JP2018150496A - Manufacturing method of red phosphor - Google Patents
Manufacturing method of red phosphor Download PDFInfo
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- JP2018150496A JP2018150496A JP2017049709A JP2017049709A JP2018150496A JP 2018150496 A JP2018150496 A JP 2018150496A JP 2017049709 A JP2017049709 A JP 2017049709A JP 2017049709 A JP2017049709 A JP 2017049709A JP 2018150496 A JP2018150496 A JP 2018150496A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims abstract description 69
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- 229910052791 calcium Inorganic materials 0.000 claims abstract description 26
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- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
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- 229910052693 Europium Inorganic materials 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
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- 239000003870 refractory metal Substances 0.000 claims description 47
- 239000013078 crystal Substances 0.000 claims description 38
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 2
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- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical group Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
Description
本発明は、一般式がＭＡｌＳｉＮ３（Ｍは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｅｕの群の中から選択される一種以上の元素である）で示される赤色蛍光体の製造方法に関する。 The present invention relates to a method for producing a red phosphor represented by a general formula MAlSiN 3 (M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Eu).
白色発光ダイオード（以降、発光ダイオードをＬＥＤとも記載する）は、半導体発光素子と蛍光体との組み合わせにより疑似白色光を発光するデバイスであり、その代表的な例として、青色ＬＥＤと黄色のイットリウム・アルミニウム・ガーネット蛍光体（以降ＹＡＧ蛍光体と記載する）の組み合わせが知られている。しかし、この方式の白色ＬＥＤは、その色度座標値としては白色領域に入るものの、赤色発光成分が不足しているために、照明用途に用いると演色性が低く、液晶バックライトのような画像表示装置では色再現性が悪いという問題がある。そのため、不足している赤色発光成分を補うために、ＹＡＧ蛍光体とともに、赤色を発光する窒化物又は酸窒化物蛍光体を併用することが提案されている（特許文献１）。 A white light emitting diode (hereinafter, light emitting diode is also referred to as an LED) is a device that emits pseudo white light by a combination of a semiconductor light emitting element and a phosphor. As a typical example, a blue LED and a yellow yttrium A combination of an aluminum garnet phosphor (hereinafter referred to as a YAG phosphor) is known. However, although this type of white LED falls within the white region as its chromaticity coordinate value, it lacks a red light-emitting component, so when used in lighting applications, it has a low color rendering property, such as an image like a liquid crystal backlight. The display device has a problem of poor color reproducibility. Therefore, it has been proposed to use a nitride or oxynitride phosphor that emits red light together with the YAG phosphor in order to compensate for the insufficient red light-emitting component (Patent Document 1).
赤色を発光する窒化物蛍光体としては、一般式がＭＡｌＳｉＮ３（Ｍは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｅｕの群の中から選択される一種以上の元素である）で示され、例えばＣａＡｌＳｉＮ３結晶相と同一の結晶構造を有する無機化合物を母体結晶として、さらに光学活性な元素で付活したものが知られている。なかでもＥｕ２＋で付活したＣａＡｌＳｉＮ３蛍光体は特に高輝度で発光するとされている（特許文献２）。また、特許文献２には、Ｃａの一部をＳｒで置換することにより、発光ピーク波長が短波長側にシフトした蛍光体が得られることが記載されている。このＥｕ２＋付活した（Ｓｒ，Ｃａ）ＡｌＳｉＮ３蛍光体は、ＣａＡｌＳｉＮ３蛍光体よりも発光波長が短く、視感度が高い領域のスペクトル成分が増えることから、高輝度白色ＬＥＤ用の赤色蛍光体として有望である。なお、本発明では、ＣａＡｌＳｉＮ３蛍光体と（Ｓｒ，Ｃａ）ＡｌＳｉＮ３蛍光体をまとめて、ＣＡＳＮ系蛍光体と呼ぶ。 A nitride phosphor that emits red light has a general formula of MAlSiN 3 (M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Eu). For example, CaAlSiN A compound in which an inorganic compound having the same crystal structure as that of the three crystal phases is used as a base crystal and activated with an optically active element is known. Among them, the CaAlSiN 3 phosphor activated with Eu 2+ is said to emit light with particularly high luminance (Patent Document 2). Patent Document 2 describes that a phosphor having an emission peak wavelength shifted to the short wavelength side can be obtained by replacing a part of Ca with Sr. Since this Eu 2+ activated (Sr, Ca) AlSiN 3 phosphor has a shorter emission wavelength than the CaAlSiN 3 phosphor and increases the spectral components in the region with high visibility, the red phosphor for high-intensity white LEDs As promising. In the present invention, the CaAlSiN 3 phosphor and the (Sr, Ca) AlSiN 3 phosphor are collectively referred to as a CASN phosphor.
ＣＡＳＮ系蛍光体は、波長が長く深みのある赤色領域にスペクトル成分を多く含むため、高い演色性を実現できる反面、視感度の低いスペクトル成分が多くなり、白色ＬＥＤとしての輝度は低くなってしまうという課題があった。なお、特に実際に蛍光体を製造する場合においては、蛍光体の主要な組成を最適化することのみならず、例えば蛍光体を焼成する温度や焼成時の環境など、一般的には見落としやすい製造中の様々な因子が輝度をはじめとする蛍光体の特性に影響を及ぼすことがあり、それら因子の影響については十分に把握されてなかった。そこで焼成容器の素材としても用いられる高融点金属が、最終的に本発明の赤色蛍光体の特性に及ぼす影響について調べ、本発明は、輝度の優れた赤色蛍光体の製造方法を提供することを目的とした。そして本発明者らは、上記課題を解決すべく鋭意検討した結果、原料混合体を焼成する際に高融点金属を共存させると、輝度が優れた赤色蛍光体となることを見出し、本発明の完成に至った。 Since the CASN phosphor contains many spectral components in the deep red region with a long wavelength, high color rendering can be realized, but on the other hand, there are many spectral components with low visibility and the luminance as a white LED is low. There was a problem. In particular, when actually manufacturing a phosphor, not only optimizing the main composition of the phosphor, but also generally easy to overlook, such as the temperature at which the phosphor is fired and the environment during firing Various factors may affect the characteristics of phosphors such as luminance, and the effects of these factors have not been fully understood. Therefore, the influence of the refractory metal used also as a material for the firing container on the properties of the red phosphor of the present invention was finally investigated, and the present invention provides a method for producing a red phosphor with excellent luminance. It was aimed. And as a result of intensive studies to solve the above problems, the present inventors have found that when a refractory metal coexists when firing a raw material mixture, a red phosphor having excellent luminance is obtained. Completed.
