JP2016098270A - Phosphor powder showing high emission intensity maintenance factor in continuous emission and method for producing the same - Google Patents
Phosphor powder showing high emission intensity maintenance factor in continuous emission and method for producing the same Download PDFInfo
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本発明は、改質された蛍光体粉末及びその製造方法に関する。 The present invention relates to a modified phosphor powder and a method for producing the same.
蛍光体粉末は、例えば、ＰＤＰ（プラズマディスプレイパネル）、希ガスランプ、ＬＥＤランプ（発光ダイオードランプ）の可視光源として広く利用されている。ＰＤＰ及び希ガスランプでは、蛍光体粉末の励起光として、一般にキセノンガスの放電により発生する波長１４６ｎｍ（共鳴線発光）及び波長１７３ｎｍ（分子線発光）の真空紫外光が利用されている。白色ＬＥＤランプでは、蛍光体粉末の励起光として、一般に青色ＬＥＤもしくは紫外光ＬＥＤから発生する青色光もしくは波長３５０〜４３０ｎｍの紫外光が利用されている。 The phosphor powder is widely used as a visible light source of, for example, a PDP (plasma display panel), a rare gas lamp, and an LED lamp (light emitting diode lamp). In PDPs and rare gas lamps, vacuum ultraviolet light having a wavelength of 146 nm (resonant line emission) and a wavelength of 173 nm (molecular beam emission) generated by discharge of xenon gas is generally used as the excitation light of the phosphor powder. In white LED lamps, blue light generated from blue LEDs or ultraviolet LEDs or ultraviolet light having a wavelength of 350 to 430 nm is generally used as the excitation light of the phosphor powder.
特許文献１には、真空紫外線励起による発光輝度の寿命特性が良好な真空紫外線励起発光素子用蛍光体の製造方法として、蛍光体とアルミニウム系カップリング剤を混合し、焼成する方法が記載されている。この文献の実施例では、ＢａＭｇＡｌ10Ｏ17：Ｅｕ（青色発光蛍光体）とアルミニウム系カップリング剤との混合物を大気中において４５０℃で３０分焼成して、真空紫外線励起発光素子用蛍光体を製造した例が記載されている。そして、この真空紫外線励起発光素子用蛍光体は、圧力が１３．２Ｐａで５体積％Ｘｅ−９５体積％Ｎｅの組成のガス雰囲気中に設置し、１００Ｗのプラズマに１時間曝露させたときの輝度の低下は、プラズマ曝露前に比較して１５％であると記載されている。 Patent Document 1 describes a method for producing a phosphor for a vacuum ultraviolet ray-excited light-emitting element having good emission luminance lifetime characteristics by vacuum ultraviolet ray excitation, and mixing and firing the phosphor and an aluminum-based coupling agent. Yes. In the example of this document, a mixture of BaMgAl 10 O 17 : Eu (blue light-emitting phosphor) and an aluminum-based coupling agent was baked at 450 ° C. for 30 minutes in the air to obtain a phosphor for a vacuum ultraviolet ray-excited light emitting device A manufactured example is described. And this fluorescent substance for vacuum ultraviolet ray excitation light emitting elements is installed in the gas atmosphere of the composition of 5 volume% Xe-95 volume% Ne with a pressure of 13.2 Pa, and the brightness | luminance when exposed to 100 W plasma for 1 hour Reduction is described as 15% compared to before plasma exposure.
特許文献２には、発光強度が高く、耐湿性が高いケイ酸塩蛍光体として、ケイ酸塩蛍光体１００質量部に対してフッ化アンモニウムを０．５〜１５質量部の範囲にて含む混合物を２００〜６００℃の温度にて加熱する方法により得られた、フッ素含有化合物被覆ケイ酸塩蛍光体が記載されている。但し、この文献には、連続発光時での発光強度維持率に関する記載はない。 Patent Document 2 discloses a mixture containing ammonium fluoride in a range of 0.5 to 15 parts by mass with respect to 100 parts by mass of a silicate phosphor as a silicate phosphor having high emission intensity and high moisture resistance. Fluorine-containing compound-coated silicate phosphors obtained by heating at a temperature of 200 to 600 ° C. are described. However, this document does not describe the emission intensity maintenance rate during continuous emission.
