JP2010209210A - Process for producing phosphor, amorphous red phosphor - Google Patents

Process for producing phosphor, amorphous red phosphor Download PDF

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JP2010209210A
JP2010209210A JP2009056671A JP2009056671A JP2010209210A JP 2010209210 A JP2010209210 A JP 2010209210A JP 2009056671 A JP2009056671 A JP 2009056671A JP 2009056671 A JP2009056671 A JP 2009056671A JP 2010209210 A JP2010209210 A JP 2010209210A
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JP5366200B2 (en
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Yoshiyuki Kojima
芳行 小嶋
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Nihon University
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel process for producing an amorphous red phosphor. <P>SOLUTION: A process for producing an amorphous red phosphor represented by general formula M1<SB>x</SB>Eu<SB>y</SB>SiO<SB>2+x+1.5y</SB>(wherein M1 is at least one element selected from Ca, Sr and Ba; 0.6≤x+1.5y≤0.9) includes calcining a phosphor precursor obtained by a solution method at 800-930°C. An amorphous red phosphor is represented by general formula M1<SB>x</SB>Eu<SB>y</SB>SiO<SB>2+x+1.5y</SB>(wherein M1 is at least one element selected from Ca, Sr and Ba; 0.6≤x+1.5y≤0.9). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、新規な蛍光体の製造方法及び非晶質赤色蛍光体に関する。   The present invention relates to a novel phosphor manufacturing method and an amorphous red phosphor.

白色ＬＥＤは、近紫外線や青色光を発するＬＥＤと、ＬＥＤの発する光を吸収して、赤色に発光する蛍光体および緑色に発光する蛍光体とを組み合わせて作製されている。
白色ＬＥＤに使用される赤色蛍光体としては、ＣａＡｌＳｉＮ３：Ｅｕ（以下、「ＣＡＳＮ」と略記する）が知られている。しかし、ＣＡＳＮは１２００〜２２００℃の高温で合成されるため、特別な設備が必要となる。また、原料として、カルシウム、アルミニウム、珪素の窒化物を使用しており（特許文献１参照）、これらは一般的に高価である。このため、得られる蛍光体も高価になる。
そこで、安価で簡単に作製できる赤色蛍光体が望まれている。 The white LED is manufactured by combining an LED that emits near-ultraviolet light or blue light with a phosphor that absorbs light emitted from the LED and emits red light and a phosphor that emits green light.
As a red phosphor used for a white LED, CaAlSiN 3 : Eu (hereinafter abbreviated as “CASN”) is known. However, since CASN is synthesized at a high temperature of 1200 to 2200 ° C., special equipment is required. Moreover, the nitride of calcium, aluminum, and silicon is used as a raw material (refer patent document 1), and these are generally expensive. For this reason, the phosphor obtained is also expensive.
Therefore, a red phosphor that is inexpensive and can be easily produced is desired.

一方、比較的低温で蛍光体を合成する方法としては、メタケイ酸ナトリウム水溶液を原料としたゾルゲル法により得られたゲルを、還元性雰囲気中で８００〜１４００℃で焼成し、ｍＭ１Ｏ・ｎＭ２Ｏ・２ＳｉＯ２（式中、Ｍ１は、Ｃａ、Ｓｒ及びＢａから選ばれる１以上、Ｍ２は、Ｍｇ及びＺｎから選ばれる１以上、０．５≦ｍ≦３．５、０．５≦ｎ≦２．５）で表される、１４６ｎｍで励起すると青色に発光するケイ酸塩蛍光体を製造する方法（例えば特許文献２参照）や、ｐＨ１〜３にしたメタケイ酸ナトリウム水溶液とアルカリ性水溶液を反応させて得られた前駆体を、１２６０℃で焼成し、（Ｚｎ(２-ｘ)Ｍｎｘ）ＳｉＯ４（式中、０＜ｘ≦０．３）で表される、１４６ｎｍで励起すると緑色に発光するＰＤＰパネル用ケイ酸亜鉛マンガン蛍光体を製造する方法（例えば特許文献３参照）が提案されている。 On the other hand, as a method of synthesizing a phosphor at a relatively low temperature, a gel obtained by a sol-gel method using a sodium metasilicate aqueous solution as a raw material is baked at 800 to 1400 ° C. in a reducing atmosphere, and mM1O.nM2O.2SiO. 2 (wherein M1 is 1 or more selected from Ca, Sr and Ba, M2 is 1 or more selected from Mg and Zn, 0.5 ≦ m ≦ 3.5, 0.5 ≦ n ≦ 2.5) ) And a method for producing a silicate phosphor that emits blue light when excited at 146 nm (see, for example, Patent Document 2), or by reacting a sodium metasilicate aqueous solution adjusted to pH 1 to 3 with an alkaline aqueous solution. The PDP panel which emits green light when fired at 1260 ° C. and excited at 146 nm represented by (Zn (2-x) Mn x ) SiO 4 (where 0 <x ≦ 0.3) For silicic acid Method of manufacturing a lead manganese phosphor (for example, see Patent Document 3) are proposed.