課題を解決するための手段、即ち本発明は以下に示す（１）〜（７）である。
（１）一般式がＭＡｌＳｉＮ３（Ｍは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｅｕの群の中から選択される一種以上の元素である）で示される赤色蛍光体の製造方法であって、前記赤色蛍光体の原料化合物を混合して原料混合体を形成する混合工程と、焼成容器内において、前記原料混合体と、焼成温度の最高値より高い融点を有する高融点金属とを、共存させて焼成する焼成工程とを有する、赤色蛍光体の製造方法である。
（２）前記（１）記載の赤色蛍光体の製造方法では、原料混合体の平均粒子径が０．１μｍ〜１００μｍであることが好ましい。
（３）前記（１）または（２）記載の赤色蛍光体の製造方法では、焼成工程が、原料混合体と高融点金属とを、原料混合体の単位質量に対する高融点金属の接触面積が１．４０ｃｍ２／ｇ以上 ５．００ｃｍ２／ｇ以下の割合で接触させ共存させる工程であることが好ましい。
（４）前記（１）〜（３）いずれか一項に係る高融点金属は、鉄より高い融点を持つ金属の単体、複合体または合金であることが好ましい。
（５）さらに前記（１）〜（４）いずれか一項に係る高融点金属は、モリブデン、タンタル、タングステンの群の中から選択される一種以上の金属の単体、複合体または合金であることが好ましい。
（６）前記（１）〜（５）に係る赤色蛍光体の製造方法は、ＣａＡｌＳｉＮ３である結晶相と同一の結晶構造を母体結晶とする蛍光体の製造に好ましく適用される。
（７）前記（１）〜（５）に係る赤色蛍光体の製造方法は、（Ｓｒ，Ｃａ）ＡｌＳｉＮ３である結晶相と同一の結晶構造を母体結晶とする蛍光体の製造に好ましく適用される。
Means for solving the problem, that is, the present invention is the following (1) to (7).
(1) A method for producing a red phosphor represented by the general formula MAlSiN 3 (M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Eu), A mixing step of mixing a raw material compound of a red phosphor to form a raw material mixture, and in the firing vessel, the raw material mixture and a refractory metal having a melting point higher than the highest firing temperature It is a manufacturing method of a red fluorescent substance which has a baking process to bake.
(2) In the method for producing a red phosphor according to (1), the average particle size of the raw material mixture is preferably 0.1 μm to 100 μm.
(3) In the method for producing a red phosphor according to the above (1) or (2), the firing step includes the raw material mixture and the refractory metal, and the contact area of the refractory metal with respect to the unit mass of the raw material mixture is 1 It is preferably a step in which they are brought into contact with each other at a ratio of 40 cm 2 / g to 5.00 cm 2 / g.
(4) The refractory metal according to any one of (1) to (3) is preferably a single metal, a composite or an alloy having a melting point higher than that of iron.
(5) Further, the refractory metal according to any one of the above (1) to (4) is a simple substance, a composite or an alloy of one or more metals selected from the group consisting of molybdenum, tantalum and tungsten. Is preferred.
(6) The method for producing a red phosphor according to the above (1) to (5) is preferably applied to the production of a phosphor having a crystal structure identical to the crystal phase of CaAlSiN 3 as a base crystal.
(7) The method for producing a red phosphor according to the above (1) to (5) is preferably applied to the production of a phosphor having a crystal structure identical to the crystal phase of (Sr, Ca) AlSiN 3 as a base crystal. The
本発明の赤色蛍光体の製造方法の実施により、輝度の高い赤色蛍光体、特にＣａＡｌＳｉＮ３系蛍光体を得ることができる。またＬＥＤと前記赤色蛍光体とを組み合わせることにより、高輝度な発光素子やさらに照明装置などの発光装置をも提供することができるようになる。 By carrying out the method for producing a red phosphor of the present invention, a red phosphor having a high luminance, particularly a CaAlSiN 3 -based phosphor can be obtained. Further, by combining the LED and the red phosphor, it is possible to provide a light-emitting device such as a high-luminance light-emitting element and a lighting device.
以下に本発明を実施するための形態について説明する。 The form for implementing this invention is demonstrated below.
＜赤色蛍光体＞
本発明は、赤色蛍光体の原料を混合して原料混合体を形成する混合工程と、前記原料混合体と高融点金属とを焼成容器内で共存させて焼成する焼成工程とを備える、赤色蛍光体の製造方法である。また本発明の製造方法に係る赤色蛍光体は、一般式がＭＡｌＳｉＮ３（Ｍは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｅｕの群の中から選択される一種以上の元素である）で示される赤色蛍光体である。一般式中、Ｍｇはマグネシウム、Ｃａはカルシウム、Ｓｒはストロンチウム、Ｂａはバリウム、Ｅｕはユーロピウムであり、またＡｌはアルミニウム、Ｓｉはケイ素、Ｎは窒素の各元素を示す。）前記赤色蛍光体は、より具体的には、ＣａＡｌＳｉＮ３または（Ｓｒ，Ｃａ）ＡｌＳｉＮ３である結晶相と同一の結晶構造を母体結晶とする蛍光体、即ちＣＡＳＮ系蛍光体であることが好ましい。なお、蛍光体が（Ｓｒ，Ｃａ）ＡｌＳｉＮ３である結晶相と同一の結晶構造を母体結晶とする蛍光体である場合には、Ｓｔ原子のモル数を、Ｓｒ原子とＣａ原子の合計モル数で除した値は、０．３５以上０．９５以下であることが好ましく、更に好ましくは０．４０以上０．９０以下である。蛍光体の主結晶相がＣａＡｌＳｉＮ３結晶、または（Ｓｒ，Ｃａ）ＡｌＳｉＮ３結晶相と同一の構造か否かは、粉末Ｘ線回折測定を利用して確認することができる。結晶構造がＣａＡｌＳｉＮ３、または（Ｓｒ，Ｃａ）ＡｌＳｉＮ３結晶相と異なる場合、発光色が赤色でなくなったり、蛍光強度が大きく低下したりするので、好ましくない。例えばＣＡＳＮ系蛍光体の結晶の骨格構造は、（Ｓｉ，Ａｌ）−Ｎ４の正四面体が結合することにより構成され、その間隙にＣａ原子やＳｒ原子が位置したものである。ＣａやＳｒの一部が、発光中心として作用するＥｕで置換されることにより赤色蛍光体として機能するようになる。
<Red phosphor>
The present invention comprises a red phosphor comprising: a mixing step of mixing a raw material of a red phosphor to form a raw material mixture; and a firing step of firing the raw material mixture and a refractory metal together in a firing container. It is a manufacturing method of a body. The red phosphor according to the production method of the present invention has a red color represented by a general formula MAlSiN 3 (M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Eu). It is a phosphor. In the general formula, Mg is magnesium, Ca is calcium, Sr is strontium, Ba is barium, Eu is europium, Al is aluminum, Si is silicon, and N is nitrogen. ) More specifically, the red phosphor is preferably a phosphor having a crystal structure identical to the crystal phase of CaAlSiN 3 or (Sr, Ca) AlSiN 3 as a host crystal, that is, a CASN phosphor. . When the phosphor is a phosphor having the same crystal structure as that of the crystal phase of (Sr, Ca) AlSiN 3 as a host crystal, the number of moles of St atoms is the total number of moles of Sr atoms and Ca atoms. The value divided by is preferably 0.35 or more and 0.95 or less, more preferably 0.40 or more and 0.90 or less. Whether the main crystal phase of the phosphor has the same structure as the CaAlSiN 3 crystal or the (Sr, Ca) AlSiN 3 crystal phase can be confirmed using powder X-ray diffraction measurement. When the crystal structure is different from the CaAlSiN 3 or (Sr, Ca) AlSiN 3 crystal phase, the emission color is not red and the fluorescence intensity is greatly reduced, which is not preferable. For example, the skeletal structure of the crystal of the CASN phosphor is formed by bonding (Si, Al) -N4 tetrahedrons, and Ca atoms and Sr atoms are located in the gaps. A part of Ca and Sr functions as a red phosphor by being replaced with Eu acting as a light emission center.