希ガスランプ及び白色ＬＥＤランプのようなランプは夜間に連続的に点灯させることが多いため、ランプの可視光源として使用する蛍光体粉末は連続的に発光させたときの発光強度の低下が少ないこと、すなわち発光強度の維持率が高いことが望ましい。しかしながら、本発明の発明者の検討によると、特許文献１に記載されている蛍光体粉末とアルミニウム系カップリング剤を混合し、焼成する方法によって製造された蛍光体は、連続的に発光させたときの発光強度の維持率が、ランプ用として使用するには充分とは言えない場合がある。また、本発明の発明者の検討によると、特許文献１に記載されている方法によって製造された蛍光体粉末は、外部量子効率（蛍光体に照射した光の量子数に対する蛍光体が発光した光の量子数の比率）がアルミニウム系カップリング剤で処理する前の蛍光体粉末よりも大きく低減する傾向があることが判明した。 Since lamps such as rare gas lamps and white LED lamps are often continuously lit at night, the phosphor powder used as the visible light source of the lamp has little decrease in emission intensity when continuously emitting light. That is, it is desirable that the maintenance rate of the emission intensity is high. However, according to the study of the inventor of the present invention, the phosphor manufactured by the method of mixing and firing the phosphor powder and the aluminum coupling agent described in Patent Document 1 continuously emitted light. In some cases, the maintenance rate of the emission intensity is not sufficient for use as a lamp. Further, according to the study of the inventor of the present invention, the phosphor powder produced by the method described in Patent Document 1 has an external quantum efficiency (light emitted from the phosphor with respect to the quantum number of light irradiated on the phosphor). It has been found that the ratio of the quantum number) tends to be significantly lower than that of the phosphor powder before being treated with the aluminum coupling agent.
従って、本発明の目的は、連続的に発光させたときの発光強度の維持率が高い蛍光体を、外部量子効率を大きく低減させずに製造することが可能な方法を提供することにある。 Accordingly, an object of the present invention is to provide a method capable of producing a phosphor having a high emission intensity maintenance rate when continuously emitting light without greatly reducing the external quantum efficiency.
本発明の発明者は、蛍光体粉末とフッ化アンモニウムとの混合物を２００〜６００℃の範囲の温度にて加熱処理する工程と、加熱処理した蛍光体粉末の表面にアルミニウム系カップリング剤を付着させ、次いで４００℃以上の温度にて加熱する工程の二段階処理を行なった蛍光体粉末は、蛍光体粉末とアルミニウム系カップリング剤を混合し、焼成する方法で製造された従来の蛍光体粉末と比較して、外部量子効率が高く、かつ連続的に発光させたときの発光強度の維持率が大きく向上することを見出して、本発明を完成させた。 The inventor of the present invention heat-treats a mixture of phosphor powder and ammonium fluoride at a temperature in the range of 200 to 600 ° C., and attaches an aluminum coupling agent to the surface of the heat-treated phosphor powder. The phosphor powder that has been subjected to the two-step process of heating at a temperature of 400 ° C. or higher is then mixed with the phosphor powder and the aluminum coupling agent and then fired. As compared with the above, the inventors have found that the external quantum efficiency is high and the maintenance ratio of the emission intensity when continuously emitting light is greatly improved, thereby completing the present invention.
従って、本発明は、蛍光体粉末とフッ化アンモニウムとの混合物を２００〜６００℃の範囲の温度にて加熱処理する工程、そして加熱処理した蛍光体粉末の表面にアルミニウム系カップリング剤を付着させ、次いで４００℃以上の温度にて加熱する工程を含むことを特徴とする改質された蛍光体粉末の製造方法にある。 Therefore, the present invention includes a step of heat-treating a mixture of phosphor powder and ammonium fluoride at a temperature in the range of 200 to 600 ° C., and attaching an aluminum-based coupling agent to the surface of the heat-treated phosphor powder. Then, there is a method for producing a modified phosphor powder characterized by including a step of heating at a temperature of 400 ° C. or higher.
本発明の改質された蛍光体粉末の製造方法の好ましい態様は、次の通りである。
（１）アルミニウム系カップリング剤を付着させた蛍光体粉末を５７０〜７００℃の範囲の温度にて加熱する。
（２）蛍光体粉末が、ケイ酸塩蛍光体の粉末である。
（３）ケイ酸塩蛍光体が、組成式がＭ1 3-x-yＭ2 xＭｇＳｉ2Ｏ8：Ｅｕy、但し、Ｍ1は、Ｃａ、Ｓｒ及びＢａからなる群より選ばれる少なくとも一つのアルカリ土類金属元素であり、Ｍ2は、Ｓｃ、Ｙ、Ｇｄ、Ｔｂ及びＬａからなる群より選ばれる少なくとも一つの希土類元素であり、ｘは、０〜０．０３の範囲の数であり、ｙは、０．０１〜０．１０の範囲の数である、で表される蛍光体である。
A preferred embodiment of the method for producing the modified phosphor powder of the present invention is as follows.