しかしながら、これらの蛍光体は励起光が１４６ｎｍの紫外線であるため主としてＰＤＰ用であり、また、赤色蛍光体を開示するものではない。   However, these phosphors are mainly for PDP because the excitation light is ultraviolet light having a wavelength of 146 nm, and do not disclose a red phosphor.

特開２００５−３３６２５３号公報JP 2005-336253 A 特開２００５−８９６８８号公報JP 2005-89688 A 特開２００６−３２１６９２号公報JP 2006-321692 A

そこで本発明の目的は、合成に特殊な装置を必要とせず、比較的低温で合成できる、近紫外から青色で励起すると赤色に発光する蛍光体およびその製造方法を提案することである。   Accordingly, an object of the present invention is to propose a phosphor that can be synthesized at a relatively low temperature without requiring a special device for synthesis and emits red light when excited from near ultraviolet to blue, and a method for producing the same.

本発明の蛍光体の製造方法のうち請求項１に係るものは、溶液反応により得られた蛍光体前駆体を８００〜９３０℃で焼成し、一般式Ｍ１ｘＥｕｙＳｉＯ２＋ｘ＋１．５ｙ（式中、Ｍ１は、Ｃａ、Ｓｒ及びＢａから選ばれる１以上の元素、０．６≦ｘ＋１．５ｙ≦０．９）で表される非晶質赤色蛍光体を得ることを特徴とする。 According to the first aspect of the method for producing a phosphor of the present invention, the phosphor precursor obtained by the solution reaction is baked at 800 to 930 ° C., and the general formula M1 x Eu y SiO 2 + x + 1.5y (wherein , M1 is characterized by obtaining an amorphous red phosphor represented by one or more elements selected from Ca, Sr and Ba, 0.6 ≦ x + 1.5y ≦ 0.9).

請求項２に係るものは、請求項１の蛍光体の製造方法において、前記溶液反応において、Ｓｉ原料がメタケイ酸ナトリウム、水ガラスまたはアルコキシシランであり、Ｅｕ原料がＥｕ（III）の塩またはアルコキシドであり、Ｍ１原料がＭ１元素の塩またはアルコキシドであることを特徴とする。   According to a second aspect of the present invention, in the phosphor manufacturing method of the first aspect, in the solution reaction, the Si raw material is sodium metasilicate, water glass or alkoxysilane, and the Eu raw material is a salt or alkoxide of Eu (III). The M1 raw material is a salt or alkoxide of the M1 element.

請求項３に係るものは、請求項１または２に記載の蛍光体の製造方法において、前記一般式において、Ｍ１がＣａであることを特徴とする。   According to a third aspect of the present invention, in the phosphor manufacturing method according to the first or second aspect, in the general formula, M1 is Ca.

請求項４に係るものは、請求項１ないし３のいずれかに記載の蛍光体の製造方法において、前記蛍光体前駆体の焼成温度を８６０〜８８０℃とする。   According to a fourth aspect of the present invention, in the phosphor manufacturing method according to any one of the first to third aspects, the firing temperature of the phosphor precursor is set to 860 to 880 ° C.

請求項５に係る蛍光体は、請求項１から４のいずれかの蛍光体の製造方法により得られることを特徴とする。   The phosphor according to claim 5 is obtained by the phosphor manufacturing method according to any one of claims 1 to 4.