なお本発明の赤色蛍光体の製造方法は、本発明でいう前記赤色蛍光体をなるべく高純度で得ることを目的とした製造方法であり、前記結晶が単相で得られることが好ましいが、前記赤色蛍光体の他に副生成物や異相を全く生成しないような製造方法を意味しているわけではなく、蛍光体特性に大きな影響がない限り、副生成物や異相を含んでいても構わない。また本発明の製造方法により得られる赤色蛍光体には、不可避的成分として微量の酸素原子が含まれることもある。蛍光体の組成パラメータであるＣａ原子及びＳｒ原子の割合、Ｓｉ／Ａｌモル数比やＮ／Ｏモル数比などは、赤色蛍光体の結晶構造を維持しながら、全体として電気的中性が保たれるように調整される。 The production method of the red phosphor of the present invention is a production method aiming to obtain the red phosphor as high as possible in the present invention, and the crystal is preferably obtained in a single phase, It does not mean a manufacturing method that does not generate any by-product or heterogeneous phase in addition to the red phosphor, and may contain by-products and heterogeneous phases as long as the phosphor characteristics are not greatly affected. . The red phosphor obtained by the production method of the present invention may contain a trace amount of oxygen atoms as an inevitable component. The ratio of Ca and Sr atoms, Si / Al mole ratio, N / O mole ratio, etc., which are the composition parameters of the phosphor, maintain the electrical neutrality as a whole while maintaining the crystal structure of the red phosphor. Adjusted to sag.
＜赤色蛍光体の原料混合体＞
本発明に係る一般式がＭＡｌＳｉＮ３（Ｍは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｅｕの群の中から選択される一種以上の元素である）で示される赤色蛍光体の原料は、これを構成する元素の酸化物や窒化物、特に窒化物が好ましく用いられる。例えば赤色蛍光体がＣＡＳＮ系蛍光体である場合は、原料化合物としてＣＡＳＮ系蛍光体を構成する元素の窒化物、即ち窒化アルミニウム、窒化ケイ素、窒化カルシウム及び窒化ストロンチウム、窒化ユーロピウムを好ましく用いることができる。またユーロピウムを含む原料化合物としては、入手が容易な酸化ユーロピウムも好ましく用いることができる。本発明では、これらの窒化物を混合工程で混合して原料混合体とする。
<Red phosphor raw material mixture>
The red phosphor raw material represented by the general formula MAlSiN 3 (M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Eu) according to the present invention constitutes this Oxides and nitrides of the elements to be used, particularly nitrides are preferably used. For example, when the red phosphor is a CASN phosphor, nitrides of elements constituting the CASN phosphor, that is, aluminum nitride, silicon nitride, calcium nitride, strontium nitride, and europium nitride can be preferably used as a raw material compound. . As a raw material compound containing europium, europium oxide, which is easily available, can also be preferably used. In the present invention, these nitrides are mixed in the mixing step to obtain a raw material mixture.
＜混合工程＞
本発明でいう混合工程は、目的とする赤色蛍光体が得られるように秤量した各原料化合物を、混合して粉末状の原料混合体と成す工程である。原料化合物を混合する方法は特に限定されないが、例えば、乳鉢、ボールミル、Ｖ型混合機、遊星ミル、ジェットミルなどの混合装置を用いて十分に混合する方法がある。なお、空気中の水分や酸素と激しく反応する窒化カルシウム、窒化ストロンチウム、窒化ユーロピウム等は、内部が不活性雰囲気で置換されたグローブボックス内や混合装置を用いて取り扱うことが適切である。
<Mixing process>
The mixing step referred to in the present invention is a step of mixing each raw material compound weighed so as to obtain the target red phosphor to form a powdery raw material mixture. The method of mixing the raw material compounds is not particularly limited, and there is, for example, a method of sufficiently mixing using a mixing device such as a mortar, ball mill, V-type mixer, planetary mill, or jet mill. In addition, it is appropriate to handle calcium nitride, strontium nitride, europium nitride, or the like that reacts violently with moisture or oxygen in the air, in a glove box in which the inside is replaced with an inert atmosphere or using a mixing device.
本発明の蛍光体の付活元素であるＥｕ含有率は、あまりに少ないと発光への寄与が小さくなる傾向にあり、あまりに多いとＥｕ同士間のエネルギー伝達による蛍光体の濃度消光現象が起こりやすくなる傾向にあるため、０．０１モル％以上０．３モル％以下であることが好ましく、さらに好ましくは０．０４モル％以上０．２モル％以下であり、さらに好ましくは０．０６モル％以上０．１５モル％以下である。 If the Eu content, which is an activation element of the phosphor of the present invention, is too small, the contribution to light emission tends to be small. If it is too large, the concentration quenching phenomenon of the phosphor due to energy transfer between Eu tends to occur. Therefore, it is preferably 0.01 mol% or more and 0.3 mol% or less, more preferably 0.04 mol% or more and 0.2 mol% or less, and further preferably 0.06 mol% or more. It is 0.15 mol% or less.
＜原料混合体の平均粒子径＞
本発明の製造方法は、原料混合体の粒子径や粒子の形状まで規定するものではないが、原料混合体の平均粒子径を測定した場合には、０．１μｍ以上１００μｍ以下であることが焼成工程における反応性の観点から好ましい。原料混合体の平均粒子径が０．１μｍ未満であるとハンドリング性が悪くなり生産性に欠け、平均粒子径が１００μｍを超えると焼成工程での反応が進みにくくなるため、目的とする赤色蛍光体が十分得られず、蛍光体の輝度が低下する傾向が高まる。
<Average particle diameter of raw material mixture>
The production method of the present invention does not prescribe the particle diameter or particle shape of the raw material mixture, but when the average particle diameter of the raw material mixture is measured, it is calcined to be 0.1 μm or more and 100 μm or less. It is preferable from the viewpoint of reactivity in the process. When the average particle size of the raw material mixture is less than 0.1 μm, the handling property is poor and the productivity is poor, and when the average particle size exceeds 100 μm, the reaction in the firing process is difficult to proceed. Is not sufficiently obtained, and the tendency of the luminance of the phosphor to decrease increases.