(1) The phosphor powder to which the aluminum coupling agent is attached is heated at a temperature in the range of 570 to 700 ° C.
(2) The phosphor powder is a silicate phosphor powder.
(3) The silicate phosphor has a composition formula of M 1 3-xy M 2 x MgSi 2 O 8 : Eu y , where M 1 is at least one alkali selected from the group consisting of Ca, Sr and Ba It is an earth metal element, M 2 is at least one rare earth element selected from the group consisting of Sc, Y, Gd, Tb and La, x is a number in the range of 0 to 0.03, y Is a phosphor having a number in the range of 0.01 to 0.10.
本発明はまた、上記の本発明の製造方法により得られた蛍光体粉末にもある。 The present invention also resides in the phosphor powder obtained by the production method of the present invention described above.
本発明の製造方法を利用することによって、連続発光時に高い発光強度維持率を示す蛍光体粉末を工業的に有利に製造することができる。本発明の蛍光体粉末は、連続発光時に高い発光強度維持率を示すことから、希ガスランプ及びＬＥＤランプのようなランプの可視光源として有利に使用することができる。 By utilizing the production method of the present invention, a phosphor powder exhibiting a high emission intensity maintenance rate during continuous light emission can be advantageously produced industrially. Since the phosphor powder of the present invention exhibits a high emission intensity maintenance rate during continuous light emission, it can be advantageously used as a visible light source for lamps such as rare gas lamps and LED lamps.
本発明の蛍光体粉末の製造方法は、原料の蛍光体粉末とフッ化アンモニウムとの混合物を２００〜６００℃の範囲の温度にて加熱処理する工程（以下、第一の処理ともいう）と、加熱処理した蛍光体粉末の表面にアルミニウム系カップリング剤を付着させ、次いで４００℃以上の温度にて加熱する工程（以下、第二の処理ともいう）の二段階の処理を含むことを特徴とする。 The phosphor powder production method of the present invention includes a step of heat-treating a mixture of a raw material phosphor powder and ammonium fluoride at a temperature in the range of 200 to 600 ° C. (hereinafter also referred to as a first treatment), Including a two-step process of attaching an aluminum coupling agent to the surface of the heat-treated phosphor powder, and then heating at a temperature of 400 ° C. or higher (hereinafter also referred to as a second process). To do.
原料の蛍光体粉末の例としては、ケイ酸塩蛍光体の粉末及びアルミン酸塩蛍光体の粉末を挙げることができる。蛍光体粉末は、ケイ酸塩蛍光体の粉末であることが好ましい。ケイ酸塩蛍光体の例としては、（Ｂａ，Ｓｒ，Ｃａ）3ＭｇＳｉ2Ｏ8をＥｕで賦活したケイ酸塩青色発光蛍光体、（Ｂａ，Ｓｒ，Ｃａ）2ＳｉＯ4をＥｕで賦活したケイ酸塩緑色発光蛍光体、及び（Ｂａ，Ｓｒ，Ｃａ）3ＭｇＳｉ2Ｏ8をＥｕとＭｎで賦活したケイ酸塩赤色発光蛍光体を挙げることができる。上記のケイ酸塩蛍光体は、さらにＥｕ以外の希土類元素を含有していてもよい。Ｅｕ以外の希土類元素の例としては、Ｓｃ、Ｙ、Ｇｄ、Ｔｂ及びＬａを挙げることができる。 Examples of the raw material phosphor powder include silicate phosphor powder and aluminate phosphor powder. The phosphor powder is preferably a silicate phosphor powder. Examples of silicate phosphors include (Ba, Sr, Ca) 3 MgSi 2 O 8 activated with Eu and silicate blue light emitting phosphor activated with (Ba, Sr, Ca) 2 SiO 4 activated with Eu. Examples thereof include silicate green light-emitting phosphors and silicate red light-emitting phosphors obtained by activating (Ba, Sr, Ca) 3 MgSi 2 O 8 with Eu and Mn. The silicate phosphor may further contain a rare earth element other than Eu. Examples of rare earth elements other than Eu include Sc, Y, Gd, Tb, and La.
ケイ酸塩蛍光体の具体例としては、下記の組成式で表される蛍光体を挙げることができる。
Ｍ1 3-x-yＭ2 xＭｇＳｉ2Ｏ8：Ｅｕy
但し、Ｍ1は、Ｃａ、Ｓｒ及びＢａからなる群より選ばれる少なくとも一つのアルカリ土類金属元素であり、Ｍ2は、Ｓｃ、Ｙ、Ｇｄ、Ｔｂ及びＬａからなる群より選ばれる少なくとも一つの希土類元素であり、ｘは、０〜０．０３の範囲の数であり、ｙは、０．０１〜０．１０の範囲の数である。
Specific examples of the silicate phosphor include phosphors represented by the following composition formula.