請求項６に係る非晶質赤色蛍光体は、一般式Ｍ１ｘＥｕｙＳｉＯ２＋１ｘ＋１．５ｙ（式中、Ｍ１は、Ｃａ、Ｓｒ及びＢａから選ばれる１以上の元素、０．６≦ｘ＋１．５ｙ≦０．９）で表されることを特徴とする。 The amorphous red phosphor according to claim 6 has a general formula M1 x Eu y SiO 2 + 1x + 1.5y (where M1 is one or more elements selected from Ca, Sr and Ba, 0.6 ≦ x + 1.5y) ≦ 0.9).

本発明によれば、非晶質赤色蛍光体を８００〜９３０℃で合成できるので、特殊な装置を必要としない。
また、蛍光体が非晶質であるため、ＣＡＳＮなどの結晶性蛍光体であれば濃度消光が発生するような付活剤の添加量であっても、濃度消光が起きない。 According to the present invention, since the amorphous red phosphor can be synthesized at 800 to 930 ° C., no special apparatus is required.
Further, since the phosphor is amorphous, concentration quenching does not occur even if the amount of the activator added is such that concentration quenching occurs if the phosphor is a crystalline phosphor such as CASN.

実施例１の蛍光体のＸ線回折図形を示すThe X-ray diffraction pattern of the fluorescent substance of Example 1 is shown. 実施例１の蛍光体の励起及び発光スペクトルを示すThe excitation and emission spectra of the phosphor of Example 1 are shown. 実施例１〜４の蛍光体の発光スペクトルを示すThe emission spectrum of the fluorescent substance of Examples 1-4 is shown. 実施例５、６及び比較例１、２の蛍光体のＸ線回折図形を示すThe X-ray diffraction patterns of the phosphors of Examples 5 and 6 and Comparative Examples 1 and 2 are shown. 実施例５、６及び比較例１、２の蛍光体の発光スペクトルを示すThe emission spectra of the phosphors of Examples 5 and 6 and Comparative Examples 1 and 2 are shown.

本発明の蛍光体の製造方法は、まず、溶液反応により蛍光体前駆体を製造する。具体的には、Ｓｉ原料を含む溶液と、Ｅｕ(III)原料とＭ１原料を含む溶液とを反応させることにより、蛍光体前駆体を製造することができる。   In the phosphor production method of the present invention, first, a phosphor precursor is produced by a solution reaction. Specifically, the phosphor precursor can be produced by reacting a solution containing the Si raw material with a solution containing the Eu (III) raw material and the M1 raw material.

Ｓｉ原料としては、オルトケイ酸ナトリウム９水和物、水ガラス、アルコキシシランなどが挙げられるが、安価で反応しやすいオルトケイ酸ナトリウム９水和物が好ましい。
Ｓｉ原料を溶解させる溶媒としては、アルコールなどの有機溶媒、水などが挙げられるが、Ｓｉ原料がオルトケイ酸ナトリウム９水和物、水ガラスの場合は水、アルコキシシランの場合は有機溶媒が好ましい。 Examples of the Si raw material include sodium orthosilicate nonahydrate, water glass, alkoxysilane and the like, but sodium orthosilicate nonahydrate which is inexpensive and easily reacts is preferable.
Examples of the solvent for dissolving the Si raw material include organic solvents such as alcohol, water, and the like. However, when the Si raw material is sodium orthosilicate nonahydrate, water glass, water and alkoxysilane are preferable.

Ｍ１原料としては、Ｍ１元素の塩またはアルコキシドが挙げられる。Ｍ１の塩としては、溶媒に溶解すれば特に限定されず、塩化物、硝酸塩、酢酸塩などが挙げられる。Ｍ１のアルコキシドのアルコキシ基としては、メトキシ基、エトキシ基、プロピオキシ基、ブトキシ基などが挙げられる。
Ｍ１原料を溶解させる溶液としては、アルコールなどの有機溶媒、水などが挙げられるが、Ｓｉ原料を溶解させた溶媒と同じものを用いるのが好ましい。 Examples of the M1 raw material include salts and alkoxides of the M1 element. The salt of M1 is not particularly limited as long as it is dissolved in a solvent, and examples thereof include chlorides, nitrates, and acetates. Examples of the alkoxy group of the alkoxide of M1 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the solution for dissolving the M1 raw material include organic solvents such as alcohol, water, and the like, but it is preferable to use the same solvent as that for dissolving the Si raw material.