＜高融点金属＞
本発明の赤色蛍光体の製造方法に係る高融点金属は、焼成工程における焼成温度の最高値よりも高い融点を有する金属であり、前記金属は単体でも、複数の金属単体からなる複合体でも、合金でもよい。なお焼成温度の最高値よりも高い融点とは、より具体的な設定として鉄の融点（１５３８℃）と定めることが好ましい。このような高融点金属としては、ニオブ、モリブデン、タンタル、タングステン、レニウム、オスミウム、イリジウムの群の中から選択される一種以上の金属の単体、複合体または合金を挙げることができる。ハンドリング性、工業的生産性などを考慮するとモリブデン、タンタル、タングステンの単体が更に好ましい。本発明では、焼成容器内に原料混合体と高融点金属とを共存させて焼成する。この場合、高融点金属の形状等には特に規定はないが、形状としては板状、箔状が好ましい。原料混合体と接触する側の面の一部または全面を高融点金属とした焼成容器を用いるようにしても良い。また前記高融点金属製の焼成容器も好ましく用いることができる。
<High melting point metal>
The high melting point metal according to the method for producing a red phosphor of the present invention is a metal having a melting point higher than the highest firing temperature in the firing step, and the metal may be a simple substance or a composite composed of a plurality of simple metals, An alloy may be used. The melting point higher than the highest firing temperature is preferably determined as the melting point of iron (1538 ° C.) as a more specific setting. Examples of such a refractory metal include a simple substance, a composite, or an alloy of one or more metals selected from the group consisting of niobium, molybdenum, tantalum, tungsten, rhenium, osmium, and iridium. In consideration of handling properties, industrial productivity, etc., simple substances of molybdenum, tantalum and tungsten are more preferable. In the present invention, the raw material mixture and the refractory metal coexist in the firing container and fired. In this case, the shape of the refractory metal is not particularly limited, but the shape is preferably a plate shape or a foil shape. You may make it use the baking container which made a part or the whole surface of the side in contact with a raw material mixture a refractory metal. Moreover, the baking container made from the said refractory metal can also be used preferably.
高融点金属材の形状は、本発明の範囲内であれば特に制限はないが、焼成工程後に高融点金属を除去することを考慮すると、形状としてはワイヤー状、粒子状、タブレット状、棒状、箔状、板状が挙げられ、また焼成容器そのものでも構わない。箔状や板状である場合は、ハンドリング性、反応性の観点から、その厚みが０．１ｍｍ以上３ｍｍ以下であることが好ましい。 The shape of the refractory metal material is not particularly limited as long as it is within the scope of the present invention, but considering the removal of the refractory metal after the firing step, the shape is a wire shape, a particle shape, a tablet shape, a rod shape, A foil shape and a plate shape may be mentioned, and the firing container itself may be used. In the case of a foil shape or a plate shape, the thickness is preferably 0.1 mm or more and 3 mm or less from the viewpoint of handling properties and reactivity.
＜焼成容器内における原料混合体と高融点金属との共存＞
本発明では焼成容器内に原料混合体と高融点金属とを共存させて焼成する必要がある。本発明でいう共存とは、少なくとも同じ反応系内、例えば焼成容器内に原料混合体と高融点金属とが存在していることを意味している。この場合、高融点金属が原料混合体の赤色蛍光体への焼成に及ぼす、好ましい効果を期待するものであるから、両者はなるべく接近していることが好ましく、原料混合体が高融点金属に接触していることがより好ましい。このとき、高融点金属に接触するのは全ての原料混合体ではなく原料混合体の一部である。原料混合体の一部と表現したのは、原料混合体が粉末の集合体であることを考慮した表現であり、原料混合体を構成している多数の粒子のうちの限られた一部が高融点金属に接触している状態を表すものである。なお原料混合体と高融点金属とが接触している場合、原料混合体と高融点金属の相対的な関係としては、原料混合体の単位質量に対する高融点金属材の接触面積が、１．４０ｃｍ２／ｇ以上５．００ｃｍ２／ｇ以下となるように、より好ましくは１．５０ｃｍ２／ｇ以上３．２０ｃｍ２／ｇ以下となるように、設定することが好ましい。なおここでいう接触面積とは、高融点金属に接触している原料混合体を一体物と見なし、その一体物が覆っている面積の合計である。原料混合体と高融点金属の接触面積が１．４０ｃｍ２／ｇ以上であれば、得られる赤色蛍光体中への不純物元素、特に酸素原子の混入を抑えることができ、その結果赤色蛍光体の輝度を高くできる。また接触面積が、５．００ｃｍ２／ｇ以下であれば、得られる赤色蛍光体中への高融点金属元素の混入を抑制し、蛍光体の輝度の低下を抑制できるため好ましい。さらに、原料混合体が高融点金属と直に接触してない場合でも、両者間の距離は、直線距離にして１０ｃｍの範囲内に納めることが好ましく、５ｃｍの範囲内であればさらに好ましい。
<Coexistence of raw material mixture and refractory metal in firing container>
In the present invention, it is necessary to fire the raw material mixture and the refractory metal in the firing container. The coexistence in the present invention means that the raw material mixture and the refractory metal are present at least in the same reaction system, for example, in a firing vessel. In this case, since the high melting point metal is expected to have a favorable effect on the firing of the raw material mixture to the red phosphor, it is preferable that both are as close as possible, and the raw material mixture is in contact with the high melting point metal. More preferably. At this time, it is not all the raw material mixture but a part of the raw material mixture that contacts the refractory metal. The expression of a part of the raw material mixture is an expression considering that the raw material mixture is an aggregate of powder, and a limited part of the many particles constituting the raw material mixture It represents a state in contact with a refractory metal. When the raw material mixture and the refractory metal are in contact, the relative relationship between the raw material mixture and the refractory metal is that the contact area of the refractory metal material with respect to the unit mass of the raw material mixture is 1.40 cm. so that 2 / g or more 5.00 cm 2 / g or less, more preferably to be equal to or less than 1.50 cm 2 / g or more 3.20Cm 2 / g, it is preferable to set. Here, the contact area is the total of the area covered by the raw material mixture in contact with the refractory metal as an integral object. If the contact area between the raw material mixture and the refractory metal is 1.40 cm 2 / g or more, it is possible to suppress the mixing of impurity elements, particularly oxygen atoms, into the resulting red phosphor. Brightness can be increased. Moreover, it is preferable if the contact area is 5.00 cm 2 / g or less, since mixing of the refractory metal element into the resulting red phosphor can be suppressed, and a decrease in luminance of the phosphor can be suppressed. Furthermore, even when the raw material mixture is not in direct contact with the refractory metal, the distance between the two is preferably within a range of 10 cm as a linear distance, and more preferably within a range of 5 cm.
