phosphorescent material |
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| JP3956551B2 true JP3956551B2 (en) | 2007-08-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002088355A (en) * | 2000-09-12 | 2002-03-27 | Sumitomo Chem Co Ltd | Method for producing aluminate phosphor |
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| JP4524887B2 (en) * | 1999-10-06 | 2010-08-18 | 住友化学株式会社 | Method for producing aluminate phosphor |
| EP2980184B1 (en) * | 2013-03-29 | 2018-08-01 | Sakai Chemical Industry Co., Ltd. | Use of a mechanoluminescent material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002088355A (en) * | 2000-09-12 | 2002-03-27 | Sumitomo Chem Co Ltd | Method for producing aluminate phosphor |
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