Ｅｕ（III）原料としては、Ｅｕ（III）の塩またはアルコキシドが挙げられる。Ｅｕ（III）の塩としては、溶媒に溶解すれば特に限定されず、塩化ユウロピウム６水和物、硝酸ユウロピウム６水和物などが挙げられる。Ｅｕ（III）のアルコキシドのアルコキシ基としては、メトキシ基、エトキシ基、プロピオキシ基、ブトキシ基などが挙げられる。   Examples of the Eu (III) raw material include Eu (III) salts and alkoxides. The salt of Eu (III) is not particularly limited as long as it is dissolved in a solvent, and examples thereof include europium chloride hexahydrate and europium nitrate hexahydrate. Examples of the alkoxy group of the alkoxide of Eu (III) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Ｓｉ原料、Ｍ１原料、Ｅｕ（III）原料の配合比は、得ようとする蛍光体のＳｉ：Ｍ１：Ｅｕ（III）のモル比とほぼ同じにすればよい。
Ｓｉ原料を含む溶液と、Ｅｕ（III）原料及びＭ１原料を含む溶液とを、通常２０〜９０℃、好ましくは４０〜６０℃で、通常１〜１２０分間、好ましくは１０〜６０分間、撹拌混合することにより白色生成物が生成する。 The mixing ratio of the Si raw material, the M1 raw material, and the Eu (III) raw material may be substantially the same as the molar ratio of Si: M1: Eu (III) of the phosphor to be obtained.
The solution containing the Si raw material and the solution containing the Eu (III) raw material and the M1 raw material are usually stirred at 20 to 90 ° C., preferably 40 to 60 ° C., usually 1 to 120 minutes, preferably 10 to 60 minutes. This produces a white product.

この生成物をろ過することにより固体が得られる。得られた固体を水または有機溶媒により洗浄した後、必要に応じて３００℃以下で乾燥することにより、蛍光体前駆体が得られる。   A solid is obtained by filtering the product. After the obtained solid is washed with water or an organic solvent, the phosphor precursor is obtained by drying at 300 ° C. or lower as necessary.

本発明においては、得られた蛍光体前駆体を８００〜９３０℃、好ましくは８６０〜９１０℃、特に好ましくは８６５〜８７５℃の温度で焼成し、蛍光体前駆体に含まれる付着水、構造水およびＯＨ基をほぼ完全に除去して、非晶質蛍光体を得ることが特徴である。   In the present invention, the obtained phosphor precursor is baked at a temperature of 800 to 930 ° C., preferably 860 to 910 ° C., particularly preferably 865 to 875 ° C., and the adhering water and structural water contained in the phosphor precursor are used. It is characteristic that an amorphous phosphor is obtained by almost completely removing OH groups.

焼成時間が短すぎると蛍光体前駆体に含まれる水およびＯＨ基をほぼ完全に除去することができない。一方、焼成時間が長すぎるとウォラストナイトの結晶が生成するので、非晶質が維持される程度の時間であることが必要である。焼成時間は、焼成に供される蛍光体前駆体の量や蛍光体前駆体の乾燥状態などにより異なるが、通常５分間〜３時間、好ましくは１０〜７０分間、特に好ましくは１０〜３０分間である。
焼成は、大気雰囲気などの酸化雰囲気で行う。還元雰囲気だとＥｕ(III)がＥｕ(II)に還元され、蛍光体の発光色が赤色ではなくなるので好ましくない。 If the firing time is too short, water and OH groups contained in the phosphor precursor cannot be removed almost completely. On the other hand, if the firing time is too long, crystals of wollastonite are generated, so it is necessary that the time is sufficient to maintain the amorphous state. The firing time varies depending on the amount of the phosphor precursor subjected to firing and the dry state of the phosphor precursor, but is usually 5 minutes to 3 hours, preferably 10 to 70 minutes, particularly preferably 10 to 30 minutes. is there.
Firing is performed in an oxidizing atmosphere such as an air atmosphere. A reducing atmosphere is not preferable because Eu (III) is reduced to Eu (II) and the emission color of the phosphor is not red.