＜焼成工程＞
本発明の赤色蛍光体の製造方法において、その焼成工程では、前記の原料混合体と高融点金属とが焼成容器内で共存するよう、好ましくは原料混合体の一部が高融点金属と接触するように、焼成容器内部に充填して焼成する。前記焼成容器は、気密性を高められる構造を備えていることが好ましく、容器内部はアルゴン、ヘリウム、水素、窒素等の非酸化性ガスの雰囲気ガスで満たすことが好ましい。焼成容器は、高温の雰囲気ガス下において安定で、原料混合体及びその反応生成物と反応しにくい材質で構成されることが好ましく、例えば窒化ホウ素製、カーボン製の容器や、モリブデンやタンタルやタングステン等の高融点金属製の容器を使用することが好ましい。原料混合体に含まれる不純物元素、特に酸素原子が高融点金属と反応することが推定され、目的とする赤色蛍光体に不純物元素が取り込まれることを抑制することができる。
<Baking process>
In the method for producing a red phosphor according to the present invention, in the firing step, preferably, a part of the raw material mixture is in contact with the refractory metal so that the raw material mixture and the refractory metal coexist in the firing container. Thus, the inside of the firing container is filled and fired. The firing container preferably has a structure capable of enhancing airtightness, and the interior of the container is preferably filled with an atmosphere gas of a non-oxidizing gas such as argon, helium, hydrogen, and nitrogen. The firing container is preferably made of a material that is stable in a high-temperature atmosphere gas and hardly reacts with the raw material mixture and its reaction product. For example, a container made of boron nitride or carbon, molybdenum, tantalum, or tungsten. It is preferable to use a container made of a refractory metal such as. It is presumed that impurity elements contained in the raw material mixture, particularly oxygen atoms, react with the refractory metal, and it is possible to prevent the impurity elements from being taken into the target red phosphor.
＜焼成温度＞
焼成工程では、原料混合体を充填した焼成容器を速やかに焼成炉内に置き、焼成雰囲気に例えば窒素ガスを用い、１０００℃以上２０００℃以下で焼成する。この温度範囲であれば、焼成工程終了後の未反原料を少なくでき、また主結晶相の分解を抑制できるため好ましい。好ましい焼成温度の範囲は１５００℃以上２０００℃以下であり、さらに好ましくは１６００℃以上２０００℃以下の範囲である。
<Baking temperature>
In the firing step, the firing container filled with the raw material mixture is quickly placed in a firing furnace, and fired at 1000 ° C. or more and 2000 ° C. or less using, for example, nitrogen gas in the firing atmosphere. If it is this temperature range, since the unstretched raw material after completion | finish of a baking process can be decreased and decomposition | disassembly of a main crystal phase can be suppressed, it is preferable. The range of preferable baking temperature is 1500 degreeC or more and 2000 degrees C or less, More preferably, it is the range of 1600 degreeC or more and 2000 degrees C or less.
＜焼成雰囲気ガスの種類＞
焼成工程における焼成雰囲気ガスの種類としては、例えば元素としての窒素を含むガスを好ましく用いることができる。具体的には、窒素（Ｎ２）及び／又はアンモニアを挙げることができ、特に窒素が好ましい。また同様に、アルゴン、ヘリウム等の不活性ガスも好ましく用いることができる。なお焼成雰囲気ガスは１種類のガスで構成されていても、複数の種類のガスの混合ガスであっても構わない。
<Types of firing atmosphere gas>
As a kind of the firing atmosphere gas in the firing step, for example, a gas containing nitrogen as an element can be preferably used. Specific examples include nitrogen (N 2 ) and / or ammonia, and nitrogen is particularly preferable. Similarly, an inert gas such as argon or helium can be preferably used. The firing atmosphere gas may be composed of one type of gas or a mixed gas of a plurality of types of gases.
＜焼成雰囲気ガスの圧力＞
焼成雰囲気ガスの圧力焼成雰囲気ガスの圧力は、焼成温度に応じて選択されるが、通常０．１ＭＰaＧ以上１０ＭＰａＧ以下とする加圧状態である。本発明に係る赤色蛍光体は、約１８００℃までの温度では大気圧下で安定して存在することができるが、１８００℃以上の温度で焼成する場合は、赤色蛍光体の分解を抑制するため、さらに加圧状態することが好ましい。即ち圧力はより好ましくは０．２ＭＰａＧ以上２．０ＭＰａＧ以下であり、さらに好ましくは０．５ＭＰａＧ以上２．０ＭＰａＧ以下であり、さらに好ましくは０．５ＭＰａＧ以上１．５ＭＰａＧ以下である。雰囲気圧力が高いほど、蛍光体の分解温度は高くなるが、工業的生産性を考慮すると０．５ＭＰａＧ以上１ＭＰａＧ以下とすることが好ましい。
<Baking atmosphere gas pressure>
The pressure of the firing atmosphere gas The pressure of the firing atmosphere gas is selected according to the firing temperature, but is usually a pressurized state of 0.1 MPaG or more and 10 MPaG or less. The red phosphor according to the present invention can exist stably under atmospheric pressure at temperatures up to about 1800 ° C., but in order to suppress decomposition of the red phosphor when fired at a temperature of 1800 ° C. or higher. Further, it is preferable to apply a pressure. That is, the pressure is more preferably 0.2 MPaG or more and 2.0 MPaG or less, further preferably 0.5 MPaG or more and 2.0 MPaG or less, and further preferably 0.5 MPaG or more and 1.5 MPaG or less. The higher the atmospheric pressure is, the higher the decomposition temperature of the phosphor is. However, considering industrial productivity, it is preferably 0.5 MPaG or more and 1 MPaG or less.
＜焼成時間＞
焼成工程における焼成時間は、未反応物が多く存在したり、赤色蛍光体の粒子が成長不足であったり、或いは生産性の低下という不都合が生じない時間範囲が選択される。本発明の赤色蛍光体の製造方法では、焼成時間は０．５時間以上４８時間以下であることが好ましく、２時間以上２４時間以下であることがより好ましい。
<Baking time>
As the firing time in the firing step, a time range in which a large amount of unreacted substances are present, red phosphor particles are insufficiently grown, or inconveniences such as a decrease in productivity does not occur is selected. In the method for producing the red phosphor of the present invention, the firing time is preferably 0.5 hours or more and 48 hours or less, and more preferably 2 hours or more and 24 hours or less.
焼成後、高融点金属材を除去した焼成物の状態は、原料配合や焼成条件によって、粉体状、塊状と様々である。蛍光体として実際に使用する場合に備えて、焼成物を所定のサイズの粉末にする解砕・粉砕工程及び／又は分級操作工程を備えていてもよい。なお蛍光体の平均粒子径は、励起光の吸収効率及び十分な発光効率を得るという点から、ＬＥＤ用蛍光体として好適に使用する場合には、蛍光体の平均粒子径が５〜３０μｍとなる様に調整するのが好ましい。また前記解砕・粉砕工程では、その処理に由来する不純物の混入を防ぐため、蛍光体と接触する機器の部材が、窒化ケイ素、アルミナ、サイアロンといった高靭性セラミックス製であることが好ましい。 After firing, the state of the fired product from which the refractory metal material has been removed varies depending on the raw material composition and firing conditions, such as powder and lump. In preparation for actual use as a phosphor, a pulverization / pulverization step and / or a classification operation step for converting the fired product into powder of a predetermined size may be provided. In addition, the average particle diameter of the phosphor is 5 to 30 μm when the phosphor is suitably used as a phosphor for LED from the viewpoint of obtaining the absorption efficiency of excitation light and sufficient luminous efficiency. It is preferable to adjust in such a manner. In the pulverization / pulverization step, it is preferable that the member of the device in contact with the phosphor is made of high toughness ceramics such as silicon nitride, alumina, and sialon in order to prevent the impurities derived from the treatment from being mixed.