M 1 3-xy M 2 x MgSi 2 O 8 : Eu y
M 1 is at least one alkaline earth metal element selected from the group consisting of Ca, Sr and Ba, and M 2 is at least one selected from the group consisting of Sc, Y, Gd, Tb and La. It is a rare earth element, x is a number in the range of 0 to 0.03, and y is a number in the range of 0.01 to 0.10.
第一の処理において、蛍光体粉末とフッ化アンモニウムとの混合物に含まれるフッ化アンモニウムの量は、蛍光体粉末１００質量部に対する量として一般に０．５〜１５質量部の範囲の量、好ましくは１〜１０質量部の範囲の量である。この混合物の調製方法としては、蛍光体粉末とフッ化アンモニウム水溶液とを混合する方法、蛍光体粉末とフッ化アンモニウム粉末とを混合する方法のいずれの方法も用いることができるが、後者の蛍光体粉末とフッ化アンモニウム粉末とを混合する方法が好ましい。 In the first treatment, the amount of ammonium fluoride contained in the mixture of phosphor powder and ammonium fluoride is generally in the range of 0.5 to 15 parts by mass, preferably as an amount with respect to 100 parts by mass of phosphor powder, preferably The amount is in the range of 1 to 10 parts by mass. As a method for preparing this mixture, either a method of mixing phosphor powder and an aqueous ammonium fluoride solution or a method of mixing phosphor powder and ammonium fluoride powder can be used. A method of mixing powder and ammonium fluoride powder is preferred.
蛍光体粉末とフッ化アンモニウムとの混合物の加熱処理は、蓋が閉じられた耐熱性容器の中、即ちフッ化アンモニウムを閉じ込めた状態で行なうことが好ましい。この混合物の加熱温度は、好ましくは２００〜５００℃の範囲、より好ましくは２００〜４８０℃の範囲、特に好ましくは３００〜４８０℃の範囲である。混合物の加熱時間は、一般に１０分〜１０時間の範囲にある。 The heat treatment of the mixture of phosphor powder and ammonium fluoride is preferably performed in a heat-resistant container with the lid closed, that is, in a state where ammonium fluoride is confined. The heating temperature of this mixture is preferably in the range of 200 to 500 ° C, more preferably in the range of 200 to 480 ° C, and particularly preferably in the range of 300 to 480 ° C. The heating time of the mixture is generally in the range of 10 minutes to 10 hours.
第二の処理において、蛍光体粉末の表面に付着させるアルミニウム系カップリング剤は、親水基と疎水基とを有する化合物であることが好ましい。親水基は炭素原子数が１〜６のアルコキシル基であって、疎水基は炭素原子数が８〜２０のアルキル基であることが好ましい。アルミニウム系カップリング剤は、アセトアルコキシアルミニウムジイソプロピレートであることが好ましい。アルミニウム系カップリング剤としては、味の素株式会社製のプレンアクトＡＬ−Ｍを用いることができる。蛍光体粉末の表面に付着させるアルミニウム系カップリング剤の量は、蛍光体粉末１００質量部に対する量として一般に０．１〜１５質量部の範囲の量、好ましくは０．２〜１０質量部の範囲の量である。 In the second treatment, the aluminum coupling agent attached to the surface of the phosphor powder is preferably a compound having a hydrophilic group and a hydrophobic group. The hydrophilic group is preferably an alkoxyl group having 1 to 6 carbon atoms, and the hydrophobic group is preferably an alkyl group having 8 to 20 carbon atoms. The aluminum coupling agent is preferably acetoalkoxyaluminum diisopropylate. As an aluminum coupling agent, Anomoto Co., Ltd. Preneact AL-M can be used. The amount of the aluminum coupling agent attached to the surface of the phosphor powder is generally in the range of 0.1 to 15 parts by mass, preferably in the range of 0.2 to 10 parts by mass with respect to 100 parts by mass of the phosphor powder. Is the amount.