このようにして得られる蛍光体は、非晶質であり、一般式Ｍ１ｘＥｕｙＳｉＯ２＋ｘ＋１．５ｙで表される。
一般式中、Ｍ１は、Ｃａ、Ｓｒ及びＢａから選ばれる１以上の元素を表し、ｘ、ｙは、０．６≦ｘ＋１．５ｙ≦０．９、好ましくは０．７≦ｘ＋１．５ｙ≦０．８で表される数である。酸素は２＋ｘ＋１．５ｙで表される量より欠損していてもよい。また、一般式で表される非晶質蛍光体は、蛍光体１モルに対し、水換算で０．１モル未満の水またはＯＨ基を含んでいてもよいが、含まないのが好ましい。 The phosphor thus obtained is amorphous and is represented by the general formula M1 x Eu y SiO 2 + x + 1.5y .
In the general formula, M1 represents one or more elements selected from Ca, Sr and Ba, and x and y are 0.6 ≦ x + 1.5y ≦ 0.9, preferably 0.7 ≦ x + 1.5y ≦ 0. .8. Oxygen may be deficient from the amount represented by 2 + x + 1.5y. Further, the amorphous phosphor represented by the general formula may contain less than 0.1 mol of water or OH group in terms of water with respect to 1 mol of the phosphor, but preferably does not contain it.

蛍光体の組成は、得られた非晶質蛍光体が塩酸に溶解しにくいことから、蛍光体前駆体のＣａ、Ｅｕ及びＳｉの量を測定し、焼成によってこれらの元素は揮発しないとして、蛍光体の組成を決定した。蛍光体前駆体の組成は、蛍光体前駆体を塩酸で溶解した後、ＩＣＰ（誘導結合プラズマ発光分析）などによりＣａ、Ｅｕ及びＳｉの量を測定することにより割合を決定した。Ｏの割合は、便宜的に、Ｃａのモル数に対して１倍、Ｅｕのモル数に対して１．５倍、Ｓｉのモル数に対して２倍して得られた数を和することにより決定した。また、非晶質蛍光体に含まれる水及びＯＨ基の量は、ＴＧ（示差熱分析）の１００〜８００℃の減量により決定した。   The composition of the phosphor is that the obtained amorphous phosphor is difficult to dissolve in hydrochloric acid. Therefore, the amount of Ca, Eu and Si of the phosphor precursor is measured, and these elements are not volatilized by firing. The body composition was determined. The composition of the phosphor precursor was determined by measuring the amount of Ca, Eu and Si by ICP (inductively coupled plasma emission analysis) after dissolving the phosphor precursor with hydrochloric acid. For the sake of convenience, the ratio of O is 1 times the number of moles of Ca, 1.5 times the number of moles of Eu, and 2 times the number of moles of Si. Determined by. The amounts of water and OH groups contained in the amorphous phosphor were determined by reducing TG (differential thermal analysis) at 100 to 800 ° C.

蛍光体が非晶質であることは、Ｘ線回折により確認することができる。
このようにして得られる本発明の非晶質蛍光体は、３９５ｎｍの近紫外線により励起され、６００〜６２０ｎｍの範囲に主発光ピークを有する。 It can be confirmed by X-ray diffraction that the phosphor is amorphous.
The amorphous phosphor of the present invention thus obtained is excited by near ultraviolet light of 395 nm and has a main emission peak in the range of 600 to 620 nm.

本発明の非晶質赤色蛍光体は、近紫外線の照射により、赤色に高い発光強度を示すので、近紫外線ＬＥＤを用いた白色ＬＥＤに極めて有用である。   Since the amorphous red phosphor of the present invention exhibits high emission intensity in red when irradiated with near ultraviolet rays, it is extremely useful for white LEDs using near ultraviolet LEDs.

以下、本発明の実施例について図面を参照して説明する。
塩化カルシウム（例えば関東化学株式会社製）１．１３２１ｇ（０．０５モル）を純水２００ｍｌに溶解した溶液に塩化ユウロピウム（III）６水和物（例えば関東化学株式会社製）１．１９５６ｇ（０．０１６モル）を固体で添加、溶解させてこの溶液を５０℃に保持した。 Embodiments of the present invention will be described below with reference to the drawings.
Europium chloride (III) hexahydrate (for example, manufactured by Kanto Chemical Co., Ltd.) 1.19556 g (0) in a solution obtained by dissolving 1.1321 g (0.05 mol) of calcium chloride (for example, manufactured by Kanto Chemical Co., Ltd.) in 200 ml of pure water. .016 mol) was added and dissolved as a solid to keep the solution at 50 ° C.