本発明の赤色蛍光体の製造方法では、焼成工程終了後、得られた赤色蛍光体の特性を改善するため、赤色蛍光体中の不純物を除去する酸処理工程、赤色蛍光体の結晶性を向上するアニール工程をさらに実施することができる。 In the method for producing a red phosphor according to the present invention, after the firing process is completed, in order to improve the characteristics of the obtained red phosphor, an acid treatment process for removing impurities in the red phosphor, and the crystallinity of the red phosphor is improved. An annealing step can be further performed.
＜酸処理工程＞
酸処理工程を実施する場合、特に手順や方法に特に限定はないが、例えば塩酸、蟻酸、酢酸、硫酸、硝酸の群から選ばれる１種以上の酸の水溶液中に、焼成工程で得た赤色蛍光体を粉砕したものを分散させ、数分から数時間撹拌した後に、さらに液が沸騰するまで加温して沸騰状態を数分から数時間維持しながら撹拌し、最後に水洗する方法を挙げることができる。酸処理工程により、得られた赤色蛍光体中に含まれる、原料化合物由来の不純物元素、焼成容器由来の不純物元素、焼成工程で生じた異相、粉砕工程にて混入した不純物元素を溶解除去することができる。
<Acid treatment process>
When carrying out the acid treatment step, the procedure and method are not particularly limited, but for example, the red color obtained in the firing step in an aqueous solution of one or more acids selected from the group of hydrochloric acid, formic acid, acetic acid, sulfuric acid and nitric acid After dispersing the pulverized phosphor, stirring for several minutes to several hours, further heating until the liquid boils, stirring while maintaining the boiling state for several minutes to several hours, and finally washing with water it can. By the acid treatment step, the impurity element derived from the raw material compound, the impurity element derived from the firing container, the foreign phase generated in the firing step, and the impurity element mixed in the grinding step contained in the obtained red phosphor are dissolved and removed. Can do.
＜アニール工程＞
アニール工程における赤色蛍光体の加熱温度は、少なくとも３５０℃以上であって、赤色蛍光体が分解しない温度範囲内とすることができる。
<Annealing process>
The heating temperature of the red phosphor in the annealing step is at least 350 ° C. or more and can be within a temperature range in which the red phosphor does not decompose.
以下、本発明の赤色蛍光体の製造方法を、実施例及び比較例により、さらに具体的に説明する。 Hereinafter, the production method of the red phosphor of the present invention will be described more specifically with reference to Examples and Comparative Examples.
（実施例１）
赤色蛍光体の原料化合物として、α型窒化ケイ素粉末（ＳＮ−Ｅ１０グレード、宇部興産社製）５２．０質量％、窒化アルミニウム粉末（Ｅグレード、トクヤマ社製）４５．６質量％、酸化ユーロピウム（ＲＵグレード、信越化学工業社製）２．４質量％を、ナイロン製ポットと窒化ケイ素製ボールを用い、また混合溶媒としてエタノールを使用して、ボールミル混合を行った。溶媒を乾燥除去後、目開き７５μｍの篩を用いて分級し、篩下の粉末を回収した。
Example 1
As a raw material compound of a red phosphor, α-type silicon nitride powder (SN-E10 grade, manufactured by Ube Industries) 52.0 mass%, aluminum nitride powder (E grade, manufactured by Tokuyama Corp.) 45.6 mass%, europium oxide ( RU grade (manufactured by Shin-Etsu Chemical Co., Ltd.) was ball milled using 2.4% by mass using a nylon pot and silicon nitride balls, and ethanol as a mixed solvent. After removing the solvent by drying, it was classified using a sieve having an opening of 75 μm, and the powder under the sieve was collected.
前記篩下の粉末を、水分１質量ｐｐｍ以下、酸素１質量ｐｐｍ以下の窒素雰囲気を保持することができるグローブボックス中に移動させ、そこで窒化ストロンチウム(Ｍａｔｅｒｉｏｎ社製)、窒化カルシウム(太平洋セメント社製)をさらに配合し、乾式混合した。配合比は、前記の篩下粉末：窒化ストロンチウム：窒化カルシウム＝４９．５質量％：４８．１質量％：２．４質量％とした。乾式にて混合した原料粉末の大きさを揃えるため、再度、目開き２５０μｍのナイロン製篩で分級し、篩下からの回収粉末を、実施例１の原料混合体とした。 The powder under the sieve is moved into a glove box capable of maintaining a nitrogen atmosphere having a moisture content of 1 mass ppm or less and an oxygen content of 1 mass ppm or less, where strontium nitride (Matterion), calcium nitride (Pacific Cement) ) Was further blended and dry mixed. The blending ratio was set to the above-mentioned under-sieving powder: strontium nitride: calcium nitride = 49.5 mass%: 48.1 mass%: 2.4 mass%. In order to equalize the size of the raw material powder mixed in the dry method, it was classified again with a nylon sieve having an opening of 250 μm, and the recovered powder from under the sieve was used as the raw material mixture of Example 1.
焼成容器である蓋付きの円筒型窒化ホウ素製容器（Ｎ−１グレード、デンカ社製）中に、０．３ｍｍ厚のタングステン箔を入れ、さらに前記実施例１の原料混合体を２３０ｇ充填した。このとき原料混合体とタングステン箔の接触面積は３５０ｃｍ２であった。なお焼成容器の蓋は完全密閉するものではない（以降も同様）。 A cylindrical boron nitride container (N-1 grade, manufactured by Denka Co., Ltd.) with a lid, which is a firing container, was charged with 0.3 mm thick tungsten foil, and 230 g of the raw material mixture of Example 1 was further filled. At this time, the contact area between the raw material mixture and the tungsten foil was 350 cm 2 . Note that the lid of the baking container is not completely sealed (the same applies hereinafter).
原料混合体を充填した焼成容器をグローブボックスから取り出し、カーボンヒーターを備える電気炉内に速やかに置いて、電気炉内をいったん０．１ＰａＧ以下まで十分に真空排気した。真空排気したまま加熱を開始し、６００℃からは窒素ガスを電気炉内に導入し、炉内雰囲気圧力を０．９ＭＰａＧとした。窒素ガス導入後もそのまま１８００℃まで昇温し、１８００℃で４時間の焼成を実施した。 The firing container filled with the raw material mixture was taken out of the glove box and immediately placed in an electric furnace equipped with a carbon heater, and the inside of the electric furnace was once sufficiently evacuated to 0.1 PaG or less. Heating was started with evacuation, nitrogen gas was introduced into the electric furnace from 600 ° C., and the atmospheric pressure in the furnace was set to 0.9 MPaG. After the introduction of nitrogen gas, the temperature was raised to 1800 ° C. as it was, and firing was carried out at 1800 ° C. for 4 hours.