蛍光体粉末の表面にアルミニウム系カップリング剤を付着させる方法としては、蛍光体粉末とアルミニウム系カップリング剤とを混合する方法を用いることができる。アルミニウム系カップリング剤は有機溶媒で希釈して、蛍光体粉末と混合してもよい。有機溶媒の例としては、鉱油、ＤＯＰ、ヘキサン、トルエン、キシレン、ＭＥＫ、酢酸ブチル、酢酸エチル、クロロホルム、プロパノールを挙げることができる。 As a method for attaching the aluminum coupling agent to the surface of the phosphor powder, a method of mixing the phosphor powder and the aluminum coupling agent can be used. The aluminum coupling agent may be diluted with an organic solvent and mixed with the phosphor powder. Examples of the organic solvent include mineral oil, DOP, hexane, toluene, xylene, MEK, butyl acetate, ethyl acetate, chloroform, and propanol.
アルミニウム系カップリング剤を付着させた蛍光体粉末の加熱は、蓋が閉じられた耐熱性容器の中、即ちアルミニウム系カップリング剤を閉じ込めた状態で行なうことが好ましい。この蛍光体粉末の加熱温度は、好ましくは５００℃以上、特に好ましくは５７０℃以上である。加熱温度の上限は一般に７００℃である。蛍光体粉末の加熱時間は、一般に１０分〜１０時間の範囲にある。 It is preferable to heat the phosphor powder to which the aluminum coupling agent is adhered in a heat-resistant container with the lid closed, that is, in a state where the aluminum coupling agent is confined. The heating temperature of the phosphor powder is preferably 500 ° C. or higher, particularly preferably 570 ° C. or higher. The upper limit of the heating temperature is generally 700 ° C. The heating time of the phosphor powder is generally in the range of 10 minutes to 10 hours.
上記の二段階処理を行なって製造された本発明の蛍光体粉末が、蛍光体粉末とアルミニウム系カップリング剤を混合し、焼成する方法によって製造された従来の蛍光体粉末と比較して、外部量子効率が高く、かつ連続的に発光させたときの発光強度の維持率が大きく向上する理由は必ずしも明確ではないが次のように考えられる。本発明の蛍光体粉末は、第一の処理にて、蛍光体粉末の表面とフッ化アンモニウムもしくはその熱分解物とが反応することによって形成されたフッ素含有化合物層と、第二の処理にて、フッ素含有化合物層の表面とアルミニウム系カップリング剤もしくはその熱分解物とが反応することによって形成されたアルミニウム含有化合物層とを有する。蛍光体粉末とフッ素含有化合物層とは、蛍光体粉末の金属元素とフッ素含有化合物層中のフッ素とが結合することによって互いに強く密着し、フッ素含有化合物層とアルミニウム含有化合物層とは、フッ素含有化合物層中のフッ素とアルミニウム含有化合物層中のアルミニウムとが結合することによって互いに強く密着する。このように、本発明の蛍光体粉末は、表面がフッ素含有化合物層とアルミニウム含有化合物層の二層で被覆されていて、蛍光体粉末の表面、フッ素含有化合物層そしてアルミニウム含有化合物層がそれぞれ互いに強く密着することによって、従来の蛍光体粉末と比較して、外部量子効率が高く、かつ連続的に発光させたときの発光強度の維持率が大きく向上すると考えられる。本発明の蛍光体粉末は、例えば、波長が１４６ｎｍの真空紫外光を励起光として１２０分間連続発光させたときの発光強度維持率が、発光開始直後の発光強度を基準として通常は９５％以上、特に９８％以上と高い値を示す。 The phosphor powder of the present invention manufactured by performing the above-mentioned two-stage treatment is compared with the conventional phosphor powder manufactured by a method in which the phosphor powder and the aluminum coupling agent are mixed and fired. The reason why the retention rate of the emission intensity when the quantum efficiency is high and the light is continuously emitted is greatly improved is not necessarily clear, but is considered as follows. In the phosphor powder of the present invention, the fluorine-containing compound layer formed by the reaction of the surface of the phosphor powder with ammonium fluoride or a thermal decomposition product thereof in the first treatment, and the second treatment The surface of the fluorine-containing compound layer and the aluminum-containing compound layer formed by the reaction of the aluminum-based coupling agent or the thermal decomposition product thereof. The phosphor powder and the fluorine-containing compound layer are in close contact with each other by bonding the metal element of the phosphor powder and the fluorine in the fluorine-containing compound layer, and the fluorine-containing compound layer and the aluminum-containing compound layer are fluorine-containing. The fluorine in the compound layer and the aluminum in the aluminum-containing compound layer are bonded to each other so as to be strongly adhered to each other. Thus, the surface of the phosphor powder of the present invention is coated with two layers of the fluorine-containing compound layer and the aluminum-containing compound layer, and the surface of the phosphor powder, the fluorine-containing compound layer, and the aluminum-containing compound layer are each mutually By sticking firmly, it is considered that the external quantum efficiency is higher than the conventional phosphor powder, and the maintenance ratio of the emission intensity when continuously emitting light is greatly improved. The phosphor powder of the present invention, for example, the emission intensity maintenance rate when continuously emitting for 120 minutes using vacuum ultraviolet light having a wavelength of 146 nm as excitation light, is usually 95% or more based on the emission intensity immediately after the start of emission, In particular, it shows a high value of 98% or more.