メタケイ酸ナトリウム９水和物（ナカライテスク（株）製）３．６７２３ｇ（０．０６６モル）を純水２００ｍｌに溶解して、５０℃に保持した。酸化カルシウムと塩化ユウロピウムを含む溶液と、メタケイ酸ナトリウムを含む溶液とを混合したところ白色生成物が得られた。これを５０℃に保持しながら、３０分間撹拌して反応を完結させた。   3.6723 g (0.066 mol) of sodium metasilicate nonahydrate (manufactured by Nacalai Tesque) was dissolved in 200 ml of pure water and kept at 50 ° C. When a solution containing calcium oxide and europium chloride was mixed with a solution containing sodium metasilicate, a white product was obtained. While maintaining this at 50 ° C., the reaction was completed by stirring for 30 minutes.

反応生成物を吸引ろ過し、得られた固体を純水１００ｍｌで洗浄、ろ過した後、40℃で24時間乾燥させ、蛍光体前駆体を得た。得られた蛍光体前駆体の組成をＩＣＰを用いて測定した結果、ＣａＯ：１５．３mass％,Ｅｕ２Ｏ３：２２．９mass％，ＳｉＯ２：３７．０mass%,Ｈ２Ｏ：２４．８mass%であった。 The reaction product was suction filtered, and the resulting solid was washed with 100 ml of pure water, filtered, and then dried at 40 ° C. for 24 hours to obtain a phosphor precursor. As a result of measuring the composition of the obtained phosphor precursor using ICP, CaO: 15.3 mass%, Eu 2 O 3 : 22.9 mass%, SiO 2 : 37.0 mass%, H 2 O: 24.8 mass %Met.

得られた蛍光体前駆体を８７０℃に維持した電気炉に導入し、３０分間焼成を行い、蛍光体を得た。得られた蛍光体のＴＧにおける１００〜８００℃の減量は観察されず、蛍光体の組成はＣａ０．４４Ｅｕ０．２１ＳｉＯ２．７６であった。 The obtained phosphor precursor was introduced into an electric furnace maintained at 870 ° C. and baked for 30 minutes to obtain a phosphor. The obtained phosphor had a weight loss of 100 to 800 ° C. in TG, and the composition of the phosphor was Ca 0.44 Eu 0.21 SiO 2.76 .

得られた蛍光体の結晶性をＣｕ-Ｋαを用いるＸ線回折により確認した。結果を図１に示す。図１より明らかなように得られた蛍光体は非晶質であった。また、得られた蛍光体の励起スペクトル及び発光スペクトルを日立社製Ｆ−４５００を用いて測定した。この結果を図２に示す。さらに、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図３に示す。 The crystallinity of the obtained phosphor was confirmed by X-ray diffraction using Cu-K alpha. The results are shown in FIG. As apparent from FIG. 1, the obtained phosphor was amorphous. Moreover, the excitation spectrum and emission spectrum of the obtained phosphor were measured using Hitachi F-4500. The result is shown in FIG. Further, when the obtained phosphor was irradiated with near ultraviolet rays having a wavelength of 395 nm, light emission was confirmed in the vicinity of a wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

塩化カルシウムを１．０２８６ｇ（０．０４４モル）、塩化ユウロピウム（III）６水和物を１．３９６６ｇ（０．０１９モル）、メタケイ酸ナトリウムを３．５７４８ｇ（０．０６３モル）とした他は、実施例１と同様に行い、蛍光体を得た。   Other than using 1.0286 g (0.044 mol) of calcium chloride, 1.3966 g (0.019 mol) of europium (III) chloride hexahydrate, and 3.5748 g (0.063 mol) of sodium metasilicate. In the same manner as in Example 1, a phosphor was obtained.

得られた蛍光体の組成はＣａ0.38Ｅｕ0.33ＳｉＯ2.875で、Ｘ線回折の結果、非晶質であった。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図３に示す。 The composition of the obtained phosphor was Ca 0.38 Eu 0.33 SiO 2.875 , and was amorphous as a result of X-ray diffraction. Further, when the obtained phosphor was irradiated with near ultraviolet rays having a wavelength of 395 nm, light emission was confirmed in the vicinity of a wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

塩化カルシウムを０．８３７２ｇ（０．０３６モル）、塩化ユウロピウム（III）６水和物を１．７６８３ｇ（０．０２４モル）、メタケイ酸ナトリウム３．３９４５ｇ(０．０６０モル)とした他は、実施例１と同様に行い、蛍光体を得た。   In addition to 0.8372 g (0.036 mol) of calcium chloride, 1.7683 g (0.024 mol) of europium (III) chloride hexahydrate, and 3.3945 g (0.060 mol) of sodium metasilicate, The same procedure as in Example 1 was performed to obtain a phosphor.