電気炉への通電を止めて常温（２５℃）にまで冷却した後、焼成容器内のタングステン箔を取り除いた。焼成体はボールミルを用いて解砕し、さらに目開き４５μｍの振動篩により分級し、実施例１の赤色蛍光体を得た。 After stopping energization to the electric furnace and cooling to room temperature (25 ° C.), the tungsten foil in the baking container was removed. The fired body was crushed using a ball mill, and further classified with a vibrating sieve having an opening of 45 μm, whereby the red phosphor of Example 1 was obtained.
（比較例１）
高融点金属を原料混合体と共存させなかったこと以外は、実施例１と同じ方法で比較例１の赤色蛍光体を作製した。
(Comparative Example 1)
A red phosphor of Comparative Example 1 was produced in the same manner as in Example 1 except that the refractory metal did not coexist with the raw material mixture.
（実施例２）
焼成容器として高融点金属でもあるモリブデン製ルツボを使用し、またタングステン箔を用いなかったこと以外は、実施例１と同じ方法で、実施例２の赤色蛍光体を作製した。なおモリブデン製ルツボと実施例２の原料混合体とが接触する面積は３００ｃｍ２であった。
(Example 2)
A red phosphor of Example 2 was produced in the same manner as in Example 1 except that a molybdenum crucible, which is also a refractory metal, was used as the firing container and no tungsten foil was used. The area of contact between the molybdenum crucible and the raw material mixture of Example 2 was 300 cm 2 .
（実施例３）
焼成容器内には０．３ｍｍ厚のタングステン箔と０．３ｍｍ厚のモリブデン箔を入れて焼成したこと以外は、実施例１と同じ方法で実施例３の赤色蛍光体を作製した。実施例３の原料混合体と高融点金属との接触面積の合計は４５０ｃｍ２であった。
(Example 3)
A red phosphor of Example 3 was produced in the same manner as in Example 1 except that a 0.3 mm thick tungsten foil and a 0.3 mm thick molybdenum foil were placed in the firing container and fired. The total contact area between the raw material mixture of Example 3 and the refractory metal was 450 cm 2 .
（実施例４〜７）
実施例１と同じ原料混合体を使用し、表１に示す原料混合体充填量、高融点金属の箔を用い、即ち原料混合体と高融点金属との接触面積を変えて、実施例１と同じ条件で実施例４〜７の蛍光体を作製した。
(Examples 4 to 7)
Using the same raw material mixture as in Example 1, using the raw material mixture filling amount shown in Table 1, using a refractory metal foil, that is, changing the contact area between the raw material mixture and the refractory metal, The phosphors of Examples 4 to 7 were produced under the same conditions.
（粉末Ｘ線回折測定）
得られた実施例１〜７、比較例１の赤色蛍光体に対して、粉末Ｘ線回折測定装置（株式会社リガク製ＵｌｔｉｍａＩＶ）を用い、ＣｕＫα線を用いた粉末Ｘ線回折を行った。得られたＸ線回折パターンは、全て（Ｓｒ，Ｃａ）ＡｌＳｉＮ３結晶と同一の回折パターンが認められ、実施例１〜７、比較例１の赤色蛍光体は、主結晶相が（Ｓｒ，Ｃａ）ＡｌＳｉＮ３結晶と同一の結晶構造を有することが確認された。
(Powder X-ray diffraction measurement)
The obtained red phosphors of Examples 1 to 7 and Comparative Example 1 were subjected to powder X-ray diffraction using CuKα rays using a powder X-ray diffractometer (Ultima IV manufactured by Rigaku Corporation). The obtained X-ray diffraction patterns all have the same diffraction pattern as that of the (Sr, Ca) AlSiN 3 crystal. The red phosphors of Examples 1 to 7 and Comparative Example 1 have a main crystal phase of (Sr, Ca). ) It was confirmed to have the same crystal structure as the AlSiN 3 crystal.
（蛍光スペクトルの測定）
実施例１〜７、比較例１の赤色蛍光体が示す蛍光スペクトルを、ローダミンＢと副標準光源により補正を行った分光蛍光光度計（日立ハイテクノロジーズ社製、Ｆ−７０００）を用いて測定した。測定には、光度計に付属の固体試料ホルダーを使用し、励起波長４５５ｎｍでの蛍光スペクトルを測定した。なお蛍光スペクトルのピーク波長は全て６２５ｎｍであった。また蛍光体の輝度は、蛍光スペクトルのピーク波長におけるピーク強度を指標として評価した。実施例１〜７、比較例１の比較では、比較例１のピーク強度を１００％とした場合の相対値として示し、５％以上の改善、即ち１０５％を超えるピーク強度を示した場合、輝度が改善されたと評価した。
(Measurement of fluorescence spectrum)
The fluorescence spectra shown by the red phosphors of Examples 1 to 7 and Comparative Example 1 were measured using a spectrofluorometer (F-7000, manufactured by Hitachi High-Technologies Corporation) corrected with rhodamine B and a sub-standard light source. . For the measurement, a solid sample holder attached to the photometer was used, and a fluorescence spectrum at an excitation wavelength of 455 nm was measured. The peak wavelength of the fluorescence spectrum was 625 nm. The luminance of the phosphor was evaluated using the peak intensity at the peak wavelength of the fluorescence spectrum as an index. In the comparison between Examples 1 to 7 and Comparative Example 1, it is shown as a relative value when the peak intensity of Comparative Example 1 is set to 100%. When the peak intensity exceeds 5%, that is, the peak intensity exceeds 105%, the luminance is Rated as improved.
実施例１〜７、比較例１を製造する際の、焼成容器中への原料混合体の充填量、用いた高融点金属の材質、原料混合体と高融点金属との接触面積、原料混合体の単位質量に対する高融点金属の接触面積、発光ピーク強度、発光ピーク強度から得られる蛍光体輝度の判定結果（改善されたものに○印）を表１に示した。 Examples 1-7, filling amount of raw material mixture in firing container when producing Comparative Example 1, material of refractory metal used, contact area between raw material mixture and refractory metal, raw material mixture Table 1 shows the determination results of phosphor brightness obtained from the contact area of the refractory metal with respect to the unit mass, the emission peak intensity, and the emission peak intensity (circles for improvement).