本発明の蛍光体粉末は、連続発光時に高い発光強度維持率を示すことから、ランプの可視光源として有利に使用することができる。本発明の蛍光体粉末は、ＬＥＤランプの可視光源として有利に利用することができる。ＬＥＤランプの例としては、本発明の蛍光体粉末を透明樹脂材料もしくはガラス中に分散させた蛍光体粉末含有組成物を、青色発光ダイオードもしくは紫外光発光ダイオードなどの励起光源の周囲に配置した構成のものを挙げることができる。 Since the phosphor powder of the present invention exhibits a high emission intensity maintenance ratio during continuous light emission, it can be advantageously used as a visible light source for a lamp. The phosphor powder of the present invention can be advantageously used as a visible light source of an LED lamp. As an example of the LED lamp, the phosphor powder-containing composition in which the phosphor powder of the present invention is dispersed in a transparent resin material or glass is arranged around an excitation light source such as a blue light emitting diode or an ultraviolet light emitting diode. Can be mentioned.
［実施例１］
組成がＳｒ2.94ＭｇＳｉ2Ｏ8：Ｅｕ0.06のケイ酸塩蛍光体粉末１０ｇに０．６ｇのフッ化アンモニウム粉末を添加混合して粉末混合物を得た。次いで、この粉末混合物をアルミナ坩堝に入れて大気中にて４８０℃の温度で６時間加熱処理した後、室温まで放冷した。次に、この加熱処理済の蛍光体粉末１０ｇとアルミニウム系カップリング剤（プレンアクトＡＬ−Ｍ、味の素株式会社製）０．１ｇとを乳鉢にて混合して、加熱処理済の蛍光体粉末の表面にアルミニウム系カップリング剤を付着させた。次いで、この蛍光体粉末をアルミナ坩堝に入れて電気炉にて６００℃の温度で３時間加熱した後、室温まで放冷した。
上記の処理を行なった蛍光体粉末について、波長４００ｎｍの紫外光を照射したときの外部量子効率及び波長１４６ｎｍの真空紫外光を照射したときの連続発光時の発光強度維持率を下記の方法により測定した。表１に、その結果を示す。
[Example 1]
A powder mixture was obtained by adding 0.6 g of ammonium fluoride powder to 10 g of silicate phosphor powder having a composition of Sr 2.94 MgSi 2 O 8 : Eu 0.06 . Next, this powder mixture was put in an alumina crucible and heat-treated in the atmosphere at a temperature of 480 ° C. for 6 hours, and then allowed to cool to room temperature. Next, 10 g of this heat-treated phosphor powder and 0.1 g of an aluminum coupling agent (Plenact AL-M, manufactured by Ajinomoto Co., Inc.) are mixed in a mortar, and the surface of the heat-treated phosphor powder An aluminum coupling agent was adhered to the substrate. Next, this phosphor powder was put in an alumina crucible and heated in an electric furnace at a temperature of 600 ° C. for 3 hours, and then allowed to cool to room temperature.
For the phosphor powder subjected to the above treatment, the external quantum efficiency when irradiated with ultraviolet light having a wavelength of 400 nm and the emission intensity maintenance rate during continuous light emission when irradiated with vacuum ultraviolet light having a wavelength of 146 nm are measured by the following methods. did. Table 1 shows the results.
［外部量子効率の測定方法］
分光蛍光光度計（ジャスコエンジニアリング株式会社製ＦＰ−８５００）を用いて、以下の手順にて測定した。
１）標準白板を積分球の内側底部に取り付け、その標準白板の表面に、その表面に対して垂直にピーク波長４００ｎｍの紫外光を照射して、標準白板の表面にて散乱した光のスペクトルを積分球にて測定した。そして、得られたスペクトル中の波長３８０〜４１０ｎｍの光のピーク面積を励起光の量子数（Ｌ）として算出した。
２）蛍光体粉末試料を試料ホルダーに充填し、試料ホルダーを積分球の内側底部に取り付けた。次に、この試料ホルダーの蛍光体粉末試料の表面に、その表面に対して垂直にピーク波長４００ｎｍの紫外光を照射して、蛍光体粉末試料の表面にて散乱した光と蛍光体粉末試料が発光した光のスペクトルを積分球で測定した。そして、得られたスペクトル中の波長４１０〜６００ｎｍの光（蛍光体粉末試料が発光した光）のピーク面積を発光光の量子数（Ｅ）として算出した。そして、ケイ酸塩蛍光体試料の外部量子効率を下記の式を用いて算出した。
外部量子効率（％）＝１００×Ｅ／Ｌ
[Measurement method of external quantum efficiency]
Using a spectrofluorometer (FP-8500 manufactured by Jusco Engineering Co., Ltd.), the measurement was performed in the following procedure.