得られた蛍光体の組成はＣａ0.17Ｅｕ0.31ＳｉＯ2.635で、Ｘ線回折の結果、非晶質であった。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図３に示す。 The composition of the obtained phosphor was Ca 0.17 Eu 0.31 SiO 2.635 , and was amorphous as a result of X-ray diffraction. Further, when the obtained phosphor was irradiated with near ultraviolet rays having a wavelength of 395 nm, light emission was confirmed in the vicinity of a wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

塩化カルシウムを１．４７９６ｇ（０．０６３モル）、塩化ユウロピウム（III）６水和物を０．５２０９ｇ（０．００７モル）、メタケイ酸ナトリウム３．９９９５ｇ(０．０７０モル)とした他は、実施例１と同様に行い、蛍光体を得た。   Except for calcium chloride of 1.4796 g (0.063 mol), europium chloride (III) hexahydrate of 0.5209 g (0.007 mol), and sodium metasilicate 3.995 g (0.070 mol), The same procedure as in Example 1 was performed to obtain a phosphor.

得られた蛍光体の組成はＣａ0.70Ｅｕ0.10ＳｉＯ2.85で、Ｘ線回折の結果、非晶質であった。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図３に示す。 The composition of the obtained phosphor was Ca 0.70 Eu 0.10 SiO 2.85 , and was amorphous as a result of X-ray diffraction. Further, when the obtained phosphor was irradiated with near ultraviolet rays having a wavelength of 395 nm, light emission was confirmed in the vicinity of a wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

実施例１において、得られた蛍光体前駆体を８００℃に維持した電気炉に導入した他は実施例１と同様に行い、蛍光体を得た。   In Example 1, a phosphor was obtained in the same manner as in Example 1 except that the obtained phosphor precursor was introduced into an electric furnace maintained at 800 ° C.

得られた蛍光体の結晶性をＸ線回折により確認したところ、非晶質であった。結果を図５に示す。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、発光波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図４に示す。   When the crystallinity of the obtained phosphor was confirmed by X-ray diffraction, it was amorphous. The results are shown in FIG. Further, when the obtained phosphor was irradiated with near ultraviolet rays of 395 nm, light emission was confirmed in the vicinity of an emission wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

実施例１において、得られた蛍光体前駆体を９００℃に維持した電気炉に導入した他は実施例１と同様に行い、蛍光体を得た。   In Example 1, a phosphor was obtained in the same manner as in Example 1 except that the obtained phosphor precursor was introduced into an electric furnace maintained at 900 ° C.

得られた蛍光体の結晶性をＸ線回折により確認したところ、非晶質であった。結果を図５に示す。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、発光波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図４に示す。   When the crystallinity of the obtained phosphor was confirmed by X-ray diffraction, it was amorphous. The results are shown in FIG. Further, when the obtained phosphor was irradiated with near ultraviolet rays of 395 nm, light emission was confirmed in the vicinity of an emission wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

＜比較例１＞
実施例１において、得られた蛍光体前駆体を７００℃に維持した電気炉に導入した他は実施例１と同様に行い、蛍光体を得た。得られた蛍光体の結晶性をＸ線回折により確認したところ、非晶質であった。結果を図５に示す。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、発光波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図４に示す。得られた蛍光体のＴＧにおける１００〜８００℃の減量をＨ２Ｏ換算すると、蛍光体１モルに対して０．１モルの水に相当した。 <Comparative Example 1>
In Example 1, a phosphor was obtained in the same manner as in Example 1 except that the obtained phosphor precursor was introduced into an electric furnace maintained at 700 ° C. When the crystallinity of the obtained phosphor was confirmed by X-ray diffraction, it was amorphous. The results are shown in FIG. Further, when the obtained phosphor was irradiated with near ultraviolet rays of 395 nm, light emission was confirmed in the vicinity of an emission wavelength of 613 nm. The emission spectrum at this time is shown in FIG. When the loss of 100 to 800 ° C. in TG of the obtained phosphor was converted to H 2 O, it corresponded to 0.1 mol of water with respect to 1 mol of the phosphor.