（実施例８）
赤色蛍光体の原料化合物として、α型窒化ケイ素粉末（ＳＮ−Ｅ１０グレード、宇部興産社製）５２．９質量％、窒化アルミニウム粉末（Ｅグレード、トクヤマ社製）４６．３質量％、酸化ユーロピウム（ＲＵグレード、信越化学工業社製）０．８質量％を、ナイロン製ポットと窒化ケイ素製ボールを用い、また混合溶媒としてエタノールを使用して、ボールミル混合を行った。溶媒を乾燥除去後、目開き７５μｍの篩を用いて分級し、篩下の粉末を回収した。
(Example 8)
As a raw material compound of the red phosphor, α-type silicon nitride powder (SN-E10 grade, manufactured by Ube Industries) 52.9 mass%, aluminum nitride powder (E grade, manufactured by Tokuyama Corporation) 46.3 mass%, europium oxide ( RU grade (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.8% by mass was subjected to ball mill mixing using a nylon pot and silicon nitride balls, and ethanol as a mixed solvent. After removing the solvent by drying, it was classified using a sieve having an opening of 75 μm, and the powder under the sieve was collected.
前記篩下の粉末を、水分１質量ｐｐｍ以下、酸素１質量ｐｐｍ以下の窒素雰囲気を保持することができるグローブボックス中に移動させ、そこで窒化カルシウム(太平洋セメント社製)をさらに配合し、乾式混合した。配合比は、前記篩下の粉末：窒化カルシウム＝６４．３質量％：３５．７質量％とした。乾式にて混合した原料粉末の大きさを揃えるため、再度、目開き２５０μｍのナイロン製篩で分級し、篩下からの回収粉末を、実施例８の原料混合体とした。 The powder under the sieve is moved into a glove box capable of maintaining a nitrogen atmosphere with a moisture content of 1 mass ppm or less and oxygen of 1 mass ppm or less, where calcium nitride (manufactured by Taiheiyo Cement Co., Ltd.) is further blended and dry mixed. did. The blending ratio was set to the powder under the sieve: calcium nitride = 64.3% by mass: 35.7% by mass. In order to equalize the size of the raw material powder mixed in the dry method, it was classified again with a nylon sieve having an opening of 250 μm, and the recovered powder from under the sieve was used as the raw material mixture of Example 8.
焼成容器である蓋付きの円筒型窒化ホウ素製容器（Ｎ−１グレード、デンカ社製）中に、０．３ｍｍ厚のタングステン箔を入れ、さらに前記実施例８の原料混合体を２３０ｇ充填した。このとき原料混合体とタングステン箔の接触面積は４５０ｃｍ２であった。 In a cylindrical boron nitride container with a lid (N-1 grade, manufactured by Denka Co., Ltd.) as a firing container, a 0.3 mm thick tungsten foil was placed, and 230 g of the raw material mixture of Example 8 was further filled. At this time, the contact area between the raw material mixture and the tungsten foil was 450 cm 2 .
原料混合体を充填した焼成容器をグローブボックスから取り出し、カーボンヒーターを備える電気炉内に速やかに置いて、電気炉内をいったん０．１ＰａＧ以下まで十分に真空排気した。真空排気したまま加熱を開始し、６００℃からは窒素ガスを電気炉内に導入し、炉内雰囲気圧力を０．１ＭＰａＧとした。窒素ガス導入後もそのまま１８００℃まで昇温し、１８００℃で４時間の焼成を実施した。 The firing container filled with the raw material mixture was taken out of the glove box and immediately placed in an electric furnace equipped with a carbon heater, and the inside of the electric furnace was once sufficiently evacuated to 0.1 PaG or less. Heating was started with evacuation, nitrogen gas was introduced into the electric furnace from 600 ° C., and the atmospheric pressure in the furnace was set to 0.1 MPaG. After the introduction of nitrogen gas, the temperature was raised to 1800 ° C. as it was, and firing was carried out at 1800 ° C. for 4 hours.
電気炉への通電を止めて常温（２５℃）にまで冷却した後、焼成容器内のタングステン箔を取り除いた。焼成体はボールミルを用いて解砕し、さらに目開き４５μｍの振動篩により分級し、実施例８の赤色蛍光体を得た。 After stopping energization to the electric furnace and cooling to room temperature (25 ° C.), the tungsten foil in the baking container was removed. The fired body was pulverized using a ball mill, and further classified with a vibrating sieve having an opening of 45 μm to obtain a red phosphor of Example 8.
(比較例２)
高融点金属材を原料混合体と共存させなかったこと以外は、実施例８と同じ方法にて比較例２の赤色蛍光体を作製した。
(Comparative Example 2)
A red phosphor of Comparative Example 2 was produced in the same manner as in Example 8 except that the refractory metal material did not coexist with the raw material mixture.
得られた実施例８と比較例２の赤色蛍光体に対して、実施例１と同じ方法で粉末Ｘ線回折測定を実施した。得られたＸ線回折パターンは、どちらもＣａＡｌＳｉＮ３結晶と同一の回折パターンが認められ、実施例８、比較例２の赤色蛍光体は、主結晶相がＣａＡｌＳｉＮ３結晶と同一の結晶構造を有することが確認された。 Powder X-ray diffraction measurement was performed on the obtained red phosphors of Example 8 and Comparative Example 2 in the same manner as in Example 1. Both of the obtained X-ray diffraction patterns have the same diffraction pattern as the CaAlSiN 3 crystal, and the red phosphors of Example 8 and Comparative Example 2 have the same crystal structure as the main crystal phase of the CaAlSiN 3 crystal. It was confirmed.
実施例８及び比較例２の赤色蛍光体に関して、実施例１と同じ方法で、蛍光スペクトルを測定し、それらの蛍光スペクトルのピーク波長、ピーク強度を測定した。なお、ピーク波長はどちらも６４５ｎｍであった。実施例８、比較例２の比較では、比較例２のピーク強度を１００％とした場合の相対値として示し、５％以上の改善、即ち１０５％を超えるピーク強度を示した場合、輝度が改善されたと評価した。 For the red phosphors of Example 8 and Comparative Example 2, fluorescence spectra were measured by the same method as in Example 1, and the peak wavelength and peak intensity of those fluorescence spectra were measured. Both peak wavelengths were 645 nm. In the comparison between Example 8 and Comparative Example 2, it is shown as a relative value when the peak intensity of Comparative Example 2 is set to 100%, and when the improvement is 5% or more, that is, the peak intensity exceeds 105%, the luminance is improved. Rated.
実施例８、比較例２を製造する際の、焼成容器への原料混合体の充填量、用いた高融点金属の材質、原料混合体との接触面積、原料混合体の単位質量あたりの接触面積、発光ピーク強度、発光ピーク強度から得られる蛍光体輝度の判定結果（改善されたものに○印）を表２に示した。 In the production of Example 8 and Comparative Example 2, the filling amount of the raw material mixture into the firing container, the material of the refractory metal used, the contact area with the raw material mixture, the contact area per unit mass of the raw material mixture Table 2 shows the emission peak intensity and the determination result of the phosphor luminance obtained from the emission peak intensity (circles for improved ones).
表1〜２に示される結果から、本発明の赤色蛍光体の製造方法を実施することにより、得られる赤色蛍光体の輝度が向上することがわかる。 From the results shown in Tables 1 and 2, it can be seen that the luminance of the obtained red phosphor is improved by carrying out the method for producing the red phosphor of the present invention.
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