1) A standard white plate is attached to the inner bottom of the integrating sphere, and the surface of the standard white plate is irradiated with ultraviolet light having a peak wavelength of 400 nm perpendicular to the surface, and the spectrum of light scattered on the surface of the standard white plate is obtained. Measured with an integrating sphere. And the peak area of the light of wavelength 380-410 nm in the obtained spectrum was computed as a quantum number (L) of excitation light.
2) The phosphor powder sample was filled in the sample holder, and the sample holder was attached to the inner bottom of the integrating sphere. Next, the surface of the phosphor powder sample of this sample holder is irradiated with ultraviolet light having a peak wavelength of 400 nm perpendicular to the surface, and the light scattered on the surface of the phosphor powder sample and the phosphor powder sample are The spectrum of the emitted light was measured with an integrating sphere. Then, the peak area of light having a wavelength of 410 to 600 nm (light emitted from the phosphor powder sample) in the obtained spectrum was calculated as the quantum number (E) of the emitted light. And the external quantum efficiency of the silicate fluorescent substance sample was computed using the following formula.
External quantum efficiency (%) = 100 × E / L
［連続発光時の発光強度維持率の測定方法］
蛍光体粉末試料に波長１４６ｎｍの真空紫外光を連続的に照射して、蛍光体粉末試料を発光させながら、蛍光体粉末試料の発光開始直後から３０分毎に、蛍光体粉末試料の発光スペクトルを測定した。得られた発光スペクトル中の波長４１０〜５００ｎｍの範囲にある発光光の最大強度を発光強度として計測した。
発光強度維持率は、下記の式より算出した。
発光強度の維持率（％）＝１００×蛍光体粉末試料の連続発光中での発光強度／蛍光体粉末試料の発光開始直後の発光強度
また、後述の参考例１の蛍光体粉末の発光開始直後の発光強度を基準とした発光強度維持率を下記の式より算出した。その結果を表１に併せて示す。
発光強度の維持率（％）＝１００×蛍光体粉末試料の連続発光中での発光強度／参考例１の蛍光体粉末の発光開始直後の発光強度
[Measurement method of emission intensity maintenance rate during continuous emission]
While the phosphor powder sample is continuously irradiated with vacuum ultraviolet light having a wavelength of 146 nm to cause the phosphor powder sample to emit light, the emission spectrum of the phosphor powder sample is measured every 30 minutes immediately after the start of light emission of the phosphor powder sample. It was measured. The maximum intensity of the emitted light in the wavelength range of 410 to 500 nm in the obtained emission spectrum was measured as the emission intensity.
The emission intensity maintenance rate was calculated from the following formula.
Emission intensity maintenance rate (%) = 100 × luminescence intensity during continuous emission of phosphor powder sample / luminescence intensity immediately after starting emission of phosphor powder sample Also immediately after starting emission of phosphor powder of Reference Example 1 described later The emission intensity maintenance rate based on the emission intensity was calculated from the following formula. The results are also shown in Table 1.
Emission intensity maintenance rate (%) = 100 × luminescence intensity during continuous emission of phosphor powder sample / luminescence intensity immediately after the start of emission of the phosphor powder of Reference Example 1
［比較例１］
実施例１で原料として用いた蛍光体粉末と同じ蛍光体粉末１０ｇとアルミニウム系カップリング剤０．１ｇとを乳鉢にて混合して、蛍光体粉末の表面にアルミニウム系カップリング剤を付着させた。次いで、この蛍光体粉末をアルミナ坩堝に入れて、電気炉にて４５０℃の温度（特許文献１の実施例１に記載されている焼成温度）で３時間加熱したこと以外は、実施例１と同様な処理を行なった。この処理済の蛍光体粉末について、外部量子効率及び連続発光時の発光強度維持率を前記の方法により測定した。表１に、その結果を示す。
[Comparative Example 1]
The same phosphor powder 10 g as the raw material used in Example 1 and 0.1 g of the aluminum coupling agent were mixed in a mortar, and the aluminum coupling agent was adhered to the surface of the phosphor powder. . Next, the phosphor powder was placed in an alumina crucible and heated in an electric furnace at a temperature of 450 ° C. (firing temperature described in Example 1 of Patent Document 1) for 3 hours, except for Example 1. Similar processing was performed. About this processed fluorescent substance powder, the external quantum efficiency and the emitted-light-intensity maintenance factor at the time of continuous light emission were measured by the said method. Table 1 shows the results.