＜比較例２＞
実施例１において、得られた蛍光体前駆体を９５０℃に維持した電気炉に導入した他は実施例１と同様に行い、蛍光体を得た。 <Comparative example 2>
A phosphor was obtained in the same manner as in Example 1 except that the phosphor precursor obtained in Example 1 was introduced into an electric furnace maintained at 950 ° C.

得られた蛍光体の結晶性をＸ線回折により確認したところ、ウォラストナイトが生成していた。結果を図５に示す。また、得られた蛍光体に３９５ｎｍの近紫外線を照射したところ、発光波長６１３ｎｍ付近に発光が確認された。このときの発光スペクトルを図４に示す。   When the crystallinity of the obtained phosphor was confirmed by X-ray diffraction, wollastonite was generated. The results are shown in FIG. Further, when the obtained phosphor was irradiated with near ultraviolet rays of 395 nm, light emission was confirmed in the vicinity of an emission wavelength of 613 nm. The emission spectrum at this time is shown in FIG.

本発明により得られる非晶質赤色蛍光体は、近紫外線の照射により、赤色に高い発光強度を示すので、近紫外線ＬＥＤを用いた白色ＬＥＤに極めて有用である。また、ＥＬ素子用の蛍光体、バックライト用のパネル、面発光体、照明体、掲示板などに用いられる。
The amorphous red phosphor obtained by the present invention exhibits a high emission intensity in red when irradiated with near ultraviolet rays, and is thus extremely useful for white LEDs using near ultraviolet LEDs. Further, it is used for phosphors for EL elements, panels for backlights, surface light emitters, illumination bodies, bulletin boards, and the like.

Claims (6)

溶液反応により得られた蛍光体前駆体を８００〜９３０℃で焼成し、一般式Ｍ１ｘＥｕｙＳｉＯ２＋ｘ＋１．５ｙ（式中、Ｍ１は、Ｃａ、Ｓｒ及びＢａから選ばれる１以上の元素、０．６≦ｘ＋１．５ｙ≦０．９）で表される非晶質赤色蛍光体を得ることを特徴とする蛍光体の製造方法。 The phosphor precursor obtained by the solution reaction is baked at 800 to 930 ° C., and the general formula M1 x Eu y SiO 2 + x + 1.5y (where M1 is one or more elements selected from Ca, Sr and Ba, 0 .. 6 ≦ x + 1.5y ≦ 0.9) to obtain an amorphous red phosphor. 前記溶液反応において、Ｓｉ原料がメタケイ酸ナトリウム、水ガラスまたはアルコキシシランであり、Ｅｕ原料がＥｕ（III）の塩またはアルコキシドであり、Ｍ１原料がＭ１元素の塩またはアルコキシドであることを特徴とする請求項１に記載の蛍光体の製造方法。 In the solution reaction, the Si raw material is sodium metasilicate, water glass or alkoxysilane, the Eu raw material is Eu (III) salt or alkoxide, and the M1 raw material is M1 element salt or alkoxide. The manufacturing method of the fluorescent substance of Claim 1. 前記一般式において、Ｍ１がＣａであることを特徴とする請求項１または２に記載の蛍光体の製造方法。 3. The method for producing a phosphor according to claim 1, wherein M1 is Ca in the general formula. 前記蛍光体前駆体の焼成温度を８６０〜８８０℃とすることを特徴とする請求項１ないし３のいずれかに記載の蛍光体の製造方法。 The method for producing a phosphor according to any one of claims 1 to 3, wherein a firing temperature of the phosphor precursor is set to 860 to 880 ° C. 請求項１ないし４のいずれに記載の蛍光体の製造方法により得られることを特徴とする非晶質赤色蛍光体。 An amorphous red phosphor obtained by the method for producing a phosphor according to any one of claims 1 to 4. 一般式Ｍ１ｘＥｕｙＳｉＯ２＋ｘ＋１．５ｙ（式中、Ｍ１は、Ｃａ、Ｓｒ及びＢａから選ばれる１以上の元素、０．６≦ｘ＋１．５ｙ≦０．９）で表される非晶質赤色蛍光体。
Amorphous red represented by the general formula M1 x Eu y SiO 2 + x + 1.5y (where M1 is one or more elements selected from Ca, Sr and Ba, 0.6 ≦ x + 1.5y ≦ 0.9) Phosphor.
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