［参考例１］
実施例１で原料として用いたケイ酸塩蛍光体粉末と同じケイ酸塩蛍光体粉末について、外部量子効率及び連続発光時の発光強度維持率を前記の方法により測定した。表１に、その結果を示す。
[Reference Example 1]
About the same silicate phosphor powder as the silicate phosphor powder used as a raw material in Example 1, the external quantum efficiency and the emission intensity maintenance rate at the time of continuous light emission were measured by the above methods. Table 1 shows the results.
表１
────────────────────────────────────────
外部量 発光強度維持率（％）
子効率 ──────────────────────────────
（％） 発光開始直後 ３０分後 ６０分後 ９０分後 １２０分後
────────────────────────────────────────
参考例１ ６８ １００ ８３ ７３ ６８ −
────────────────────────────────────────
実施例１ ６６ １００ １００ １００ １００ １００
(９７．１) (９７．１) (９７．１) (９７．１) (９７．１)
────────────────────────────────────────
比較例１ ６２ １００ １００ ９７．６ ９５．６ ９３．１
(９１．２) (９１．２) (８９．０) (８７．２) (８４．９)
────────────────────────────────────────
注）発光強度維持率の括弧内の数値は、参考例１の蛍光体粉末の発光開始直後の発光強度を基準とした維持率である。
Table 1
────────────────────────────────────────
External quantity Emission intensity maintenance rate (%)
Child efficiency ──────────────────────────────
(%) Immediately after the start of light emission 30 minutes later 60 minutes 90 minutes later 120 minutes later ──────────────────────────────── ────────
Reference Example 1 68 100 83 73 68-
────────────────────────────────────────
Example 1 66 100 100 100 100 100 100
(97.1) (97.1) (97.1) (97.1) (97.1)
────────────────────────────────────────
Comparative Example 1 62 100 100 97.6 95.6 93.1
(91.2) (91.2) (89.0) (87.2) (84.9)
────────────────────────────────────────
Note) The numerical value in parentheses of the emission intensity maintenance rate is the maintenance rate based on the emission intensity immediately after the start of emission of the phosphor powder of Reference Example 1.
表１の結果から、実施例１の蛍光体粉末（本発明の二段階処理を行なった蛍光体粉末）は、比較例１の蛍光体粉末（アルミニウム系カップリング剤の加熱分解物による表面処理のみを行なった蛍光体粉末）と比較して、外部量子効率が高く、また発光強度の維持率が高いことが分かる。一方、実施例１の蛍光体粉末と参考例１の蛍光体粉末（未処理の蛍光体粉末）とを比較すると、実施例１の蛍光体粉末の方が外部量子効率及び発光開始直後の発光強度の維持率は僅かに低い値を示すが、参考例１の蛍光体粉末は発光強度の維持率が実施例１の蛍光体粉末より低く、発光開始から３０分後には、実施例１の蛍光体粉末よりも発光強度が低くなることが分かる。従って、本発明の蛍光体粉末は連続的に発光させたときの発光強度の維持率が高く、このため可視光源として実用性が高いことが分かる。 From the results shown in Table 1, the phosphor powder of Example 1 (the phosphor powder subjected to the two-step treatment of the present invention) is the phosphor powder of Comparative Example 1 (surface treatment only with a thermal decomposition product of an aluminum coupling agent). It can be seen that the external quantum efficiency is high and the emission intensity maintenance rate is high as compared with the phosphor powder obtained by the above. On the other hand, when the phosphor powder of Example 1 is compared with the phosphor powder of Reference Example 1 (untreated phosphor powder), the phosphor powder of Example 1 has the external quantum efficiency and the emission intensity immediately after the start of light emission. Although the phosphor powder of Reference Example 1 has a lower emission intensity maintenance rate than the phosphor powder of Example 1, 30 minutes after the start of light emission, the phosphor of Example 1 has a slightly lower value. It can be seen that the emission intensity is lower than that of the powder. Therefore, it can be seen that the phosphor powder of the present invention has a high retention rate of the emission intensity when continuously emitting light, and thus is highly practical as a visible light source.
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